Influence of histidine as an electrolyte additive on the electrochemical performance of Al electrodes in 4.0 M KOH electrolyte

In this study, the influence of histidine as an electrolyte additive on the electrochemical performance of Al electrodes in 4.0 M KOH electrolyte is studied by measuring open-circuit potential–time curves, potentiodynamic polarization, potentiostatic oxidation, and electrochemical impedance spectroscopy. The surface morphology of Al electrodes is characterized by scanning electron microscopy. The results show that the battery performance is significantly improved by adding histidine. Samples with 50 mM histidine exhibit the highest corrosion resistance and discharging current density among all the specimens, with the corrosion current density (I_corr) being 7.471 mA/cm² and corrosion inhibition efficiency (η) being 43.33%.     

Initial corrosion protection of Zn–Mn alloys electrodeposited from alkaline solution

The effects of a deposition current density (c.d.) on the corrosion behaviour of Zn–Mn alloy coatings, deposited from alkaline pyrophosphate solution, were investigated by atomic absorption spectrophotometry (AAS), X-ray diffraction (XRD), atomic force microscopy (AFM), optical microscopy, electrochemical impedance spectroscopy (EIS) and measurement of corrosion potential (E_corr). XRD analysis disclosed that zinc hydroxide chloride was the main corrosion product on Zn–Mn coatings immersed in 0.5 mol dm⁻³ NaCl solution. EIS investigations revealed that less porous protective layer was produced on the alloy coating deposited at c.d. of 30 mA cm⁻² as compared to that deposited at 80 mA cm⁻².     

掺硼和掺磷的氢化纳米硅薄膜及其应用于类叠层太阳电池的研究

采用射频等离子体增强化学气相沉积法,制备了掺硼和掺磷的氢化纳米硅薄膜(nc-Si∶H),并将其应用于纳米硅薄膜类叠层太阳电池中。分析了薄膜样品的光学性能及表面形貌,结果表明:P型掺硼纳米硅薄膜的光学带隙为2.189 eV,电导率为8.01 S/cm,霍尔迁移率为0.521 cm2/(V.S),载流子浓度为9.61×1019/cm3;N型掺磷纳米硅薄膜的光学带隙为1.994 eV,电导率为1.93 S/cm,霍尔迁移率为1.694 cm2/(V.S),载流子浓度为7.113×1018/cm3;两者的晶粒尺寸都在3～5 nm之间,晶态比都在35%～45%之间,并且颗粒沉积紧密,大小比较均匀。制备了大小为20 mm×20 mm,结构为Al/AZO/p-nc-Si∶H/i-nc-Si∶H/n-nc-Si∶H/p-nc-Si∶H/i-nc-Si∶H/n-c-Si/Al背电极的纳米硅薄膜类叠层太阳电池,通过I-V曲线测试,其VOC达到544.3 mV,ISC达到85.6 mA,填充因子为65.7%。     

Effects of pretreatment on the aluminium etch pit formation

The effect of chemical pretreatments on the electrochemical etching behavior of aluminium was investigated with the topographic studies of surface and the analysis of initial potential transients. Two-step pretreatments with H₃PO₄ and H₂SiF₆ result in a high density of pre-etch pits on aluminium surface by the incorporation of phosphate ion inside the oxide film and the removal of surface layer by aggressive fluorosilicic acid solution. It generates a high density of etch pits during electrochemical etching and results in the capacitance increase of etched Al electrode by expanding the surface area, up to 61.3 μF/cm² with the pretreatment solution of 0.5 M H₃PO₄ at 65 °C and 10 mM H₂SiF₆ at 45 °C.     

Effect of adding potassium hydroxide to an agar binder for use as the anode in Zn–air batteries

Agar–KOH was used for the Zn-powder binder at different concentrations in order to achieve the desired conductivity and physical properties. The presence of KOH causes the growth of a ZnO needle structure that covers the Zn-active materials. The formation of ZnO is proven by microscopy and structural measurements. To further understand the effect of KOH in the agar binder, Zn–air batteries are fabricated. The results show that the Zn–agar binder without KOH gives the highest discharge capacity of 505.0 mA h g⁻¹. The results contradict earlier expectations that a ‘small’ amount of KOH in agar could increase the battery’s capacity.     

