Surface oxide layers play a significant role in forming secondary oxidation inclusions during the casting process.In this study,three typical Mg-RE alloys(Mg-3Nd(NZ30K),Mg-3Nd-3Gd(EV33)and Mg-3Nd-4Y(WE43A))are selecte...Surface oxide layers play a significant role in forming secondary oxidation inclusions during the casting process.In this study,three typical Mg-RE alloys(Mg-3Nd(NZ30K),Mg-3Nd-3Gd(EV33)and Mg-3Nd-4Y(WE43A))are selected.Their surface oxide layers formed during the solidification are characterized in detail,and the corresponding oxidation mechanisms are discussed.The results reveal that RE elements obviously influence the characteristics of surface oxide layers,which depends on their ability to purify the formed MgO in the melt via the reaction(2RE+3MgO=3Mg+RE_(2)O_(3)).On the one hand,as Nd and Gd do not easily displace MgO already formed in the melt,the loose oxide layers in NZ30K and EV33 alloys are mainly composed of MgO matrix with embedded RE-rich oxide particles.On the other hand,due to the strong ability of Y to purify MgO in the melt,the oxide layer of WE43A alloy becomes a denser and thinner Y_(2)O_(3) oxide layer.Note that the differences in surface oxide layers well explain the different secondary inclusions that occur in three typical Mg-RE alloys during the casting process.展开更多
Mn-based layered oxides are widely recognized as cathode materials for potassium-ion batteries(KIBs)due to their high specific capacity derived from their low molar mass.However,the structural instability caused by th...Mn-based layered oxides are widely recognized as cathode materials for potassium-ion batteries(KIBs)due to their high specific capacity derived from their low molar mass.However,the structural instability caused by the Jahn-Teller effect of Mn^(3+)and the large ionic radius of K+results in poor electrochemical performance.Herein,we propose an effective structural stabilization strategy for P2-type Mn-based layered oxide cathodes of KIBs through Li-incorporation into the transition metal layer.Using the firstprinciples calculations and experiments,we demonstrate that the P2-K_(0.48)[Li_(0.1)Mn_(0.9)]O_(2)(P2-KLMO)delivers improved electrochemical performance,specific capacity and average discharge voltage of~124.4 m A h g^(-1)and~2.7 V(vs.K^(+)/K)at 0.05C(1C=260 mA g^(-1)),outperforming P2-K_(0.5)MnO_(2).Operando X-ray diffraction analysis confirms the P2-OP4 phase transition and Mn^(3+)-induced Jahn-Teller distortion are significantly suppressed in P2-KLMO.These improvements are attributed to the lithium introduction into transition metal layers,leading to strengthened structural stability and enhanced K+diffusion kinetics.Moreover,synthetic accessibility through the conventional solid-state method provides an additional advantage for practical application of Li-incorporated Mn-based P2-type cathodes in KIBs.We believe our study offers a simple yet effective strategy for designing highperformance and practical cathode materials for KIBs.展开更多
The P2-type Fe/Mn-based layered oxides,with cost advantages and high theoretical capacity,are considered one of the promising cathode materials for sodium-ion batteries(SIBs).However,the commercial development of thes...The P2-type Fe/Mn-based layered oxides,with cost advantages and high theoretical capacity,are considered one of the promising cathode materials for sodium-ion batteries(SIBs).However,the commercial development of these materials is impeded by two main factors:the MnO_(6) structure distortion induced by the Jahn-Teller(J-T)effect of Mn^(3+),and the unfavorable phase transitions that occur during the insertion and extraction of Na^(+).Here,we present a strategy to improve structural stability by incorporating cost-effective,robust Al-O bonds.This approach induces localized adjustments in the electronic structu re and a pinning effect,which limits the deformation of the transition metal(TM)layers,strengthens the electrostatic bonding within the TM layers,and expands the Na layer spacing.Consequently,the Na_(0.67)Fe_(0.4)Mn_(0.54)Al_(0.06)O_(2) cathode demonstrates a capacity of 168.8 mAh g^(-1) at 0.1 C,maintaining89.2%of its original capacity after 200 cycles at 1 C.Through in situ electrochemical impedance spectroscopy(EIS)with dynamic resistance transformation(DRT)analysis,ex situ X-ray absorption spectroscopy(XAS),and in situ X-ray diffraction(XRD),the study demonstrates a reduction in the J-T effect,enhanced kinetic performance,and the inhibition of detrimental phase transitions.This study offers new avenues to the development and design of future low-cost Fe/Mn-based cathodes.展开更多
Sodium layered oxides stand out as one of the most promising cathodes for sodium-ion batteries due to their high energy density,elemental abundance,and scalability.However,their practical applications are restricted b...Sodium layered oxides stand out as one of the most promising cathodes for sodium-ion batteries due to their high energy density,elemental abundance,and scalability.However,their practical applications are restricted by interplanar gliding,cation migration,and the formation of intragranular microcracks,which collectively lead to rapid structural degradation and capacity loss.Herein,we rationally design an ultrastable O3-type Na_(0.94)Ca_(0.03)Ni_(1/3)Fe_(1/3)Mn_(1/3)O_(2) cathode,in which Ca^(2+)cations act as pillars within the NaO_(2)slabs,suppressing the irreversible phase transitions and Na/TM cation migration commonly observed in layered oxides.Multiscale in situ and ex situ techniques,combined with post-mortem analysis,reveal that the Ca-pillared pinning effect not only effectively suppresses the interplanar gliding and stress accumulation within the crystal phase but also restrains Na/TM cation migration and surface reconstruction in near-surface regions.Benefiting from the combined effects of structural stabilization,the Ca-pillared cathode exhibits a superior cycling stability,retaining 81.6%of its capacity after 1000 cycles at 2 C within the voltage range of 2.0-4.0 V,along with significantly enhanced wide-temperature(from-40 to 80℃)performance.This work highlights another critical role of Ca pillars in suppressing cation migration and surface structural degradation beyond preventing adverse interplanar gliding,offering valuable insights for designing long-life and wide-temperature layered oxide cathodes.展开更多
