Ductilization of Ni_3Al by Alloying with Substitutional Elements

This paper reviews recent research on ductility improvement of B-undoped Ni_3Al alloys.Ni_3Al binary alloys with hypostoichiometric compositions show appreciable ductility at room temperature when the samples are prepared by recrystallization annealing after cold pressing,although the alloys with stoichiometric and hyperstoichiometric compositions remain brittle.Melt-spun ribbons with hypostoichiometric compositions contain fine anti-phase domains (APDs),while no APD can be seen in melt-spun ribbons with a hyperstoichiometric composition.The ductility in hypostoichiometric Ni_3Al alloys is associated with low ordering energy of the alloys.The addition of ternary elements,which have been classified as γ formers such as Pd,Pt,Cu,Co and Ag.improves ductility of Ni_3Al alloys.Correspondingly,the microstructure of the melt-spun ribbons consists of fine APDs.The addition of γ' formers such as Si,Ti,Zr,V,Nb and Ta leads to brittle intergranular frac- ture.No APD was observed in the melt-spun ribbons of these ternary alloys.

Design of low-alloying and high-performance solid solution-strengthened copper alloys with element substitution for sustainable development

Solid solution-strengthened copper alloys have the advantages of a simple composition and manufacturing process,high mechanical and electrical comprehensive performances,and low cost;thus,they are widely used in high-speed rail contact wires,electronic component connectors,and other devices.Overcoming the contradiction between low alloying and high performance is an important challenge in the development of solid solution-strengthened copper alloys.Taking the typical solid solution-strengthened alloy Cu-4Zn-1Sn as the research object,we proposed using the element In to replace Zn and Sn to achieve low alloying in this work.Two new alloys,Cu-1.5Zn-1Sn-0.4In and Cu-1.5Zn-0.9Sn-0.6In,were designed and prepared.The total weight percentage content of alloying elements decreased by 43%and 41%,respectively,while the product of ultimate tensile strength(UTS)and electrical conductivity(EC)of the annealed state increased by 14%and 15%.After cold rolling with a 90%reduction,the UTS of the two new alloys reached 576 and 627MPa,respectively,the EC was 44.9%IACS and 42.0%IACS,and the product of UTS and EC(UTS×EC)was 97%and 99%higher than that of the annealed state alloy.The dislocations proliferated greatly in cold-rolled alloys,and the strengthening effects of dislocations reached 332 and 356 MPa,respectively,which is the main reason for the considerable improvement in mechanical properties.

Observation of selective surface element substitution in FeTe_(0.5)Se_(0.5) superconductor thin film exposed to ambient air by synchrotron radiation spectroscopy

A systematic investigation of oxidation on a superconductive Fe Te_（0.5）Se_（0.5）thin film,which was grown on Nb-doped SrTiO_3（001） by pulsed laser deposition,has been carried out.The sample was exposed to ambient air for one month for oxidation.Macroscopically,the exposed specimen lost its superconductivity due to oxidation.The specimen was subjected to in situ synchrotron radiation photoelectron spectroscopy（PES） and x-ray absorption spectroscopy（XAS） measurements following cycles of annealing and argon ion etching treatments to unravel what happened in the electronic structure and composition after exposure to air.By the spectroscopic measurements,we found that the as-grown FeTe_（0.5）Se_（0.5）superconductive thin film experienced an element selective substitution reaction.The oxidation preferentially proceeds through pumping out the Te and forming Fe–O bonds by O substitution of Te.In addition,our results certify that in situ vacuum annealing and low-energy argon ion etching methods combined with spectroscopy are suitable for depth element and valence analysis of layered structure superconductor materials.

Dissolution Characteristics of New Titanium Alloys in Electrochemical Machining

We focus on the electrochemical dissolution characteristics of new titanium alloys such as near-αtitanium alloy Ti60,α+βtitanium alloy TC4andβtitanium alloy Ti40 which are often used for aerospace industry.The experiments are carried out by electrochemical machining tool,and the surface morphology of the specimens is observed by the scanning electron microscope(SEM)and three-dimensional video microscope(DVM).The appropriate electrolyte is selected and the relationships between surface roughness and current density are achieved.The results show that the single-phase titanium alloy Ti40 has a better surface roughness after ECM compared with theα+βtitanium alloy TC4 and the near-αtitanium alloy Ti60.The best surface roughness is Ra 0.28μm when the current density is 75A/cm2.Furthermore,the surface roughness of the near-αtitanium alloy Ti60 is the most sensitive with the current density because of the different electrochemical equivalents of substitutional elements and larger grains than TC4.Finally,the suitable current density for each titanium alloy is achieved.

