High-performance zinc-ion batteries enabled by electrochemically induced transformation of vanadium oxide cathodes

Rechargeable aqueous zinc-ion batteries(ZIBs) have become a research hotspot in recent years,due to their huge potential for high-energy,fast-rate,safe and low-cost energy storage.To realize good electrochemical properties of ZIBs,cathode materials with prominent Zn^(2+) storage capability are highly needed.Herein,we report a promising ZIB cathode material based on electrochemically induced transformation of vanadium oxides.Specifically,K_(2) V_6 O_(16)·1.5 H_(2) O nanofibers were synthesized through a simple stirring method at near room temperature and then used as cathode materials for ZIBs in different electrolytes.The cathode presented superior Zn^(2+) storage capability in Zn(OTf)_(2) aqueous electrolyte,including high capacity of 321 mAh/g,fast charge/discharge ability(96 mAh/g delivered in 35 s), high energy density of 235 Wh/kg and good cycling performance.Mechanism analysis evidenced that in Zn(OTf)_(2) electrolyte,Zn^(2+) intercalation in the first discharge process promoted K_(2) V_6 O_(16)·1.5 H_(2) O nanofibers to transform into Zn_(3+x)V_(2) O_7(OH)_(2)·2 H_(2) O nanoflakes,and the latter served as the Zn^(2+)-storage host in subsequent charge/discharge processes.Benefiting from open-framework crystal structure and sufficiently exposed surface,the Zn_(3+x)V_(2) O_7(OH)_(2)·2_H2 O nanoflakes exhibited high Zn^(2+) diffusion coefficient,smaller charge-transfer resistance and good reversibility of Zn^(2+) intercalation/de-intercalation,thus leading to superior electrochemical performance.While in ZnS04 aqueous electrolyte,the cathode material cannot sufficiently transform into Zn_(3+x)V_(2) O_7(OH)_(2)·2 H_(2) O thereby corresponding to inferior electrochemical behaviors.Underlying mechanism and influencing factors of such a transformation phenomenon was also explored.This work not only reports a high-performance ZIB cathode material based on electrochemically induced transformation of vanadium oxides,but also provides new insights into Zn^(2+)-storage electrochemistry.

Microstructural Features During Strain Induced Ferrite Transformation in 08 and 20Mn Steels

The microstructure evolution during strain induced ferrite transformation was followed in thermal-simulation tests of clean 08 and 20Mn steels. The influences of carbon equivalence and initial austenite grain size on ferrite grain refinement and the volume fraction of ferrite during straining were inspected. The results revealed that the accelerating effect of ferrite transformation by strain was increased as the carbon equivalence decreased. However, finer ferrite grains were obtained at higher carbon content. At strain of similar to1.5 ferrite grains less than 3 mum and 2 mum can be obtained in 08 and 20Mn steels respectively. Whereas the ferrite grain refinement in 08 steel was due to both effects of strain induced transformation and ferrite dynamic recrystallization, that in 20Mn was mainly due to strain induced transformation. Heavy strain can produce fine ferrite grains in coarse austenite grained 08 steel, but it would lead to band microstructure in coarse austenite grained 20Mn.

Effects of Alloying Elements on the Concentration Profile of Equilibrium Phases in Transformation Induced Plasticity Steel

With the two sublattices model, equilibrium compositions of ferrite (α) and austenite (γ) phases, as well as the volume percent of austenite (γ) in different TRIP steels are calculated. Concentration profiles of carbon, manganese, aluminum and silicon in these steels are also estimated under the lattice fixed frame of reference so as to identify if the equilibrium state is obtained. Through the comparison between the profiles after different time diffusion, the distribution of elements in phases is exhibited and the complex effect due to the mutual interaction of the elements on diffusion is discussed.

Effect of V and V-N Microalloying on Deformation-Induced Ferrite Transformation in Low Carbon Steels

Deformation-induced ferrite transformation （DIFT） has been proved to be an effective approach to refine ferrite grains. This paper shows that the ferrite grains can further be refined through combination of DIFT and V or V-N microalloying. Vanadium dissolved in γ matrix restrains DIFT. During deformation, vanadium carbonitrides rapidly precipitate due to strain-induced precipitation, which causes decrease in vanadium dissolved in matrix and indirectly accelerates DIFT. Under heavy deformation, deformation induced ferrite （DIF） grains in V microalloyed steel were finer than those in V free steel. The more V added to steel, the finer DIF grains obtained. Moreover, the addition of N to V microalloyed steels can remarkably accelerate precipitation of V, and then promote DIFT. However, DIF grains in V-N microalloyed steel easily coarsen.