High-capacity O3-type layered NiFeMn-based oxides are promising cathodes for sodium-ion batteries,though their practical deployment is constrained by the inherent limitations of Fe redox chemistry.Traditional designs ...High-capacity O3-type layered NiFeMn-based oxides are promising cathodes for sodium-ion batteries,though their practical deployment is constrained by the inherent limitations of Fe redox chemistry.Traditional designs generally enforcing stoichiometric symmetry(Ni=Mn)yield low Fe redox activity.Herein,we propose a valence engineering strategy that breaks conventional Ni/Mn stoichiometry to reconfigure Fe's local chemical environment and unlock unprecedented redox depth.Density functional theory(DFT)calculations reveal that the designed NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode exhibits a reduced Bader charge on Fe(1.598 vs.1.638 in NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2))and elevated Fe 3d orbital energy,signifying enhanced Fe redox activity.This configuration enables an exceptional Fe^(2.60+)/Fe^(3.88+)redox(1.28 e~-per Fe),delivering a reversible capacity of184.3 mAh g^(-1)within 2-4.2 V at 0.2 C,markedly exceeding the benchmark NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(161.3 mAh g^(-1))with low reaction depth of Fe^(3.01+)/Fe^(3.61+).The intensified cationic redox reaction enables an ultrahigh energy density of 596 Whkg-1.The NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode demonstrates robust performance over a broad temperature range from-15℃to 60℃.In situ and ex situ characterizations unveil a reversible O3■P3■OP2 phase transition with minimal volume change(1.88%)that circumvents detrimental deleterious O'3 intermediates and intragranular cracking.This work establishes valence engineering as a paradigm to consolidate cationic redox reaction in high-energy layered sodium oxide cathodes.展开更多
Layered oxides have attracted significant attention as cathodes for sodium-ion batteries(SIBs)due to their compositional versatility and tuneable electrochemical performance.However,these materials still face challeng...Layered oxides have attracted significant attention as cathodes for sodium-ion batteries(SIBs)due to their compositional versatility and tuneable electrochemical performance.However,these materials still face challenges such as structural phase transitions,Na^(+)/vacancy ordering,and Jahn–Teller distortion effect,resulting in severe capacity decay and sluggish ion kinetics.We develop a novel Cu/Y dual-doping strategy that leads to the formation of"Na–Y"interlayer aggregates,which act as structural pillars within alkali metal layers,enhancing structural stability and disrupting the ordered arrangement of Na^(+)/vacancies.This disruption leads to a unique coexistence of ordered and disordered Na^(+)/vacancy states with near-zero strain,which significantly improves Na^(+)diffusion kinetics.This structural innovation not only mitigates the unfavorable P2–O2 phase transition but also facilitates rapid ion transport.As a result,the doped material demonstrates exceptional electrochemical performance,including an ultra-long cycle life of 3000 cycles at 10 C and an outstanding high-rate capability of~70 mAh g^(−1)at 50 C.The discovery of this novel interlayer pillar,along with its role in modulating Na^(+)/vacancy arrangements,provides a fresh perspective on engineering layered oxides.It opens up promising new pathways for the structural design of advanced cathode materials toward efficient,stable,and high-rate SIBs.展开更多
Interfacial engineering is crucial for developing high-performance Ni-rich layered cathodes for lithiumion batteries.Here,we introduce an interfacial precipitation(IP)strategy,guided by first-principles calculations,t...Interfacial engineering is crucial for developing high-performance Ni-rich layered cathodes for lithiumion batteries.Here,we introduce an interfacial precipitation(IP)strategy,guided by first-principles calculations,to create a functionally graded cathode during precursor synthesis.Based on thermodynamic principles of bulk insolubility and phase separation kinetics,we achieved the selective precipitation of Co onto the surface of a Ni-rich hydroxide precursor.Upon high-temperature lithiation,this engineered precursor spontaneously forms a unique,bifunctional Co-rich spinel-like layer on the final LiNi_(0.88)Co_(0.06)Mn_(0.06)O_(2)(NCM)cathode.This architecture suppresses detrimental Li/Ni cation mixing and protects the active material.Consequently,the IP-driven NCM cathode demonstrates vastly superior rate capability,delivering 140.8 m A h g^(-1)at 5C,compared to 112.9 mA h g^(-1)for its conventionally prepared counterpart.This enhancement is attributed to significantly lower charge-transfer resistance and faster kinetics.Remarkably,in a full-cell configuration,the IP-driven NCM cathode maintains 81.5%capacity after 1000 cycles at an aggressive 5C rate.This work presents a thermodynamically driven,scalable strategy for designing advanced cathodes with exceptional high-power performance and stability.展开更多
High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instab...High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g^(-1) at 0.2 C,160.9 mA h g^(-1) at 2.0 C and 112.3 mA h g^(-1) at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g^(-1) after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.展开更多