Electrochemical hydrogen storage characteristics of La_(0.75-x) M_xMg_(0.25)Ni_(3.2)Co_(0.2)Al_(0.1)(M=Zr,Pr;x=0,0.1) alloys prepared by melt spinning

In order to ameliorate the electrochemical hydrogen storage performances of La-Mg–Ni system A_2B_7-type electrode alloys, the partial substitution of M (M = Zr, Pr) for La was performed. The melt spinning technology was used to fabricate the La_(0.75-x)M_xMg_0.25Ni_3.2Co_0.2Al_0.1 (M = Zr, Pr; x = 0, 0.1) electrode alloys. The influences of the melt spinning and substituting La with M (M = Zr, Pr) on the structures and the electrochemical hydrogen storage characteristics of the alloys were investigated. The analysis of XRD, SEM, and TEM reveals that the as-cast and spun alloys have a multiphase structure composed of two main phases (La, Mg)_2Ni_7 and LaNi_5 as well as a residual phase LaNi_2 . The as-spun (M = Pr) alloy displays an entire nanocrystalline structure, while an amorphous-like structure is detected in the as-spun (M = Zr) alloy, implying that the substitution of Zr for La facilitates the amorphous formation. The electrochemical measurements exhibit that the substitution of Pr for La clearly increases the discharge capacity of the alloys; however, the Zr substitution brings on an adverse impact. Meanwhile, the M (M = Zr, Pr) substitution significantly enhances its cycle stability. The melt spinning exerts an evident effect on the electrochemical performances of the alloys, whose discharge capacity and high rate discharge ability (HRD) first mount up and then fall with the growing spinning rate, whereas their cycle stabilities monotonously augment as the spinning rate increases.

Influence of the substitution of Sm, Gd, and Dy for La in La_(0.7)Sr_(0.3)MnO_3 on its magnetic and electric properties and strengthening effect on room-temperature CMR

A series of La0.7-xSmxSr0.3MnO3, La0.7-xGdxSr0.3MnO3, and La0.7-xDyxSr0.3MnO3 （x=0.00, 0.10, 0.20, 0.30） samples were prepared by the solid-state reaction method. The influence of the substitution of Sm, Gd, and Dy for La on the magnetic and electric properties and on the magnetoresistance （MR） was studied through measurements of M-T curves and p-T curves. The results showed that： lattice distortion induced by substitution of Sm, Gd, and Dy for La and extra magnetism of substitution had great influence on the magnetic and electric properties of pcrovskite manganites; substitution of magnetic rare earth element for La was an effective way to change Curie temperature and to strengthen MR in perovskite manganites; and appropriate substitution proportion would generate large MR near room temperature.

Cycle Stabilities of La_(0.7)Mg_(0.3)Ni_(2.55-x)Co_(0.45)M_x (M=Fe, Cu, Al;x=0, 0.1) Electrode Alloys Prepared by Casting and Rapid Quenching

La-Mg-Ni system (PuNi3-type) hydrogen storage alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Fe, Cu, Al; x=0, 0.1) were prepared by casting and rapid quenching. Aiming to improve the cycle stabilities of the alloys, Ni in the alloy was partly substituted by Fe, Cu and Al. The effects of the substitution of Fe, Cu and Al for Ni and the rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM indicate that the element substitution has no influence on the phase compositions of the alloys, but it changes the phase abundances of the alloys. Particularly, the substitution of Al and Cu obviously increases the amount of the LaNi2 phase. The substitution of Al and Fe leads to a great refinement of the as-quenched alloy′s grains. The substitution of Al strongly restrains the formation of the amorphous in the as-quenched alloy, but the substitution of Fe and Cu is quite helpful for the formation of an amorphous phase. The effects of the substitution of Fe, Cu and Al on the cycle stabilities of the as-cast and quenched alloys are different. The positive impact of the substitution elements on the cycle stabilities of the as-cast alloys is ranked in proper order Al>Fe>Cu, and for as-quenched alloys, the order is Fe>Al>Cu. Rapid quenching engenders an unconscious influence on the phase composition, but it markedly enhances the cycle stabilities of the alloys.

