Effect of Valence Electron Structure on Temper Process and Hardness of the Supersaturated Carburized Layer

By measuring the hardness of carburized layer of a new type supersaturated carburizing steel （35Cr3SiMnMoV） at different temper temperature for 2 h, the relationship curve between the carburized layer hardness and the temper temperature is established. The result indicates that the hardness goes down firstly, then up and down, just like a wave consistent with the temperature increase. A secondary hardening peak appears at 570 ℃ or so. Based on Empirical Election Theory （EET） of Solids and Molecules, the valence electron structures （VESs） containing α-Fe-C, α-Fe-C-Me segregation structure units and carbide are calculated. The laws of temper process and hardness change with the temper temperature are explained, and the fact that reconstruction of θ-Fe3C is prior to that of special carbide at high tempering is analyzed with the phase structure formation factor, S, being taken into consideration. Therefore, the laws of temper process and hardness change of supersaturated carburized layer at different temper temperature can be traced back to valence electron structure （VES） level of alloy phase.

Analysis of Valence Electron Structure of RE in Solid Solution in Medium and Low Carbon Steel

According to EET theory, the valence electron structures of RE in the solid solution of austenite, pearlite and martensite were calculated. The influence of RE in solid solution on phase transformation of pearlite and recrystallization of martensite was explained by the valence electron structure data of phases. Calculating results indicate that C element is favorite to enhance the number of RE in the solid solution. RE in the solute solution shortens the incubation period of proeutectoid ferrite, increases its quantity and carbon content, decreases the quantity of pearlite and thickness of its lamellas and lamellar spacing, then the strength and hardness of pearlite are improved and granular pearlite can be obtained. RE dissolved in martensite intensifies martensite, enhances tempering stability of martensite, increases its recrystallization temperature and prolongs the holding time needed during tempering.

Study Segregation of Alloying Elements in Continuous Casting Slab with Valence Electron Structure

By calculating the electron structures of the phases that phosphor, sulfur and alloying elements dissolving inγ-Fe, the reason why alloying elements can bring centerline segregation in continuous casting slab (CCS) with nA, the number of electrons on the strongest covalent bonds, and the structure formation factor S were investigated, and an electron structural criterion to control and to eliminate the centerline segregation was advanced. Basing on this, the electron structures of a part of rare earth phosphides and sulfides are calculated, the physical mechanism that rare earth elements can control the segregation of phosphor and sulfur is analyzed, and the criterion is well verified.

Structural evolution and superconductivity tuned by valence electron concentration in the Nb-Mo-Re-Ru-Rh high-entropy alloys

The crystal structure and physical properties of Nb_(25)Mo_(5+x)Re_(35)Ru_(25-x)Rh_(10)(0≤x≤10)and Nb_(5)Mo_(35-y)Re_(15+y)Ru_(35)Rh_(10)(0≤y≤15)high-entropy alloys(HEAs)have been studied by X-ray diffraction,electrical resistivity,magnetic susceptibility,and specific heat measurements.The results show that the former HEAs with valence electron concentration(VEC)values of 6.7-6.9 crystallize in a noncentrosymmetric cubicα-Mn structure,while the latter ones with VEC values of 7.1-7.25 adopt a centrosymmetric hexagonal close-packed(hcp)structure.Despite different structures,both series of HEAs are found to be bulk superconductors with a full energy gap,and the superconducting transition temperature Tc tends to decrease with the increase of VEC.Nevertheless,the Tc values of the hcp-type HEAs are higher than those of theα-Mn-type ones,likely due to a stronger electron phonon coupling.Furthermore,we show that VEC and electronegativity difference are two key parameters to control the stability ofα-Mn and hcp-type HEAs.These results not only are helpful for the design of such HEAs,but also represent the first realization of structurally different HEA superconductors without changing the constituent elements.