Creep Induced Phase Transformation in Extruded Zn-Al Alloy

Phase transformation and microstructural change of an extruded eutectoid Zn-Al alloy Zn76Al22Cu2 (wt pct) were investigated during creep testing by using SEM and X-ray diffraction techniques. Creep induced decomposition of a metastable η'T phase and a four phase transformation, α+ ε →T' +η, occurred during the creep testing. Also a microstructural change was observed from a lamellar structure into a spheroidized structure in the rupture part of the extruded alloy. It provided evidence of creep induced phase transformations which occurred in ageing process. The mechanism of creep rupture of the extruded Zn-Al alloy was also discussed.

Formation of quaternary all-d-metal Heusler alloy by Co doping fcc type Ni_(2)MnV and mechanical grinding induced B2–fcc transformation

The structure of the all-d-metal alloy Ni_(50-x)Co_(x)Mn_(25)V_(25)(x=0–50)is investigated by using theoretical and experimental methods.The first-principles calculations indicate that the most stable structure of the Ni_2MnV alloy is face-centered cubic (fcc)type structure with ferrimagnetic state and the equilibrium lattice constant is 3.60A,which is in agreement with the experimental result.It is remarkable that replacing partial Ni with Co can turn the alloy from the fcc structure to the B2-type Heusler structure as Co content x>37 by using the melting spinning method,implying that the d–d hybridization between Co/Mn elements and low-valent elements V stabilizes the Heusler structure.The Curie temperature T_(C) of all-dmetal Heuser alloy Ni_(50-x)Co_(x)Mn_(25)V_(25)(x>37)increases almost linearly with the increase of Co due to that the interaction of Co–Mn is stronger than that of Ni–Mn.A magnetic transition from ferromagnetic state to weak magnetic state accompanying with grinding stress induced transformation from B2 to the dual-phase of B2 and fcc has been observed in these all-d-metal Heusler alloys.This phase transformation and magnetic change provide a guide to overcome the brittleness and make the all-d-metal Heusler alloy interesting in stress and magnetic driving structural transition.

NEOPLASTIC TRANSFORMATION OF HUMAN EMBRYONIC NASOPHARYNGEAL EPITHELIAL CELLS INDUCED BY N,N'-DINITROSOPIPERAZINE (DNP) IN VITRO

This experiment is the first report on N, N'-dini-trosopiperazine (DNF)-induced neoplastic transformation of human embryonic nasopharyngeal (HENPE) cells. The transformed cells showed a prolonged life span, anchorage independent growth, chromosome aberration, tumorigenicity and an altered cell morphological appearance. The results demonstrated that DNP was able to induce not only nasopharyngeal carcinoma (NPC) of rats in vivo, but also neoplastic transformation of HENPE cells in vitro.

Tensile Stress Induced Phase Transformations in Zn-Al Alloy

Both furnace cooled and as-cast eutectoid Zn-Al alloys were investigated under external tensile stress at 100℃. It was observed that the external tensile stress caused decomposition of two metastable phases η'T and η'S which derived from both original state of the alloy, and a phase transformation, αf +ε→T' +η， in both furnace cooled and as-cast eutectoid Zn-Al alloys. Also spheroidized structure formed partially during tensile testing. Superplasticity of the alloy has been discussed correlating with the phase transformations and microstructural changes.

TRANSFORMATION INDUCED SUPERPLASTICITY IN 18Ni MARAGING STEEL

After exploring the influence of stress,cold-rolling reduction and cooling rate on transforma- tion induced strain,the transformation induced superplasticity forming technique of the 18Ni maraging steel(2450 MPa)was developed.Through 14 times γα′ cyclic transformation,the limited elongation of 320% can be obtained in 60% cold-rolled specimen.TEM observation revealed that the morphology of stress induced martensite is massive.

Austempering of hot rolled transformation-induced plasticity steels

Thermomechanical controlled processing （TMCP） was conducted by using a laboratory hot rolling mill. Austempering in the salt bath after hot rolling was investigated. The effect of isothermal holding time on mechanical properties was studied through examining of the microstructure and mechanical properties of the specimens. The mechanism of transformation-induced plasticity （TRIP） was discussed. The results show that the microstructure of these steels consists of polygonal ferrite, granular bainite, and a significant amount of stable retained austenite. Strain-induced transformation to martensite of retained austenite and TRIP occur in the hot rolled Si-Mn TRIP steels. Excellent mechanical properties were obtained for various durations at 400℃. Prolonged holding led to cementite precipitation, which destabilized the austenite. The mechanical properties were optimal when the specimen was held for 25 min, and the tensile strength, total elongation, and strength ductility balance reached the maximum values of 776 MPa, 33%, and 25608 MPa.%, respectively.