Structural and electrical transport properties of Cu-doped Fe1-xCuxSe single crystals

We report the structural and electrical transport properties of Fe1-xCuxSe(x=0,0.02,0.05,0.10)single crystals grown by a chemical vapor transport method.Substituting Cu for Fe suppresses both the nematicity and superconductivity of FeSe single crystal,and provokes a metal–insulator transition.Our Hall measurements show that the Cu substitution also changes an electron dominance at low temperature of un-doped Fe Se to a hole dominance of Cu-doped Fe1-xCuxSe at x=0.02 and 0.1,and reduces the sign-change temperature(TR)of the Hall coefficient(RH).

Microstructure and Thermoelectric Properties of Bi- and Cu-Substituted Ca_3Co_4O_9 Oxides

Bi- and Cu-substituted Ca3Co4O9 samples were prepared by conventional solid-state reaction method and the effect of element substitution on the microstructures and thermoelectric properties was investigated. Partial substitution of Cu for Co leads to an increase in electrical conductivity and a decrease in Seebeck coefficient due to the rise of hole concentration. The microstructure of Cu-substituted sample is almost unchanged compared with undoped Ca3Co4O9. On the other hand, partial substitution of Bi for Ca gives rise to a significant increase in the grain size, and c-axis-oriented structure can be formed in Ca2.7Bi0.3Co4O9, resulting in an obvious increase in electrical conductivity. Cu and Bi co-substitution further increases the grain growth and the electrical conductivity of Ca2.7Bi0.3Co3.7Cu0.3O9. Thus, Cu and Bi co-substitution samples possess the optimal thermoelectric performance at high temperature and the highest value of power factor can reach 3.1×10^-4 Wm^-1.K^-2 at 1000 K.

Barium-doped Pr_(2)Ni_(0.6)Cu_(0.4)O_(4+δ) with triple conducting characteristics as cathode for intermediate temperature proton conducting solid oxide fuel cell

Proton conducting solid oxide fuel cell(H-SOFC)is an emerging energy conversion device,with lower activation energy and higher energy utilization efficiency.However,the deficiency of highly active cathode materials still remains a major challenge for the development of H-SOFC.Therefore,in this work,K_(2)NiF_(4)-type cathode materials Pr_(2-x)Ba_(x)Ni_(0.6)Cu_(0.4)O_(4+δ)(x=0,0.1,0.2,0.3),single-phase tripleconducting(e-/O^(2-)/H^(+))oxides,are prepared for intermediate temperature H-SOFCs and exhibit good oxygen reduction reaction activity.The investigation demonstrates that doping Ba into Pr_(2-x)BaxNi_(0.6)Cu_(0.4)O_(4+δ) can increase its electrochemical performance through enhancing electrical conductivity,oxygen vacancy concentration and proton conductivity.EIS tests are carried at 750℃ and the minimum polarization impedances are obtained when x=0.2,which are 0.068 Ω·cm^(2) in air and 1.336 Ω·cm^(2) in wet argon,respectively.The peak power density of the cell with Pr_(1.8)Ba_(0.2)Ni_(0.6)Cu_(0.4)O_(4+δ) cathode is 298 mW·cm^(-2) at 750℃ in air with humidified hydrogen as fuel.Based on the above results,Ba-doped Pr_(2-x)Ba_(x)Ni_(0.6)Cu_(0.4)O_(4+δ) can be a good candidate material for SOFC cathode applications.

Study on numerical simulation of nodular graphite iron microstructure formation

In this paper, the mathematical and physical model was developed based on thermodynamics and solidification theory before the eutectoid transformation of nodular graphite iron occurred. The Local Element Substitute and Magnification Method was brought forward and 3-dimensional numerical simulation program based on the model and the new assistant algorithm was developed and used to calculate the samples. Results of calculation have good agreement with experimental data. To display the microstructure formation during solidification of nodular graphite iron, a 2-dimensional numerical simulation program combined with the result of the 3-dimensional numerical simulation of experimental samples was compiled.