Microstructure,phase composition and wear resistance of low valence electron concentration Al_(x)CoCrFeNiSi high-entropy alloys prepared by vacuum arc melting

The low valence electron concentration(VEC)Al_(x)CoCrFeNiSi(x=0.5,1.0,1.5 and 2.0)high-entropy alloys(HEAs)were designed by the fundamental properties of the constituent elements and prepared by vacuum arc melting method.The effects of Al addition on the crystal structure and microstructure were investigated.The microhardness and wear property were also researched.The results showed that the microstructure transformed from dendritic crystal to equiaxed crystal.It was found that FCC phase gradually decreased with the increasing Al content and disappeared until in a composition of 1.0 in Al_(x)CoCrFeNiSi HEAs.Little FCC phase was found with continuously adding Al,while the phase fraction of BCC increased from 85.0% to 91.8%,and VEC decreased from 7.00 to 6.14.The microhardness was increased gradually from 598 up to 909 HV with addition of Al from 0.5 to 2.0.It was the same of the compressive strength results,which improved from 1200 to 1920 MPa.The wear coefficient and mass loss were in line with mechanical properties evolution,which was attributed to the microstructure transformation into equiaxed crystal and the increase in BCC phase.

Effects of 4f Electron Characteristics and Alternation Valence of Rare Earths on Photosynthesis: Regulating Distribution of Energy and Activities of Spinach Chloroplast

Chloroplasts were isolated from spinach treated with taCl3, CeCl3, and NdCl3. Because of owning 4f electron characteristics and alternation valence, Ce treatment presented the highest enhancement in light absorption, energy transfer from LHC Ⅱ to PS Ⅱ, excitation energy distribution from PS Ⅰ to PS Ⅱ, and fluorescence quantum yield around 680 nm. Compared with Ce treatment, Nd treatment resulted in relatively lower enhancement in these physiological indices, as Nd did not have alternation valence. La treatment presented the lowest enhancement, as La did not have either 4f electron or alternation valence. The increase in activities of whole chain electron transport, PS ⅡDCPIP photoreduction, and oxygen evolution of chloroplasts was of the following order： Ce〉Nd 〉La〉 control. However, the photoreduction activities of spinach PS I almost did not change with La, Ce, or Nd treatments. The results suggested that 4f electron characteristics and alternation valence of rare earths had a close relationship with photosynthesis improvement.

ELECTRON TRANSFER AND PHOTOCHEMICAL VALENCE ISOMERIZATION IN ANTHRACENE AND NORBORNADIENE SYSTEMS

To harvest the sun light and to promote the amount of energy stored,a new binary compound which links a sensitizer(electron donor), anthracene,and substrate(electron acceptor),norbornadiene,in a non- conjugated manner without increase in molecular weight was synthesized.The inter-and intramolecular photosensitized isomerization and the mechanism were studied.

Correlation between electronic structure and energy band in Eu-doped CuInTe_2 semiconductor compound with chalcopyrite structure

The Eu-doped Cu（In, Eu）Te2 semiconductors with chalcopyrite structures are promising materials for their applications in the absorption layer for thin-film solar cells due to their wider band-gaps and better optical properties than those of CuInTe2. In this paper, the Eu-doped CuInTe2 （CuIn1-xEuxTe2, x = 0, 0.1, 0.2, 0.3） are studied systemically based on the empirical electron theory （EET）. The studies cover crystal structures, bonding regularities, cohesive energies, energy levels, and valence electron structures. The theoretical values fit the experimental results very well. The physical mechanism of a broadened band-gap induced by Eu doping into CuInTe2 is the transitions between different hybridization energy levels induced by electron hopping between s and d orbitals and the transformations from the lattice electrons to valence electrons for Cu and In ions. The research results reveal that the photovoltaic effect induces the increase of lattice electrons of In and causes the electric resistivity to decrease. The Eu doping into CuInTe2 mainly influences the transition between different hybridization energy levels for Cu atoms, which shows that the 3d electron numbers of Cu atoms change before and after Eu doping. In single phase CuIn1-xEuxTe2, the number of valence electrons changes regularly with increasing Eu content, and the calculated band gap Eg also increases, which implies that the optical properties of Eu-doped CuIn1-xEuxTe2 are improved.