Evaluation of metastable pitting on titanium by charge integration of current transients

The metastable pitting of titanium has been studied under potentiostatic control in solutions containing chloride ions. An approach based on the charge integration of current transients was proposed for a quantitative determination of metastable pitting. A pit density (d_mpit) was defined as the number of metastable pits per unit area per unit time (cm⁻² h⁻¹) with a typical size, instead of a size distribution. The calculated d_mpit of titanium at 0.5 V_SCE in 0.6 M NaCl was about 1.0 × 10³ cm⁻² h⁻¹ with a typical radius of 0.12 μm. An exponential potential dependence of d_mpit was obtained through the integration approach.     

Electrocrystallization of nanocrystallite calcium phosphate coatings on titanium substrate at different current densities

Calcium phosphates were electrocrystallized on titanium substrate by electrochemical deposition technique, in which the electrolyte was 0.167 M CaCl₂ and 0.1 M NH₄H₂PO₄. Different current densities (0.375, 1.5, 3, 6 mA/cm²) were applied. The pH of the solution after mixing of equal volumes was 4.6. The surface morphology, chemical composition and phase identification of the coatings were investigated by scanning electron microscopy associated with an energy dispersive spectrometer (SEM-EDXS) and X-ray diffractometry (XRD). Effects of the current density on the morphology and the structure of the coating were also discussed.The results showed that at all current densities tested, the coating is brushite (dicalcium phosphate dihydrate CaHPO₄ · 2H₂O). Furthermore, the results showed that coating thickness and weight gain are increased and the morphology changed with increasing deposition current density (from 0.375 to 6 mA/cm²). On contrary, thickness and weight gain are decreased with sodium hydroxide treatment. NaOH treatment converts brushite of Ca/P ratio 1:1 to hydroxyapatite of Ca/P ratio of 1.667. So, chemical analysis of the solution shows soluble P₂O₅ content. Coating thickness at 6 mA/cm² was about 20 and 30 µm with and without treatment, respectively. It decreased to about 9.5 and 12 µm at 0.375 mA/cm² current density, with and without treatment, respectively. However, the formed phase is not changed with increasing current density. In addition, it is found that, even at high current density (6 mA/cm²), no hydroxyapatite was directly electrocrystallized due to low corresponding potential (less than 5 V) and low corresponding voltage (468 mV).     

Direct electrosynthesis of polyaniline–montmorrilonite nanocomposite coatings on aluminum alloy 3004 and their corrosion protection performance

Homogeneous and adherent polyaniline–montmorrilonite (MMT) nanocomposite coatings were electrosynthesized on aluminum (Al) alloy 3004 (AA 3004) by using the galvanostatic polarization method. The synthesized coatings were characterized by UV–Vis absorption spectrometry, Fourier transform infrared spectroscopy, X-ray diffraction patterns and scanning electron microscopy. The corrosion protection effect of the coatings was demonstrated by performing a series of electrochemical experiments of potentiodynamic and impedance measurements on Al in 3.5 wt% aqueous NaCl electrolytes. The corrosion current (i_corr) values decreased from 6.55 μA cm⁻² for uncoated Al to 0.102 μA cm⁻² for nanocomposite-coated Al under optimal conditions.     

Influence of rare earth metals on the characteristics of anodic oxide films on aluminium and their dissolution behaviour in NaOH solution

The characteristics of oxide films on Al and Al1R alloys (R = rare earth metal = Ce, Y) galvanostatically formed (at a current density of 100 μA cm⁻²) in borate buffer solution (0.5 M H₃BO₃ + 0.05 M Na₂B₄O₇·10H₂O; pH = 7.8) were investigated by means of electrochemical impedance spectroscopy. EIS spectra were interpreted in terms of an “equivalent circuit” that completely illustrate the Al(Al1R alloy)/oxide film/electrolyte systems examined. The resistance of the oxide films was found to increase on passing from Al to Al1R alloys while the capacitance showed an opposite trend. The stability of the anodic oxide films grown in the borate buffer solution on Al and Al1R alloys was investigated by simultaneously measuring the electrode capacitance and resistance at a working frequency of 1 kHz as a function of exposure over a period of time to naturally aerated 0.01 M NaOH solution. Analyses of the electrode capacitance and resistance values indicated a decrease in chemical dissolution rate of the oxide films on passing from Al to Al1R alloys.     