Theoretical Investigations of Nonlinear Optical Properties of Transition Metal Cluster Anions

In the framework of density functional theory （DFT）, the electronic excitations and nonlinear optical （NLO） properties of six binuclear transition metal cluster anions with the formula of [Ch2M-（μ-Ch）2-M＇CN]^2- （M = Mo, W; Ch = S, Se; M＇ = Cu, Ag） have been systemically investigated at both cases of gas phase and DMF solution. The obtained electronic absorption spectra reveal that the element replacements of metals M and ligands Ch have significant influence on the absorptions, especially on the low-lying ones. In addition, the transitions of μ-Ch→M are dominant for the low-lying excitations, whereas the transitions of M＇→M as well as Ch→M are mainly responsible for the higher excitations. The calculated molecular first and second hyperpolarizabilities present the remarkable element substitution and solvent effects. The analyses show that the transitions involving μ-Ch→M charge transfer make the critical contributions to the first hyperpolarizability t, and that the charge transfers from the moieties of MCh4 to M＇CN as well as those of μ-Ch→M and M＇→M are responsible for the second hyperpolarizability y. Moreover, the introduction of solvent leads to the results that the transitions within the moieties of MCh4 and M＇CN make larger contributions to the hyperpolarizability, especially to γ.

The effect of electrochemically inactive Ti substituted for Ru in Li_(2)Ru_(1-x)Ti_xO_(3) on structure and electrochemical performance

The approach of substituting electrochemically active with inactive elements has widely been used to improve the electrochemical performance of Li-rich intercalation cathode materials. This especially is true for Li-rich compounds where almost all of the Li+ions are reversibly(de)intercalated during electrochemical cycling. The beneficial mechanism behind this substitution with electrochemically inactive elements is still not clear yet. Li_(2)RuO_(3) is chosen as basis for a model solid solution system to investigate the effect of electrochemically inactive elements owing to its high specific capacity of more than 300 m Ah g^(-1) and the significant contribution of anion redox mechanism. Herein, Li_(2)Ru_(1-x)Ti_xO_(3) solid solution series are synthesized and the effect of substituting with electrochemical inactive Ti for Ru on structure and electrochemical performance have been comprehensively investigated. The electrochemical performance is significantly improved, especially for Li_(2)Ru_(0.8)Ti_(0.2)O_(3), and the capacity retention after 50 cycles increases from 81% to 90%, as compared to the end member Li_(2)RuO_(3). Results of electrochemical impedance spectroscopy show that Ti substitution reduces the charge transfer impedance, which favors the Li+diffusion across the electrolyte–electrode interface and improves the electronic conductivity. For the first time,nuclear magnetic resonance was utilized to confirm that a small part of Ti ions exchange their position with Li ions in the Li layer. This research provides a better understanding of electrochemical inactive element substitution and strong insights for the functional design of the next generation of Li-rich cathode materials.

Highly Improved Electrochemical Performances of the Nanocrystalline and Amorphous Mg_2Ni-type Alloys by Substituting Ni with M (M=Cu,Co,Mn)