Solid-state lithium(Li)batteries are hailed as the nextgeneration energy storage technology,garnering significant attention for their potential high energy density and safety.Particularly when using Li-rich manganese ...Solid-state lithium(Li)batteries are hailed as the nextgeneration energy storage technology,garnering significant attention for their potential high energy density and safety.Particularly when using Li-rich manganese layered oxide(LRMO)as cathodes(theoretical capacity exceeding250 mAh/g),energy densities over 600 Wh/kg can be theoretically achieved[1,2].展开更多
Layered oxides present compelling potential as cathode materials for sodium-ion batteries(SIBs).However,challenges including interfacial instability and sluggish reaction kinetics critically limit their rate capabilit...Layered oxides present compelling potential as cathode materials for sodium-ion batteries(SIBs).However,challenges including interfacial instability and sluggish reaction kinetics critically limit their rate capability and cycling performance.Herein,we introduce the water-soluble sodium polyacrylate(NaPAA)binder as a promising approach to mitigating these issues in P2-type layered oxides.The NaPAA binder facilitates the formation of a uniform Na^(+) conductive interfacial film,which protects the cathode against electrolyte-induced corrosion and effectively inhibits the dissolution of transition metals in P2-Na_(0.85)Li_(0.12)Ni_(0.22)Mn_(0.66)O_(2)(NLNMO).Furthermore,we elucidate the mechanism by which the NaPAA binder dynamically regulates the coordination of free anions at the electrode-electrolyte interface.This regulation reduces solvent decomposition and promotes the formation of a stable,ionically conductive layer.Consequently,the P2-NLNMO@NaPAA integrated electrode exhibits enhanced electrochemical performance,achieving an 89.2%capacity retention after 200 cycles at 0.2 C and delivering an initial capacity of 102.9 mA h g^(-1) even at 0℃.This study advances the fundamental understanding of binder-mediated interface engineering and demonstrates a scalable and eco-friendly manufacturing pathway for high-performance SIBs.展开更多
Zirconia coatings as hydrogen permeation barriers were formed on disktype ZrHj.s substrate speci mens in phosphate solution system by microarc oxidation technique. Influence of positive voltage on hydrogen per meation...Zirconia coatings as hydrogen permeation barriers were formed on disktype ZrHj.s substrate speci mens in phosphate solution system by microarc oxidation technique. Influence of positive voltage on hydrogen per meation barriers on the surface of zirconium hydride was investigated as the main factor. The thickness of total oxide layer increased from 42.5 to 55.0 ~tm the increase of positive voltage increasing from 325 up to 425 V. The permeation reduction factor （PRF） was observed under different voltages, which increased with the increasing positive voltages. The phase structure of oxide layer was monoclinic Zr02 and tetragonal ZrO1.88. No reduction reaction occured in the process of hydrogen escaping, and it indicates that hydrogen permeation through oxide layer is restricted.展开更多
Inconel 600 alloy is widely utilized for high temperature environment application due to the corresponding good oxidation and corrosion resistance properties.In order to estimate the high temperature oxidation resista...Inconel 600 alloy is widely utilized for high temperature environment application due to the corresponding good oxidation and corrosion resistance properties.In order to estimate the high temperature oxidation resistance of Inconel 600 alloy at various temperatures,the oxidation weight gain of all specimens was measured and fitted for the curve at the temperatures of 700,800 and 900 ℃ for exposure time of 100 h.The surface morphology and the component of the oxide film were analyzed by scanning electron microscopy(SEM),energy-dispersive spectroscopy(EDS) and X-ray diffraction(XRD).The results indicate that the high temperature oxidation resistance of Inconel 600 alloy is excellent blew 800℃ due to the oxidation kinetic curves at different temperatures corresponding to the parabola dynamic rules.This means that the oxidation film protects the substrate well.The dense oxide layer formation containing Cr_(2)O_(3) and NiCr_(2)O_(4) at 700 and 800 ℃ and MnCr_(2)O_(4) at 900 ℃,respectively,is the main reason for the good oxidation resistance.In contrast,the oxide layer peels off easily under applied force as the temperature increases beyond 800℃, on account of the complicated compositions of the oxide film and the binding force between the oxide layer and the substrate weakening.Corresponding oxidation mechanism is expected to be understood and the oxidation resistance of Inconel 600 alloy is improved through binding force enhancement.展开更多
Ta/NiFe/Ta ultrathin films with and without nano-oxide layers （NOLs） were prepared by magnetron sputtering followed by a vacuum annealing process. The influence of NOLs on the magnetoresistance （MR） ratio of ultra...Ta/NiFe/Ta ultrathin films with and without nano-oxide layers （NOLs） were prepared by magnetron sputtering followed by a vacuum annealing process. The influence of NOLs on the magnetoresistance （MR） ratio of ultrathin permalloy films was studied. The results show that the influence of grain size and textures on the MR ratio becomes weak when the thickness of the NiFe layer is below 15 nm. A higher MR ratio was observed for the thinner （〈 15 nm） NiFe film with NOLs. The MR ratio of a 10 nm NiFe film can be remarkably enhanced by NOLs. The enhanced MR ratio for these ultrathin films can be attributed to the enhanced specular reflection of conduction electrons.展开更多