Tuning the electron structure enables the NiZn alloy for CO_(2) electroreduction to formate

Formate is an important liquid chemical,which can be produced by electrocatalytic carbon dioxide reduction reaction(CO_(2) RR).Most of the metal catalysts for CO_(2) RR to formate are toxic or noble metals,such as Cd,Hg,Pb and Pd,leading to the environmental pollution or increased production costs.Herein,we develop an environmentally friendly and low-cost NiZn alloy catalyst for CO_(2) RR to formate.The X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS) and transmission electron microscopy(TEM) confirm the alloy structure of the prepared NiZn catalyst. As for a catalyst for CO_(2) RR,the NiZn alloy exhibits the FE_(HCOO)^(-)(Faraday efficiency of HCOO^(-)) of 36±0.7% at-0.9 V vs.RHE in 0.1 M KHCO_(3), and remarkable stability for 40,000 s at-0.8,-0.9,-1.0 and-1.1 V vs.RHE,respectively.Theoretical calculation results indicate that the NiZn alloy exhibits the middle valence electron structure between the Zn and Ni metal,resulting in the favorable pathway for HCOOH formation but unfavorable for the hydrogen evolution reaction and CO production.The Ultraviolet Photoelectron Spectroscopy results verify the modulated valence electron structure for NiZn alloy as compared to Ni and Zn,consistent with the theoretical calculation results.This work provides new insights into design of alloy catalysts for CO_(2) RR to formate.

DETERMINATION AND APPLICATION OF LARSON-MILLER PARAMETER FOR HEAT RESISTANT STEEL 12CrlMoV AND 15CrMo

Based on the analysis and processing on relative empirical formula and data, C-values in Larson-Miller (P) expression, P= T(C + Igt), have determined for pearlitic heat resistant steel 12Cr1MoV and 15CrMo(20.62 and 20.30). The simulation experiments of high temperature aging, heated from 1.5 to 873 hours, have been designed and performed for its verification. And in combination with published information and the present nearly quantitative works, it has further been verified that both the degradations of microstructures and mechanical properties show a good accuracy and practicability using the Larson-Miller parameter with the present determined C-values. Finally, the effects of carbon content on C-value are analyzed by the empirical electron theory of solids and molecules (EET).

A New hcp Phase Formed in the Ni-Nb System during Ion-beam-assisted Deposition

The Ni80Nb20 films were prepared by ion beam assisted deposition (IBAD) with various Ar+ ion energies. A phase evolution of fcc→amorphous→Ni+Nb→Ni+hcp was observed with the increasing of ion beam energy from 2 keV to 8 keV. When bombarded by Ar+ ions of 8 keV during deposition, a new crystalline phase with hcp structure was obtained, of which the lattice parameters are a=0.286 nm and c=0.483 nm, different from those of the similar A3B-type hcp phase previously reported. The experimental results were discussed in terms of thermodynamics and restricted kinetic conditions in the far-from-equilibrium process of IBAD. The formation of hep phase may also be related to the valence electron effect.

EFFECT OF HETEROGENEOUS DISTRIBUTION OF C AND ALLOYING ELEMENTS ONγ/α′TRANSFORMATION IN A Fe-Mn-Cr-C ALLOY

The heterogeneous distribution of C and metallic alloying elements as well as the phase com- position changes before and after cold deformation of an Fe-Mn-Cr-C alloy have been stu- died by the use of Mssbauer spectroscopy.The austenites without and with C and metallic alloying elements are found in the alloy in as-solid solution state.While the martensites with- out and with C and alloying elements may be induced by cold deformation.The transforma- tion from austenite to martensite in the alloy is confirmed via theoretical computation and ex- periments to be controlled by the number of covalent electron pairs forming covalent bond in austenitic crystal cell of the alloy.The formation of strong covalent bond between C and me- tallic elements can vigorously retard the γ/α' transformation.