The element Ni in the Mg2Ni alloy is partially substituted by M（M = Cu, Co, Mn） in order to ameliorate the electrochemical hydrogen storage performances of Mg2Ni-type electrode alloys. The nanocrystalline and amorphous Mg20Ni10-xMx（M = None, Cu, Co, Mn; x = 0-4） alloys were prepared by melt spinning. The effects of the M（M = Cu, Co, Mn） content on the structures and electrochemical hydrogen storage characteristics of the as-cast and spun alloys were comparatively studied. The analyses by XRD, SEM and HRTEM reveal that all the as-cast alloys have a major phase of Mg2Ni but the M（M = Co, Mn） substitution brings on the formation of some secondary phases, MgCo2 and Mg for the（M = Co） alloy, and Mn Ni and Mg for the（M = Mn） alloy. Besides, the as-spun（M = None, Cu） alloys display an entirely nanocrystalline structure, whereas the as-spun（M = Co, Mn） alloys hold a nanocrystalline/amorphous structure, suggesting that the substitution of M（M = Co, Mn） for Ni facilitates the glass formation in the Mg2Ni-type alloys. The electrochemical measurements indicate that the variation of M（M = Cu, Co, Mn） content engenders an obvious effect on the electrochemical performances of the as-cast and spun alloys. To be specific, the cyclic stabilities of the alloys augment monotonously with increasing M（M = Cu, Co, Mn） content, and the capacity retaining rate（S20） is in an order of（M = Cu） 〉（M = Co） 〉（M = Mn） 〉（M = None） for x≤1 but changes to（M = Co） 〉（M = Mn） 〉（M = Cu） 〉（M = None） for x≥2. The discharge capacities of the as-cast and spun alloys always grow with the rising of M（M = Co, Mn） content but first mount up and then go down with increasing M（M = Cu） content. Whatever the M content is, the discharge capacities are in sequence：（M = Co） 〉（M = Mn） 〉（M = Cu） 〉（M = None）. The high rate discharge abilities（HRDs） of all the alloys grow clearly with rising M（M = Cu, Co） content except for（M = Mn） alloy, whose HRD has a maximum value with varying M（M = Mn） content. Furthermore, for the as-cast alloys, the HRD is in order of（M = Co） 〉（M = Mn） 〉（M = Cu） 〉（M = None）, while for the as-spun（20 m·s^-1） alloys, it changes from（M = Co） 〉（M = Mn） 〉（M = Cu） 〉（M = None） for x = 1 to（M = Cu） 〉（M = Co） 〉（M = None） 〉（M = Mn） for x = 4.

AB_(2)-type rare earth-based compounds with C-15 structure:Looking for reversible hydrogen storage materials

AB_(2)-type(A=rare earth,B=transition metal)intermetallic compounds with C15 structure can easily absorb large amount of hydrogen,showing their potential use as hydrogen storage materials.The crucial problem hindering their application is hydrogen induced amorphization(HIA),which leads to the irreversible hydrogen sorption process.The stability of the AB_2 Laves phase compounds,the structural properties,the hydrogenation properties and the controlling factors of HIA are discussed in this review.Comparing with other factors,the atomic radii ratio r_A/r_B is the most important one influencing the HIA.Multi-element substitution is an efficient way to suppress or limit HIA and may enable AB_2 compounds to be suitable for hydrogen storage.

Roles of metal element substitutions from the bimetallic solid state electrolytes in lithium batteries

All-solid-state lithium batteries(ASSLBs),receiving extensive attentions and studies,exhibit better safety,environmental friendliness,stability,wider electrochemical stability window and higher energy density than traditionally liquid lithium batteries.In a variety of inorganic materials,with highly replaceable,the non-lithium metal elements emerge in endlessly and affect performances in diversiform ways.Due to facile preparation,convertible structures and excellent properties,the lithium-containing bimetallic granular materials are often applied as important components of electrolytes in lithium batteries.In this review,in terms of the properties of substituted elements,changing crystal structures,increasing vacancies or defects and improving the interfacial conductions,the roles of metal element substitutions of inorganic particles on the improvement of solid-state electrolytes are expounded.And the applications of substituted strategies in ASSLBs as the host of inorganic particles electrolytes and as fillers or modifications for composite electrolytes are also investigated and discussed.It also summarizes the current concerns and obstacles that need to be broken through,as well as provides a basis guide for the selection and optimization of inorganic particles.

V-substituted pyrochlore-type polyantimonic acid for highly enhanced lithium-ion storage

Pyrochlore-structured polyantimonic acid(PAA)is a potential high-capacity electrode material,but its innately poor electroconductivity(~10^(-10)S/cm)seriously impairs its electrochemical reversibility for lithium-ion storage.Herein,we report design and synthesis of a novel V-substituted PAA(PAA-V),where V^(5+)are introduced to partially replace Sb^(5+).Owing to identical valence and close ionic radius relative to Sb^(5+),the V^(5+)cation can constitute the covalent VO_6octahedra framework without changing the pyrochlore crystal structure of PAA.As a result,the V^(5+)-substitution is capable to modulate the electronic structure of PAA with significantly improved electrical conductivity(~10^(-6)S/cm for PAA-V)and meanwhile decreases the size of crystals with reduced diffusion length for Li^(+)-ions.With varying the ratio of V^(5+)-substitution,the PAA-V with optimized substitution molar ratio(18%)exhibits the best lithium-ion storage performance,delivering a long cycling life with high reversible capacity(731 m Ah/g after 1200cycles at 1 A/g)and outstanding rate capability(279 mAh/g at 15 A/g).More importantly,by pairing the PAA-V as anode and commercial LiFePO_(4)as cathode,the full cell with a limited negative/positive capacity ratio of 1.2 exhibits decent cycling stability at 1 C after 150 cycles with 85.5%capacity retention.