X-ray photoelectron spectroscopy study of the corrosion behaviour of galvanised steel implanted with rare earths

The present paper studies the effect of ion implantation of 2 × 10¹⁶ ions/cm² of Ce⁺ and 2 × 10¹⁶ ions/cm² of La⁺ at 150 keV on the corrosion behaviour of hot-dip galvanised steel. After implantation, galvanised steel was characterised by means of XPS previous to and following immersion in the medium. The results revealed incorporation of cerium and lanthanum on the surface as Ce₂O₃ and La₂O₃, respectively. Electrochemical impedance spectroscopy was carried out in order to evaluate its corrosion behaviour in 0.6 M NaCl during 1 month of immersion. The corrosion resistance was improved by an increase in the charge transfer resistance of the implanted specimens in the medium. This effect could be associated with changes in the morphology/microstructure of the corrosion products layer rather than in its composition variations.     

Investigation of β/γ-MnO2 in composite electrodes with carbon nanotubes in a redox reaction with lithium in a model accumulator

Balastless thin-layer MnO₂/Al electrodes without an electroconducting carbon additive in combination with multiwalled carbon nanotubes (MWCNT) MnO₂/Al-MWCNT, as well as bulk-modified paste electrodes MnO₂ (MWCNT) F4/18H12X9T stainless steel electrodes, have been studied in the redox reaction with lithium in a model accumulator on the basis of propylene carbonate (PC), dimetoxiethane (DME), and 1MLiClO₄ and ethyl carbonate (EC), dimethylcarbonate (DMC), and 1M LiClO₄ electrolytes. The window of the electrochemical stability of the anode oxidation on MnO₂-Al/electrodes in the work range of the potentials for the electrolytes under study is 2.0–4.1 and 2.0–4.2 V, respectively. Because of the high contact resistance between the particles of the thin-layer β/γ-MnO₂/Al electrode, its discharge capacity cannot exceed 110–120 mA h/g; however, it is stable through 180 cycles. The discharge capacity volume paste MnO₂, F4/18H12X9T electrodes during the first cycle reaches 265–280 mA h/g and that of the reversible capacity ranges up to 185–250 mA h/g during the first 50 cycles. The role of the aluminum collector in the electrochemical transformation of MnO₂ has been discussed in thin-layer MnO₂/Al electrodes obtained by the mechanical rubbing of the active component into the aluminum matrix. The lithium chemical diffusion coefficient D_Li established in the redox reaction of MnO₂ with lithium has been estimated in thin-layer composite MnO₂ MWCNT/Al electrodes at the current peak values (around 10^?12 cm²/s) by slow cyclic voltammetry.     

Effect of 6-thioguanine,as an electrolyte additive,on the electrochemical behavior of an Al–air battery

In this study, the electrochemical behavior of an Al–air battery is improved by mixing 6-thioguanine into 4.0 M NaOH electrolyte. The electrochemical performance of the Al electrodes is analyzed using potentiodynamic polarization, potentiostatic oxidation, and electrochemical impedance spectroscopy. The surface morphology of the Al electrodes after discharging for 1,000 s is characterized using scanning electron microscopy coupled with X-ray elemental mapping for Al, O, C, N, and S. Furthermore, the utilization efficiencies of these samples are also determined. The results show that the corrosion resistance of the Al electrodes initially increases and then decreases with an increase in 6-thioguanine concentration. The presence of 6-thioguanine enhances the corrosion resistance to the maximum, with a corrosion current density (I_corr) of 6.170 mA/cm², and corrosion inhibition efficiency (η) of 36.56%, at 0.5 mM of 6-thioguanine.     

Synthesis and properties of CaCd2Sb2 and EuCd2Sb2

High density polycrystalline CaCd₂Sb₂ and EuCd₂Sb₂ intermetallics are synthesized by Spark Plasma Sintering and their thermoelectric properties are investigated. X-ray diffraction measurements reveal both materials have a structure in space group, containing a small amount of CdSb as a second phase. Thermoelectric measurements indicate both are p-type conductive materials. The figure of merit value of CaCd₂Sb₂ is 0.04 at 600 K and that of EuCd₂Sb₂ is 0.60 at 617 K. Theoretical calculations show that CaCd₂Sb₂ is a degenerate semiconductor with a band gap of 0.63 eV, while EuCd₂Sb₂ is metallic with DOS of 13.02 electrons/eV. For deeper understanding of the better thermoelectric properties of EuCd₂Sb₂, its low temperature magnetic, transport and heat capacity properties are investigated. Its Nèel temperature is 7.22 K, convinced by heat capacity anomaly at 7.13 K. Hall effect convinced that it is a p-type conductive material. It has high Hall coefficient, high carrier concentration and high carrier mobility of +1.426 cm³/C, 4.38 × 10¹⁸/cm³ and 182.40 cm²/Vs, respectively. They are all in the magnitude of good thermoelectric materials. The Eu 4f level around Fermi energy and antiferromagnetic order may count for the better thermoelectric properties of EuCd₂Sb₂ than that of CaCd₂Sb₂.     