HYDROGEN IN Pd-In ALLOYS

The equilibrium p-c-T data were determined by a microbalance in a vacuum system at hydrogen pressures up to 3.5 MPa on four Pd-In alloys between 3.64 and 14.53 at. % In as well as on Pure Pd. The results are similar to those obtained on the analogous alloys Pd-Ag and Pd-Sn and are interpreted in the same manner. In has two opposing effects upon the solubility of H in the Pd alloys, i.e., increase of the Fermi energy upon the donation of valence electrons and a lattice dilatation. At valence electron concentrations below 0.5, the lattice dilatation predominates and the H solubility is increased with addition of In. At valence electron concentrations above 0.5, the influence of the elevated Fermi energy predominates and the H solubility is lowered by addition of In. The molar enthalpy of Pd hydriding at infinite dilution is strongly increased with increasing In content, but the molar entropy is not nearly as much affected by the Presence of In. The excess chemical potential of hydrogen at small hydrogen concentrations and at a given temperature increases with an increase of In content. The apparent H-H attractive interaction energy, W H-H, is decreased by the presence of In. The trend is also similar to that found for the Pd-Ag-H and Pd-Sn-H system.

THE CALCULATION OF THE COHESIVE ENERGY OFГPHASE IN THE TRANSITIONAL LAYER FE ZN OF HEAT GALVANIZED SHEET USED IN CARS

hethesisanalysesthevalenceelectronstructuresof phase Γin Fe Zn transitionallayerof heat galvanized sheet used in cars by applying the Empirical Electron Theory of Solids andMolecules, and calculatesthebond energy ofthe major bondsand cohesiveenergy ofcrystals,from which we draw theconclusion:sincecrystal has alargercohesiveenergy, it has higherhardness, butsinceitsbondenergyisratherlow ,itiseasytobreak under pressurefrom out side, and thecrackiseasytocome up andspreadin phase Γ.

Synergistic effect between MnO and CeO_2 in the physical mixture:Electronic interaction and NO oxidation activity

MnO and CeO2 powders were mechanically mixed by a spatula and by milling to obtain loose-contact and tight-contact mixed oxides,respectively.The monoxides and their physical mixtures were characterized by X-ray diffraction（XRD）,Brunauer-Emmett-Teller（BET）,X-ray photoelectron spectroscopy（XPS）,Raman,O2 temperature-programmed desorption（O2-TPD）,H2 temperature-programmed reduction（H2-TPR） and NO temperature-programmed oxidation（NO-TPO）.The MnOx-CeO2 solid solutions did not form without any calcination process.The oxidation state of manganese tended to increase while the ionic valence of cerium decreased in the mixed oxides,accompanied with the formation of oxygen vacancies.This long-ranged electronic interaction occured more significantly in the tight-contact mixture of MnO and CeO2.The formation of more Mn4＋and oxygen vacancies promoted the catalytic oxidation of NO in an oxygen-rich atmosphere.

Effect of cerium on structure,magnetism and magnetostriction of Fe_(81)Ga_(19) alloy

FeGa alloy is a new kind of magnetostrictive material, and rare-earth cerium can improve its magnetostrictive property.（Fe（81）Ga（19））（100-x）Cex（x = 0, 0.3 at%, 0.7 at%, 1 at%） samples were prepared by doping cerium in Fe（81）Ga（19） alloy. Their microstructures and phases were studied, and valence electronic structures were investigated. Electromagnetic parameters, such as coercivity, saturation magnetization,remnant magnetization and saturation magnetostrictive coefficients（λs） of every sample were measured.Cerium atoms are distributed at grain boundaries, and the Ce-doped alloys remain the A2 structure of FeGa alloy. When x is 0.7, the value of saturation magnetism is 217.08 emu/g, which is the maximum in the Ce-doped samples. The equivalent half length of single bond is the maximum also, and reaches to0.11380 nm. At the same time, the number of covalent electrons is 3.5672, and is the minimum of the Cedoped samples. Its As is the largest in the four samples. The change of As results in the change of equivalent half length of single bond in Ce-doped alloy.