Effects of Fe-substitution for cobalt on electrochemical properties of La-Mg-Ni-based alloys

In order to improve electrochemical properties,especially cycling stability,Co was partially substituted by Fe in A2B7-type La-Mg-Ni-based alloys.The La0.74Mg0.26Ni2.55Co0.65-xFex(x=0,0.10,0.20,0.30) alloys were prepared by inductive melting,and their phase structure and electrochemical properties were studied.The XRD and SEM results showed that the alloys consisted mainly of(La,Mg)2Ni7 phase,(La,Mg)5Ni19 phase and LaNi5 phase,except for absence of LaNi5 phase in the non-substituted alloy.The(La,Mg)5Ni19 ph...

The electrochemical hydrogen storage characteristics of as-spun nanocrystalline and amorphous Mg_(20)Ni_(10-x)M_x(M=Cu, Co, Mn;x=0–4) alloys

In this paper, we comprehensively investigate the influences of M（M=Cu, Co, Mn） substitution for Ni on the structures and electrochemical hydrogen storage characteristics of the nanocrystalline and amorphous Mg20Ni10-xMx（M=Cu, Co, Mn; x = 0–4） alloys prepared by melt spinning. The as-spun（M=None, Cu） alloys display an entire nanocrystalline structure, whereas the as-spun（M=Co, Mn） alloys hold a mixed structure of both nanocrystalline and amorphous when x = 4（M content）. These results indicate that the substitution of M（M=Co, Mn） for Ni facilitates the glass formation in Mg2Ni-type alloy. All the as-spun alloys have the Mg2 Ni major phase, but M（M=Co, Mn） substitution brings on some secondary phases,such as Mg Co2, Mg phases for M=Co, and Mn Ni, Mg phases for M=Mn. The substitution of M（M=Cu, Co, Mn）for Ni also makes a positive contribution to the cycle stability of the alloys in the following orders：（M=Cu） [（M=Co） [（M=Mn） for x = 1 and（M=Co） [（M=Mn）[（M=Cu） for x = 2–4. Meanwhile, it notably enhances the discharge capacity of the alloys in the sequence of（M=Co） [（M=Mn） [（M=Cu）. As for the high rate discharge ability, it visibly upgrades with the growing of M content for（M=Cu, Co）, while it grows at first and then declines for（M=Mn）.

Structure and electrochemical properties of LaMgNi4-xCox(x=0-0.8)hydrogen storage electrode alloys

LaMgNi（4-x）Cox（x = 0-0.8） electrode alloys used for MH/Ni batteries were prepared by induction melting. The structures and electrochemical hydrogen storage properties of the alloys were investigated in detail.X-ray diffraction（XRD） and scanning electron microscopy（SEM） analysis show that LaMgNi4 phase and LaNi5 phase are obtained. The lattice parameters of the two phases increase first and then decrease with Co content increasing.The electrochemical properties of the alloy electrodes were measured by means of simulated battery tests. Results show that the addition of Co does not change the discharge voltage plateau of the alloy electrodes. However, the maximum discharge capacity increases from 319.9 mAh·g^-1（x = 0）to 347.5 mAh·g^-1（x = 0.4） and then decreases to331.7 mAh·g^-1（x = 0.8）. The effects of Co content on electrochemical kinetics of the alloy electrodes were also performed. The high rate dischargeability（HRD） first increases and then decreases with Co content increasing and reaches the maximum value（95.0 %） when x = 0.4. Test results of the electrochemical impedance spectra（EIS）,potentiodynamic polarization curves and constant potential step measurements of the alloy electrodes all demonstrate that when Co content is 0.4 at%, the alloy exhibits the best comprehensive electrochemical properties.