Chemically resistant anodic oxide layers were formed on pure aluminum substrates in oxalic acid-sulphuric acid bath.Acid dissolution tests of the obtained anodic layers were achieved in accordance with the ASTM B 680-...Chemically resistant anodic oxide layers were formed on pure aluminum substrates in oxalic acid-sulphuric acid bath.Acid dissolution tests of the obtained anodic layers were achieved in accordance with the ASTM B 680-80 specifications：35mL/L 85% H3PO4＋20g/L CrO3 at 38℃.Influence of oxalic acid concentration,bath temperature and anodic current density on dissolution rate and coating ratio was examined,when the sulphuric acid concentration was maintained at 160g/L.It was found that chemically resistant and compact oxide layers were produced under low operational temperature （5℃） and high current densities （3A/dm^2）.A beneficial effect was observed concerning the addition of oxalic acid （18g/L）.The morphology and the composition of the anodic oxide layer were examined by scanning electron microscopy （SEM）,atomic force microscopy （AFM） and glow-discharge optical emission spectroscopy （GDOES）.展开更多
The oxidation behavior and mechanism of a porous Ni?Cr?Al?Fe alloy in the temperature range from850to1000°Cwere investigated by optical microscopy,scanning electron microscopy(SEM)and energy dispersive spectrosco...The oxidation behavior and mechanism of a porous Ni?Cr?Al?Fe alloy in the temperature range from850to1000°Cwere investigated by optical microscopy,scanning electron microscopy(SEM)and energy dispersive spectroscopy(EDS),X-raydiffraction(XRD)analyses and X-ray photoelectron spectroscopy(XPS).The results show that the oxidation kinetics at950and1000°C of this porous alloy is pseudo-parabolic type.Complex layers composed of external Cr2O3/NiCr2O4and internalα-Al2O3areformed on the surface of the oxidized porous alloys.γ?phases favor the formation of NiO/Cr2O3/NiCr2O4during the initial oxidation.Many fast diffusion paths contribute to the development of the oxide layers.The decrease of the open porosity and the permeabilitywith exposure time extending and temperature increasing can be controlled within a certain range.展开更多
The oxidation behavior of a newly designed Co-Ni-based alloy with varied addition of Ti(1.4 and 2.1 wt.%,hereafterreferred as 1.4Ti and 2.1Ti alloys)was explored in air at 900℃.It is found that an outer oxide layer c...The oxidation behavior of a newly designed Co-Ni-based alloy with varied addition of Ti(1.4 and 2.1 wt.%,hereafterreferred as 1.4Ti and 2.1Ti alloys)was explored in air at 900℃.It is found that an outer oxide layer composed of CoO,anintermediate oxide layer composed of intermittent TiO,plus continuous Cr,W-rich oxides,and an inner oxidized regioncomposed of Al2O3 were formed on the surface of 1.4Ti alloy,whereas the oxide structure of 2.1Ti alloy was composed of Co0 as the outer oxide layer,continuous TiO2,Cr2O3 and WO3 as intermediate oxide layer,and Al2O3 as the inner oxidizedregion.With increasing Ti content.continuous TiO2 films formed in the intermediate oxide layer,which would lead to theformation of compact Cr2O3 and improved oxidation resistancc after 100 h oxidation at 900℃.These observations indicatedthat Ti addition can improve the high-temperature oxidation resistance of Co-Ni-based aloys.展开更多
Plasma electrolytic oxidation （PEO） is carried out on 6061 Al-alloys in a weak alkaline electrolyte containing NaOH, Na2SiO3 and NaCl. Centered on the correlation of composition and structure, analyses by means of X...Plasma electrolytic oxidation （PEO） is carried out on 6061 Al-alloys in a weak alkaline electrolyte containing NaOH, Na2SiO3 and NaCl. Centered on the correlation of composition and structure, analyses by means of X-ray diffration （XRD）, scanning electron microscope （SEM） and energy dispersive spectrometry （EDS） are conducted on the specimens, which have been PEO-treated under hybrid voltages of different direct current （DC） values （140-280 V） with constant alternate current （AC） amplitude （200 V）. Attention is paid to the composition, properties and growth mechanism of oxide layers formed with hybrid voltages. Moreover, the main effects of DC value are discussed. Ceramic layers with a double-layer structure which combines hard outer and soft inner layers are found to be consist of α-Al2O3,γ-Al2O3 and mullite. With the DC values increasing, the growth of the ceramic layers tends to have increasingly obvious three-stage feature.展开更多
The oxide layer on the surface has always been a key obstacle to achieving the diffusion bonding of Al alloys.It is a challenge for performing diffusion bonding without removing oxide layers.Herein,diffusion bonding o...The oxide layer on the surface has always been a key obstacle to achieving the diffusion bonding of Al alloys.It is a challenge for performing diffusion bonding without removing oxide layers.Herein,diffusion bonding of Al alloy retaining continuous oxide layers was successfully achieved in the air by a low-temperature and low-pressure diffusion bonding mothed using a Zn interlayer.During the bonding processes,conducted at 360℃ and 3 MPa,Zn diffused into Al through cracks of thin oxide layers to form the joint composed Al/(diffusion layer)/(oxide layer)/(Zn)/(oxide layer)/(diffusion layer)/Al.The diffusion layers were composed of Zn-Al eutectoid,and the oxide layer included nanocrystals and amorphous Al_(2)O_(3).The shear strength of joints containing continuous oxide layers was about 30 MPa.Interestingly,the migration behavior toward the joint center of the interfacial oxide layers was observed with consuming of the Zn interlayer.The cracking phenomenon,the“subcutaneous diffusion”and the migration behavior of oxide layers were verified and analyzed by the diffusion bonding of anodized 6063Al-6063Al.Subsequently,the dynamic migration mechanism of oxide layers with elements diffusion and bonding interface strengths were discussed in detail.The ability to join Al alloys in the air at low temperatures and low pressure suggests a highly practical and economic method for diffusion bonding.展开更多