Synthesis and characterization of ɛ-VOPO4 nanosheets for secondary lithium-ion battery cathode

Vanadium (III) phosphate monoclinic VPO₄·H₂O was synthesized hydrothermally. The ?-VOPO₄ nanosheets, formed by the oxidative de-intercalation of protons from monoclinic VPO₄·H₂O, can reversibly react with more than 1 mol lithium atoms in two steps. Crystal XRD analysis revealed that the structure of the ?-VOPO₄ nanosheets is monoclinic with lattice parameters of α=7.2588(4) Å, b=6.8633(2) Å and c=7.2667(4) Å. The results show that the ?-VOPO₄ nanosheets have a thickness of 200 nm and uniform crystallinity. Electrochemical characterization of the ?-VOPO₄ monoclinic nanosheets reveals that they have good electrochemical properties at high current density, and deliver high initial capacity of 230.3 mA·h/g at a current density of 0.09 mA/cm². Following the first charge cycle, reversible electrochemical lithium extraction/insertion at current density of 0.6 mA/cm² affords a capacity retention rate of 73.6% (2.0–4.3 V window) that is stable for at least 1000 cycles.     

The inhibition effect of 2,4,6-tris (2-pyridyl)-1,3,5-triazine on corrosion of tin, indium and tin-indium alloys in hydrochloric acid solution

The influence of 2,4,6-tris (2-pyridyl)-1,3,5-triazine (TPTZ) on the corrosion of tin, indium and tin-indium alloys in 0.5 M HCl solution at different temperatures was studied. Potentiodynamic cathodic polarization and extrapolation of cathodic and anodic Tafel lines techniques were used to obtained experimental data. In the case of tin, the percent inhibition efficiency (IE%) increases as both concentration of TPTZ and temperature are increased. The value of activation energy (E_a) is smaller in the presence of TPTZ than that in uninhibited solution, and decreases with increasing the concentration. However, the effect of TPTZ on indium and the investigated alloys exhibited similar behavior; so, the maximum inhibition efficiency is observed at lowest concentration (10⁻⁶ M) of TPTZ. Then, the value of inhibition efficiency starts to decrease gradually with increasing TPTZ concentration than that of 10⁻⁶ M. But at higher concentration (10⁻³ M) the corrosion current density (I_corr) is still lower than that in uninhibited solution. SEM photographs support that the higher inhibition efficiency is observed at 10⁻⁶ M of TPTZ.The plots of ln K versus 1/T in the presence of the TPTZ in the case of tin, the inhibitor showed linear behavior. The standard enthalpy, ΔH°_ads., entropy, ΔS°_ads. and free energy changes of adsorption ΔG°_ads. were evaluated using Frumkin adsorption isotherm.     

Growth behavior of Cu6Sn5 in Sn–6.5 Cu solders under DC considering trace Al: In situ observation

High resolution time-resolved X-ray imaging with synchrotron radiation has been used to in situ observe the growth behavior of Cu₆Sn₅ intermetallic compounds (IMCs) during solidification in Sn–6.5 Cu and Sn–6.5 Cu–0.2 Al (wt. %) solders under applied direct current (DC) field. The morphological evolution of Cu₆Sn₅ with I-like, X-like, Y-like and bird-like shapes is directly observed. It is shown that trace levels of Al have a marked effect on the solder microstructures and refining the size of the primary Cu₆Sn₅. The solidification pathway leading to the refinement is observed in real time using synchrotron microradiography. After adding the trace Al, I-like shapes bifurcate into X-like shapes. Furthermore, when DC field with 10 A/cm² is applied, both the growth rate and the mean size of Cu₆Sn₅ are increased but decreased when 100 A/cm² is applied. Meanwhile, the effect of thermodynamic potential barrier caused by DC field on the growth behavior of Cu₆Sn₅ is discussed.     