Hot workability of high manganese transformation induced plasticity steel

The hot deformation behavior and microstructure evolution of high manganese transformation induced plasticity steel(Fe - 20Mn - 3Si - 3Al) were investigated by using hot compression test in a temperature range from 800℃to 1 050℃and strain rate ranging from 0.01 s^(-1) to 5.0 s^(-1).The effects of temperature,strain rate,and true strain on the flow behavior and microstructures of high manganese transformation induced plasticity steel were discussed.The results show that the dynamic recrystallization occurs only at higher temperature and lower strain rate.Hot deformation behaviors of high manganese transformation induced plasticity steel were sensitive to temperature and strain rate.The apparent stress exponent and the apparent activation energy of the investigated steel were about 4.280 and 463.791 kJ/mol, respectively.The apparent activation energy of the high manganese transformation induced plasticity steel was approached to the austenitic stainless steel(400 -500 kJ/mol).The hot working equation is obtained. Hot deformation peak stress increased with increasing of the value of lnZ.Peak stress and InZ exhibits a linear variation,the linear correlation coefficient was 0.988 9.The results show that the dynamic recrystallization was prone to occur when lnZ≤43.842 26 and Z≤1.098×10^(19),and better hot deformation properties would be obtained under this condition.

Computer Simulation of Ferrite Transformation during Hot Working of Low Carbon Steel

On the basis of transformation kinetics and thermodynamics, the austenite-ferrite transformation start temperature during deformation was predicted for several grades of low-carbon steels under different processing conditions. Results indicate that Ar3d temperature mostly depended on alloying composition and processing parameters. Ar3d increased as strain rate or strain increased for the same steel grade. In view of enhancement of deformation on transformation, the basic kinetics model was established to simulate deformation induced transformation behavior, using which the influence of the deformation stored energy and effective deformation ledge on the nucleation and growth can be considered. The simulated results are in good agreement with experiment results.

Transformation behaviors,structural and magnetic characteristics of Ni-Mn-Ga films on MgO(001)

Ferromagnetic Ni-Mn-Ga films were fabricated by depositing on MgO （001） substrates at temperatures from 673 K to 923 K. Microstructure, crystal structure, martensitic transformation behavior, and magnetic properties of the films were studied. With increasing deposition temperature, the surface morphology of the films transforms from granular to continu- ous. The martensitic transformation temperature is not dependent on deposition temperature; while transformation behavior is affected substantially by deposition temperature. X-ray analysis reveals that the film deposited at 873 K has a 7M marten- site phase, and its magnetization curve provides a typical step-increase, indicating the occurrence of magnetically induced reorientation （MIR）. In situ magnetic domain structure observation on the film deposited at 873 K reflects that the marten- sitic transformation could be divided into two periods： nucleation and growth, in the form of stripe domains. The MIR occurs at the temperature at which martensitic transformation starts, and the switching field increases with the decrease of temperature due to damped thermal activation. The magnetically induced martensitic transformation is related to the difference of magnetization between martensite and austenite. A shift of martensite temperature of dT/dH = 0.43 K/T is observed, consistent with the theoretical value, 0.41 K/T.

Effect of Crystallographic Orientation on Quenching Stress during Martensitic Phase Transformation of Carbon Steel Plate

During quenching, the residual stresses are affected by the crystallographic orientation of martensite, because the nonuniform thermal stresses affect the crystallographic orientation of the lathshaped martensite and induce the anisotropic expansion. To simulate this process, the model of anisotropic transformation induced plasticity（TRIP） was built using the WLR-BM phenomenological theory. The equivalent expansion coefficient was introduced considering the thermal and plastic strains, which simplified the numerical simulation. Furthermore, the quenching residual stresses in carbon steel plates were calculated using the finite element method under ANSYS Workbench simulation environment. To evaluate the simulative results, distributions of residual stresses from the surface to the interior at the center of specimen were measured using the layer-by-layer hole-drilling method. Compared to the measured results, the simulative results considering the anisotropic expansion induced by the crystallographic orientation of martenstic laths were found to be more accurate than those without considering it.