Revealing the oxidation behavior of superalloys is crucial for optimizing material properties and extending service life.This study investigated the oxidation behavior of superalloy GH4738 under stress states at 850℃...Revealing the oxidation behavior of superalloys is crucial for optimizing material properties and extending service life.This study investigated the oxidation behavior of superalloy GH4738 under stress states at 850℃.High-throughput specimens were fabricated to withstand different stresses at the same time.Isothermal oxidation s amples were analyzed using the mass gain method to obtain oxidation kinetic curves.The results show that the external stress below 200 MPa could improve the oxidation resistance of the GH4738.With tensile stress increasing,the oxide layer becomes thinner,denser and more complete,while internal oxidation decreases.The tensile stress alters the structure of the external oxide layer from a two-layer to a threelayer configuration.The Cr_(2)O_(3) oxide layer inhibits the outward diffusion of Ti,leading to Ti enrichment at the oxide-matrix interface and altering the oxidation mechanism of GH4738.展开更多
For steam tubes used in thermal power plant,the inner and outer walls were operated in high-temperature steam and flue gas environments respectively.In this study,structure,microstructure and chemical composition of o...For steam tubes used in thermal power plant,the inner and outer walls were operated in high-temperature steam and flue gas environments respectively.In this study,structure,microstructure and chemical composition of oxide films on inner and outer walls of exservice low Cr ferritic steel G102 tube and exservice high Cr ferritic steel T91 tube were analyzed.The oxide film was composed of outer oxide layer,inner oxide layer and internal oxidation zone.The outer oxide layer on the original surface of tube had a porous structure containing Fe oxides formed by diffusion and oxidation of Fe.More specially,the outer oxide layer formed in flue gas environment would mix with coal combustion products during the growth process.The inner oxide layer below the original surface of tube was made of Fe–Cr spinel.The internal oxidation zone was believed to be the precursor stage of inner oxide layer.The formation of internal oxidation zone was due to O diffusing along grain boundaries to form oxide.There were Fe–Cr–Si oxides discontinuously distributed along grain boundaries in the internal oxidation zone of G102,while there were Fe–Cr oxides continuously distributed along grain boundaries in that of T91.展开更多
基金supported by the National Natural Science Foundation of China(Nos.U2037601 and 51821001)Major Scientific and Technological Innovation Projects in Luoyang(No.2201029A)the Research Program of Joint Research Center of Advanced Spaceflight Technologies(Nos.USCAST2020–14 and USCAST2020–31).
文摘Surface oxide layers play a significant role in forming secondary oxidation inclusions during the casting process.In this study,three typical Mg-RE alloys(Mg-3Nd(NZ30K),Mg-3Nd-3Gd(EV33)and Mg-3Nd-4Y(WE43A))are selected.Their surface oxide layers formed during the solidification are characterized in detail,and the corresponding oxidation mechanisms are discussed.The results reveal that RE elements obviously influence the characteristics of surface oxide layers,which depends on their ability to purify the formed MgO in the melt via the reaction(2RE+3MgO=3Mg+RE_(2)O_(3)).On the one hand,as Nd and Gd do not easily displace MgO already formed in the melt,the loose oxide layers in NZ30K and EV33 alloys are mainly composed of MgO matrix with embedded RE-rich oxide particles.On the other hand,due to the strong ability of Y to purify MgO in the melt,the oxide layer of WE43A alloy becomes a denser and thinner Y_(2)O_(3) oxide layer.Note that the differences in surface oxide layers well explain the different secondary inclusions that occur in three typical Mg-RE alloys during the casting process.
基金supported by the National Research Foundation of Korea funded by the Ministry of Science and ICT of Korea(RS-2024-00408156)。
文摘Mn-based layered oxides are widely recognized as cathode materials for potassium-ion batteries(KIBs)due to their high specific capacity derived from their low molar mass.However,the structural instability caused by the Jahn-Teller effect of Mn^(3+)and the large ionic radius of K+results in poor electrochemical performance.Herein,we propose an effective structural stabilization strategy for P2-type Mn-based layered oxide cathodes of KIBs through Li-incorporation into the transition metal layer.Using the firstprinciples calculations and experiments,we demonstrate that the P2-K_(0.48)[Li_(0.1)Mn_(0.9)]O_(2)(P2-KLMO)delivers improved electrochemical performance,specific capacity and average discharge voltage of~124.4 m A h g^(-1)and~2.7 V(vs.K^(+)/K)at 0.05C(1C=260 mA g^(-1)),outperforming P2-K_(0.5)MnO_(2).Operando X-ray diffraction analysis confirms the P2-OP4 phase transition and Mn^(3+)-induced Jahn-Teller distortion are significantly suppressed in P2-KLMO.These improvements are attributed to the lithium introduction into transition metal layers,leading to strengthened structural stability and enhanced K+diffusion kinetics.Moreover,synthetic accessibility through the conventional solid-state method provides an additional advantage for practical application of Li-incorporated Mn-based P2-type cathodes in KIBs.We believe our study offers a simple yet effective strategy for designing highperformance and practical cathode materials for KIBs.