Synergistic effects of immunoregulation and osteoinduction of ds-block elements on titanium surface

Ds-block elements have been gaining increasing attention in the field of biomaterials modification,owing to their excellent biological properties,such as antibiosis,osteogenesis,etc.However,their function mechanisms are not well understood and conflicting conclusions were drawn by previous studies on this issue,which are mainly resulted from the inconsistent experimental conditions.In this work,three most widely used ds-block elements,copper,zinc,and silver were introduced on titanium substrate by plasma immersion ion implantation method to investigate the rule of ds-block elements in the immune responses.Results showed that the implanted samples could decrease the inflammatory responses compared with Ti sample.The trend of anti-inflammatory effects of macrophages on samples was in correlation with cellular ROS levels,which was induced by the implanted biomaterials and positively correlated with the number of valence electrons of ds-block elements.The co-culture experiments of macrophages and bone marrow mesenchymal stem cells showed that these two kinds of cells could enhance the anti-inflammation and osteogenesis of samples by the paracrine manner of PGE2.In general,in their steady states on titanium substrate(Cu2+,Zn2+,Ag),the ds-block elements with more valence electrons exhibit better anti-inflammatory and osteogenic effects.Moreover,molecular biology experiments indicate that the PGE2-related signaling pathway may contribute to the desired immunoregulation and osteoinduction capability of ds-block elements.These findings suggest a correlation between the number of valence electrons of ds-block elements and the relevant biological responses,which provides new insight into the selection of implanted ions and surface design of biomaterials.

Prediction of alloy composition and microhardness by random forest in maraging stainless steels based on a cluster formula

Fe-Ni-Cr-based super-high-strength maraging stainless steels were generally realized by multiple-element alloying under a given heat treatment processing. A series of alloy compositions were designed with a uniform cluster formula of [Ni16Fe192]（Cr32（Ni16-x-y-z-m-n MoxTiyNbzAlmVn）） （at.%） that was developed out of a unique alloy design tool, a cluster- plus-glue-atom model. Alloy rods with a diameter of 6 mm were prepared by copper-mold suction-cast processing under the argon atmosphere. These alloy samples were solid-solutioned at 1273 K for 1 h, followed by water-quenching, and then aged at 783 K for 3 h. The effect of the valence electron concentration, characterized with the number of valence electrons per unit cluster （VE/uc） formula of 16 atoms, on microhardness of these designed maraging stainless steels at both solid- solutioned and aged states was investigated. The relationship between alloy compositions and microhardness in maraging stainless steels was firstly established by the random forest （RF, a kind of machine learning methods） based on the experimental results. It was found that not only the microhardness of any given composition alloy within the frame of cluster formula, but also the alloy composition with a maximum microhardness for any given VE/uc, could be predicted in good agreement with the guidance of the relationship by RF. The contributions of minor-alloying elements to the microhardness of the aged alloys were also discussed.

Improving high-temperature oxidation behavior by modifying Al and Co content in Al-Co-Cr-Fe-Ni high-entropy alloy

Composition modification was introduced to improve the oxidation resistance by varying Al and excluding Co from the Al-Co-Cr-Fe-Ni system. Since adjusting the composition shifted the valence electron concentration(VEC) of the alloys, the dual-phase structure of the alloys is expected to be more stable. At low temperatures(T < 1273 K), the alloys formed mixed oxide products. As oxidation temperature increased,only Cr_(2)O_(3)or Al_(2)O_(3)dominated the alloy’s surface. Compared to equiatomic AlCoCrFeNi(5-Equi), nonequiatomic AlCoCrFeNi(5-B 40) and four-component AlCrFeNi(4-B 2013) had better oxidation resistance due to monocrystalline-Al_(2)O_(3)formation. Besides the role of oxide formation, maintaining BCC and B2phases within the alloys is also beneficial to supporting the stable Cr_(2)O_(3)or Al_(2)O_(3).

Structural homology of the strength for metallic glasses

The structure-property relationship,one of the central themes in materials science,is far from being well understood for metallic glasses(MGs)due to the great complexity of their amorphous structures.Based on the analysis of published experimental data for 165 MGs from more than 15 different alloy systems,the present study reveals a universal dependence of mechanical properties(Young’s moduli,shear moduli and yield strength)on simple structural parameters(the inter-atomic distance and/or valence electron density)originating from the interatomic potential and Fermi sphere-Brillouin zone interaction.This work establishes a structure-property relationship for metallic glasses and provides insights into the fundamentals of the mechanical properties of disordered systems.