TRANSFORMATION OF RETAINED AUSTENITE IN CARBURIZED CASE DURING FATIGUE CRACK GROWTH

The morphology of the retained austenite in the carburized case of 20CrNiMo steel and its transformation during fatigue crack propagation through the case were investigated by using X-ray and TEM analysis.In the carburized case both film and block shaped retained austenite were found.Due to the crystallographic orientation relationship at the interface,the fatigue crack is inclined to pass through the block shaped retained austenite and thereby stim- ulates its strain-induced martensitie transformation.During the process of the fatigue frac- ture,most of the retained austenite structures on the crack path are transformed into the martensite,and the untranaformed parts on the fracture surface remain less than 6%.The transformation of the retained austenite,which is restrieted mainly within the plastic zone,oc- curs only during the proeess of fracture,and is independent of the magnitudes of the external stress,stress ratio and cyclic number.The volume expansion accompanying the transforma- tion creates an additional residual displacement of about 0.44μm on fracture surfaces,which is equivalent to the magnitude of the plasticity-induced residual displacement.The phase transformation induced fatigue crack closure is believed to be an important factor affecting the fatigue crack behaviors in the high carbon laver of the carburized case.

Effect of Strain Rate on the Ferrite Grain Refinement in a Low Carbon Nb-Ti Microalloyed Steel during Low Temperature Deformation

Grain refinement is one of the effective methods to develop new generation low carbon microalloyed steels possessing excellent combination of mechanical properties. The microstructural evolution and ferrite grain refinement at the deformation temperature of 865℃, above Ar3, with different strain rates were investigated using single pass isothermal hot compression experiments for a low carbon Nb-Ti microalloyed steel. The physical processes that occurred during deformation were discussed by observing the optical microstructure and analyzing the true stress-true strain responses. At strain rates of 0.001 and 0.01s^-1, there is no evidence of work hardening behavior during hot deformation and strain-induced transformation （SIT） leads to dynamic flow softening in flow curves. Optical microscopy observation shows that ultrafine and equiaxed ferrite with grain sizes of 2μm can be obtained by applying deformation with strain rate of 0.1 s^-1 due to SIT just after deformation. Furthermore, increasing the strain rate from 0.001 to 0.1 s^-1 reduces both the grain size of the equiaxed ferrite and the amount of deformed ferrite.

RELATIONSHIP BETWEEN RETAINED AUSTENITE AND STRAIN FOR Si-Mn TRIP STEEL

The equation which reflects the relationship between the retained austenite and strain has been proposed and clear TRIP can be obtained while the S value (An index of retained austenite stability) is less than 6.5 for Silicon-Manganese TRIP steel

Comparison of Ferrite Refinement Mechanisms by Different Processing Schedules in 08 and 20Mn Steels

The influence of deforming temperature on ferrite refinement was analyzed by comparing the microstructures obtained by deformation at above A(r3), in two-phase region of (alpha + gamma) and at below A(t) in clean 08 and 20Mn steels. The results indicate that ferrite refinement through strain induced transformation by deformation at above A(r3) is more effective than that by deformation simply through ferrite dynamic recrystallization. The main problem of ferrite refinement by deformation at below A(r3) is the inhomogeneity of microstructure which is controlled by the orientations and sizes of ferrite grains and the distribution of second phases. Ferrite dynamic recrystallization after strain induced transformation can further effectively refine ferrite.

A GENERAL MATHEMATICAL FRAMEWORK OF COMPLEX SYSTEMS(Ⅰ)

The fundamental and simplest structure of a complex system is a network.According to this idea,we plan to develop a general methematical framework of complex systems.In this paper,we discuss in detail the concept of systems,a general description of systems:System=(Hardware,Software,Environment),and whole-part relations,including relations between elements and systems,subsystems and systems,and between systems.The rules of operations of systems are given,and the induced transformations between hardware and software of systems are briefly discussed.

Effect of Strain Path Reversal on Austenite Grain Subdivision and Deformation Induced Ferrite Transformation Studied by Hot Torsion

The effects of large strain and strain path reversal on the deformation microstructure evolution in austenite below the recrystallisation temperature were studied by hot torsion using a non-transforming Fe-30wt%Ni model austenitic alloy.Results show that the high angle boundaries (HABs) can be generated by both microstructure mechanism through dislocation accumulation and texture mechanism via subgrain rotation.However,multiple strain path reversals lead to less well-developed HABs in the original grains compared to single reversal deformed to the same amount of total accumulative strain.This effect is attributed to the subgrain rotation mechanism being less effective at small strains.In comparison,the same hot torsion tests were conducted using a microalloyed steel at a temperature between Ae 3 and Ar 3.After single strain path reversal,substantial deformation-induced austenite-to-ferrite phase transformation was observed.Meanwhile,a test with multiple strain path reversals but with the same total strain produces much lower levels of strain-induced ferrite formation.This difference is correlated to the observations made in the Fe-30wt%Ni model alloy.It is believed that the different amount of strain-induced ferrite originated from the different levels of strain-induced HABs within the austenite which act as ferrite nucleation sites.