基金financially supported by the National Natural Science Foundation of China(52274295)the Natural Science Foundation of Hebei Province(E2025501032,E2025501028)+3 种基金the Fundamental Research Funds for the Central Universities(N2523045,N2423051,N2423005,N2423019)the Science and Technology Project of Hebei Education Department(QN2024238)the Central Guided Local Science and Technology Development Fund Project of Hebei Province(254Z1102G)the Basic Research Program Project of Shijiazhuang City for Universities Stationed in Hebei Province(241790937A)。
文摘The P2-type Fe/Mn-based layered oxides,with cost advantages and high theoretical capacity,are considered one of the promising cathode materials for sodium-ion batteries(SIBs).However,the commercial development of these materials is impeded by two main factors:the MnO_(6) structure distortion induced by the Jahn-Teller(J-T)effect of Mn^(3+),and the unfavorable phase transitions that occur during the insertion and extraction of Na^(+).Here,we present a strategy to improve structural stability by incorporating cost-effective,robust Al-O bonds.This approach induces localized adjustments in the electronic structu re and a pinning effect,which limits the deformation of the transition metal(TM)layers,strengthens the electrostatic bonding within the TM layers,and expands the Na layer spacing.Consequently,the Na_(0.67)Fe_(0.4)Mn_(0.54)Al_(0.06)O_(2) cathode demonstrates a capacity of 168.8 mAh g^(-1) at 0.1 C,maintaining89.2%of its original capacity after 200 cycles at 1 C.Through in situ electrochemical impedance spectroscopy(EIS)with dynamic resistance transformation(DRT)analysis,ex situ X-ray absorption spectroscopy(XAS),and in situ X-ray diffraction(XRD),the study demonstrates a reduction in the J-T effect,enhanced kinetic performance,and the inhibition of detrimental phase transitions.This study offers new avenues to the development and design of future low-cost Fe/Mn-based cathodes.
基金supported by the National Key R&D Program of China(2023YFB2406000)the National Natural Science Foundation of China(22479057,52172201,51732005)。
文摘Sodium layered oxides stand out as one of the most promising cathodes for sodium-ion batteries due to their high energy density,elemental abundance,and scalability.However,their practical applications are restricted by interplanar gliding,cation migration,and the formation of intragranular microcracks,which collectively lead to rapid structural degradation and capacity loss.Herein,we rationally design an ultrastable O3-type Na_(0.94)Ca_(0.03)Ni_(1/3)Fe_(1/3)Mn_(1/3)O_(2) cathode,in which Ca^(2+)cations act as pillars within the NaO_(2)slabs,suppressing the irreversible phase transitions and Na/TM cation migration commonly observed in layered oxides.Multiscale in situ and ex situ techniques,combined with post-mortem analysis,reveal that the Ca-pillared pinning effect not only effectively suppresses the interplanar gliding and stress accumulation within the crystal phase but also restrains Na/TM cation migration and surface reconstruction in near-surface regions.Benefiting from the combined effects of structural stabilization,the Ca-pillared cathode exhibits a superior cycling stability,retaining 81.6%of its capacity after 1000 cycles at 2 C within the voltage range of 2.0-4.0 V,along with significantly enhanced wide-temperature(from-40 to 80℃)performance.This work highlights another critical role of Ca pillars in suppressing cation migration and surface structural degradation beyond preventing adverse interplanar gliding,offering valuable insights for designing long-life and wide-temperature layered oxide cathodes.
基金supported by the National Natural Science Foundation of China(Grant Nos.52202282,52402054,22471283,and 52202327)Natural Science Foundation of Tianjin City(Grant Nos.22JCYBJC00040,24JCQNJC00970)。
文摘High-capacity O3-type layered NiFeMn-based oxides are promising cathodes for sodium-ion batteries,though their practical deployment is constrained by the inherent limitations of Fe redox chemistry.Traditional designs generally enforcing stoichiometric symmetry(Ni=Mn)yield low Fe redox activity.Herein,we propose a valence engineering strategy that breaks conventional Ni/Mn stoichiometry to reconfigure Fe's local chemical environment and unlock unprecedented redox depth.Density functional theory(DFT)calculations reveal that the designed NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode exhibits a reduced Bader charge on Fe(1.598 vs.1.638 in NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2))and elevated Fe 3d orbital energy,signifying enhanced Fe redox activity.This configuration enables an exceptional Fe^(2.60+)/Fe^(3.88+)redox(1.28 e~-per Fe),delivering a reversible capacity of184.3 mAh g^(-1)within 2-4.2 V at 0.2 C,markedly exceeding the benchmark NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(161.3 mAh g^(-1))with low reaction depth of Fe^(3.01+)/Fe^(3.61+).The intensified cationic redox reaction enables an ultrahigh energy density of 596 Whkg-1.The NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode demonstrates robust performance over a broad temperature range from-15℃to 60℃.In situ and ex situ characterizations unveil a reversible O3■P3■OP2 phase transition with minimal volume change(1.88%)that circumvents detrimental deleterious O'3 intermediates and intragranular cracking.This work establishes valence engineering as a paradigm to consolidate cationic redox reaction in high-energy layered sodium oxide cathodes.