Corrosion resistance of Al ion implanted AZ31 magnesium alloy at elevated temperature

The Al ion implantation into AZ31 magnesium alloy was carried out in a MEVVA 80-10 ion implantation system at an ion energy of 40-50 keV with an ion implantation dose ranging from 2 × 10¹⁶ to 1 × 10¹⁷ ions/cm² at an elevated temperature of 300 °C induced by an ion current density of 26 μA/cm². The concentration-depth profile of implanted Al in AZ31 alloy measured by Rutherford backscattering spectrometry (RBS) is a Gaussian-type-like distribution in a depth up to about 1200 nm with the maximum Al concentration of about 8 at.%. The X-ray diffraction (XRD) analysis revealed the formation of α-Mg(Al) phase, intermetallic β-Mg₁₇Al₁₂, and MgO phase on the Al ion implanted samples. The potentiodynamic anodic polarization curves of the Al ion implanted samples in the 0.01 mol/l NaCl solution with a pH value of 12 showed increases of the corrosion potential and the pitting breakdown potential, and a decrease of the passive current density, respectively. The Al ion implanted samples with 6 × 10¹⁶ ions/cm² achieved the high pitting breakdown potential to about − 480 mV (SCE). In the 0.08 mol/l NaCl solution with pH = 12, the Al ion implanted samples with 1 × 10¹⁷ ions/cm² showed an increased pitting breakdown potential to about − 1290 mV (SCE), from around − 1540 mV (SCE) of unimplanted samples. It is indicated that different corrosion mechanisms are responsible for improvement in corrosion resistance of the AZ31 magnesium alloy in the NaCl solutions with the varied concentrations.     

Characterization of inclusions of X80 pipeline steel and its correlation with hydrogen-induced cracking

In this work, the microstructures of an X80 pipeline steel were characterized, and their susceptibilities to hydrogen-induced cracking (HIC) were investigated by hydrogen-charging, electrochemical hydrogen permeation and surface characterization. It is found that the microstructure of X80 pipeline steel consists of a polygonal ferrite and bainitic ferrite matrix, with martensite/austenite (M/A) constituents distributing along grain boundaries. The inclusions existing in the steel include those enriched with Si, Al oxide, Si–ferric carbide and Al–Mg–Ca–O mixture, respectively. The majority of inclusions are Si-enriched. Upon hydrogen-charging, cracks could be initiated in the steel in the absence of external stress. The cracks are primarily associated with the Si- and Al oxide-enriched inclusions. The diffusivity of hydrogen in X80 steel at room temperature is 2.0 × 10⁻¹¹ m²/s, and the estimated hydrogen trapping density in the steel is as high as 3.33 × 10²⁷ m⁻³.     

Hydrogen permeation behavior in pure nickel implanted with phosphorus, sulphur and their mixture

The entry and transport of hydrogen in phosphorus (P)-, sulphur (S)- and their mixture (P + S)-implanted nickel specimens with a fluence range of 1 × 10¹⁵ to 1 × 10¹⁷/cm² have been investigated using an electrochemical permeation technique and etching treatment (0.2% HF solution). From the hydrogen permeation transients obtained, the effective hydrogen concentration (C_H), apparent hydrogen diffusion coefficient (D_lag) and breakthrough time (t_lag) were estimated by using the time lag method in addition to the steady state permeation current density (P_∞). It was found that at a fluence of less than 1 × 10¹⁶/cm² almost all hydrogen permeation transients of the implanted nickel specimens were affected by the defects (vacancy, compressive stress and so on) generated during ion implantation process. At a high fluence of 1 × 10¹⁷/cm² the hydrogen permeation transient had a specific behavior because of the formation of amorphous phase for P, the structure change from fcc-structure to bcc-structure for S and both of them for the mixture (P and S). However, a synergistic effect of P and S was not observed on the hydrogen permeation transient. The behavior of these parameters depending on fluence and implanting element was discussed in terms of an amount of hydrogen entry site, the degree of defects, the properties of amorphous phase and structure and so on.     

Corrosion behaviour of Al–29at%Co alloy in aqueous NaCl

Microstructure and corrosion behaviour of a binary Al–29 at%Co alloy have been studied. The alloy was prepared by arc-melting of Al and Co in high purity Ar and rapidly solidified on a water-cooled Cu mould. The alloy chemical composition and microstructure were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction. Furthermore, the corrosion behaviour was studied by potentiodynamic polarization in aqueous NaCl (0.6 mol dm⁻³) at room temperature. The alloy was found to consist of three phases: hexagonal Al₅Co₂, Z-phase and AlCo (β). The corrosion resistance of different intermetallic phases is characterized. The results are compared to previously published results of Al–TM (TM = transition metal) alloys.