基金supported by the “Pioneer” and “Leading Goose” R&D Program of Zhejiang Province of China (No. 2024C01056)the support from London South Bank University
文摘Layered oxides have attracted significant attention as cathodes for sodium-ion batteries(SIBs)due to their compositional versatility and tuneable electrochemical performance.However,these materials still face challenges such as structural phase transitions,Na^(+)/vacancy ordering,and Jahn–Teller distortion effect,resulting in severe capacity decay and sluggish ion kinetics.We develop a novel Cu/Y dual-doping strategy that leads to the formation of"Na–Y"interlayer aggregates,which act as structural pillars within alkali metal layers,enhancing structural stability and disrupting the ordered arrangement of Na^(+)/vacancies.This disruption leads to a unique coexistence of ordered and disordered Na^(+)/vacancy states with near-zero strain,which significantly improves Na^(+)diffusion kinetics.This structural innovation not only mitigates the unfavorable P2–O2 phase transition but also facilitates rapid ion transport.As a result,the doped material demonstrates exceptional electrochemical performance,including an ultra-long cycle life of 3000 cycles at 10 C and an outstanding high-rate capability of~70 mAh g^(−1)at 50 C.The discovery of this novel interlayer pillar,along with its role in modulating Na^(+)/vacancy arrangements,provides a fresh perspective on engineering layered oxides.It opens up promising new pathways for the structural design of advanced cathode materials toward efficient,stable,and high-rate SIBs.
基金supported by grants from the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(MSIT)(RS-2024-00407116)+1 种基金by the Ministry of Education(NRF-2018R1A6A1A03024231)support from the NRF grant funded by the MSIT(RS-2024-00406724)。
文摘Interfacial engineering is crucial for developing high-performance Ni-rich layered cathodes for lithiumion batteries.Here,we introduce an interfacial precipitation(IP)strategy,guided by first-principles calculations,to create a functionally graded cathode during precursor synthesis.Based on thermodynamic principles of bulk insolubility and phase separation kinetics,we achieved the selective precipitation of Co onto the surface of a Ni-rich hydroxide precursor.Upon high-temperature lithiation,this engineered precursor spontaneously forms a unique,bifunctional Co-rich spinel-like layer on the final LiNi_(0.88)Co_(0.06)Mn_(0.06)O_(2)(NCM)cathode.This architecture suppresses detrimental Li/Ni cation mixing and protects the active material.Consequently,the IP-driven NCM cathode demonstrates vastly superior rate capability,delivering 140.8 m A h g^(-1)at 5C,compared to 112.9 mA h g^(-1)for its conventionally prepared counterpart.This enhancement is attributed to significantly lower charge-transfer resistance and faster kinetics.Remarkably,in a full-cell configuration,the IP-driven NCM cathode maintains 81.5%capacity after 1000 cycles at an aggressive 5C rate.This work presents a thermodynamically driven,scalable strategy for designing advanced cathodes with exceptional high-power performance and stability.
基金supported by the National Key R&D Program of China(2021YFB3800300).
文摘High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g^(-1) at 0.2 C,160.9 mA h g^(-1) at 2.0 C and 112.3 mA h g^(-1) at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g^(-1) after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.
基金supported by the National Natural Science Foundation of China(No.22479021).
文摘Solid-state lithium(Li)batteries are hailed as the nextgeneration energy storage technology,garnering significant attention for their potential high energy density and safety.Particularly when using Li-rich manganese layered oxide(LRMO)as cathodes(theoretical capacity exceeding250 mAh/g),energy densities over 600 Wh/kg can be theoretically achieved[1,2].
基金supported by the National Natural Science Foundation of China(52374311)National Key R&D Program of China(2023YFE0203000)+3 种基金the National Natural Science Foundation of Shaanxi(2023KXJ-262,2025SYS-SYSZD-035)the Fund of the State Key Laboratory of Solidification Processing in NPU(2025-TS-10)the Fundamental Research Funds for the Central Universities(D5000250277)the Youth Innovation Team of Shaanxi Universities。
文摘Layered oxides present compelling potential as cathode materials for sodium-ion batteries(SIBs).However,challenges including interfacial instability and sluggish reaction kinetics critically limit their rate capability and cycling performance.Herein,we introduce the water-soluble sodium polyacrylate(NaPAA)binder as a promising approach to mitigating these issues in P2-type layered oxides.The NaPAA binder facilitates the formation of a uniform Na^(+) conductive interfacial film,which protects the cathode against electrolyte-induced corrosion and effectively inhibits the dissolution of transition metals in P2-Na_(0.85)Li_(0.12)Ni_(0.22)Mn_(0.66)O_(2)(NLNMO).Furthermore,we elucidate the mechanism by which the NaPAA binder dynamically regulates the coordination of free anions at the electrode-electrolyte interface.This regulation reduces solvent decomposition and promotes the formation of a stable,ionically conductive layer.Consequently,the P2-NLNMO@NaPAA integrated electrode exhibits enhanced electrochemical performance,achieving an 89.2%capacity retention after 200 cycles at 0.2 C and delivering an initial capacity of 102.9 mA h g^(-1) even at 0℃.This study advances the fundamental understanding of binder-mediated interface engineering and demonstrates a scalable and eco-friendly manufacturing pathway for high-performance SIBs.
基金supported by the National Natural Science Foundation of China(No.51164023)Inner Mongolia Natural Science Foundation(No.2009BS0801)
文摘Zirconia coatings as hydrogen permeation barriers were formed on disktype ZrHj.s substrate speci mens in phosphate solution system by microarc oxidation technique. Influence of positive voltage on hydrogen per meation barriers on the surface of zirconium hydride was investigated as the main factor. The thickness of total oxide layer increased from 42.5 to 55.0 ~tm the increase of positive voltage increasing from 325 up to 425 V. The permeation reduction factor （PRF） was observed under different voltages, which increased with the increasing positive voltages. The phase structure of oxide layer was monoclinic Zr02 and tetragonal ZrO1.88. No reduction reaction occured in the process of hydrogen escaping, and it indicates that hydrogen permeation through oxide layer is restricted.
基金financially supported by the National Key Research and Development Program of China(No.2012AA03A501)。
文摘Inconel 600 alloy is widely utilized for high temperature environment application due to the corresponding good oxidation and corrosion resistance properties.In order to estimate the high temperature oxidation resistance of Inconel 600 alloy at various temperatures,the oxidation weight gain of all specimens was measured and fitted for the curve at the temperatures of 700,800 and 900 ℃ for exposure time of 100 h.The surface morphology and the component of the oxide film were analyzed by scanning electron microscopy(SEM),energy-dispersive spectroscopy(EDS) and X-ray diffraction(XRD).The results indicate that the high temperature oxidation resistance of Inconel 600 alloy is excellent blew 800℃ due to the oxidation kinetic curves at different temperatures corresponding to the parabola dynamic rules.This means that the oxidation film protects the substrate well.The dense oxide layer formation containing Cr_(2)O_(3) and NiCr_(2)O_(4) at 700 and 800 ℃ and MnCr_(2)O_(4) at 900 ℃,respectively,is the main reason for the good oxidation resistance.In contrast,the oxide layer peels off easily under applied force as the temperature increases beyond 800℃, on account of the complicated compositions of the oxide film and the binding force between the oxide layer and the substrate weakening.Corresponding oxidation mechanism is expected to be understood and the oxidation resistance of Inconel 600 alloy is improved through binding force enhancement.
基金supported by the National Science Foundation of China (Nos.50671008,50871014,and 50831002)
文摘Ta/NiFe/Ta ultrathin films with and without nano-oxide layers （NOLs） were prepared by magnetron sputtering followed by a vacuum annealing process. The influence of NOLs on the magnetoresistance （MR） ratio of ultrathin permalloy films was studied. The results show that the influence of grain size and textures on the MR ratio becomes weak when the thickness of the NiFe layer is below 15 nm. A higher MR ratio was observed for the thinner （〈 15 nm） NiFe film with NOLs. The MR ratio of a 10 nm NiFe film can be remarkably enhanced by NOLs. The enhanced MR ratio for these ultrathin films can be attributed to the enhanced specular reflection of conduction electrons.
文摘Chemically resistant anodic oxide layers were formed on pure aluminum substrates in oxalic acid-sulphuric acid bath.Acid dissolution tests of the obtained anodic layers were achieved in accordance with the ASTM B 680-80 specifications：35mL/L 85% H3PO4＋20g/L CrO3 at 38℃.Influence of oxalic acid concentration,bath temperature and anodic current density on dissolution rate and coating ratio was examined,when the sulphuric acid concentration was maintained at 160g/L.It was found that chemically resistant and compact oxide layers were produced under low operational temperature （5℃） and high current densities （3A/dm^2）.A beneficial effect was observed concerning the addition of oxalic acid （18g/L）.The morphology and the composition of the anodic oxide layer were examined by scanning electron microscopy （SEM）,atomic force microscopy （AFM） and glow-discharge optical emission spectroscopy （GDOES）.
基金Project(51134003)supported by the National Natural Science Foundation of China
文摘The oxidation behavior and mechanism of a porous Ni?Cr?Al?Fe alloy in the temperature range from850to1000°Cwere investigated by optical microscopy,scanning electron microscopy(SEM)and energy dispersive spectroscopy(EDS),X-raydiffraction(XRD)analyses and X-ray photoelectron spectroscopy(XPS).The results show that the oxidation kinetics at950and1000°C of this porous alloy is pseudo-parabolic type.Complex layers composed of external Cr2O3/NiCr2O4and internalα-Al2O3areformed on the surface of the oxidized porous alloys.γ?phases favor the formation of NiO/Cr2O3/NiCr2O4during the initial oxidation.Many fast diffusion paths contribute to the development of the oxide layers.The decrease of the open porosity and the permeabilitywith exposure time extending and temperature increasing can be controlled within a certain range.
基金The authors are grateful to the National Key R&D Program of China(Grant No.2017YFB0702901)the National Natural Science Foundation of China(Grant Nos.51474156 and U1660201)for grant and financial support.
文摘The oxidation behavior of a newly designed Co-Ni-based alloy with varied addition of Ti(1.4 and 2.1 wt.%,hereafterreferred as 1.4Ti and 2.1Ti alloys)was explored in air at 900℃.It is found that an outer oxide layer composed of CoO,anintermediate oxide layer composed of intermittent TiO,plus continuous Cr,W-rich oxides,and an inner oxidized regioncomposed of Al2O3 were formed on the surface of 1.4Ti alloy,whereas the oxide structure of 2.1Ti alloy was composed of Co0 as the outer oxide layer,continuous TiO2,Cr2O3 and WO3 as intermediate oxide layer,and Al2O3 as the inner oxidizedregion.With increasing Ti content.continuous TiO2 films formed in the intermediate oxide layer,which would lead to theformation of compact Cr2O3 and improved oxidation resistancc after 100 h oxidation at 900℃.These observations indicatedthat Ti addition can improve the high-temperature oxidation resistance of Co-Ni-based aloys.
基金Changwon National University in 2008 and National IT Industry Program Agency(NIPA-2009-C-C1090-0903-0007)
文摘Plasma electrolytic oxidation （PEO） is carried out on 6061 Al-alloys in a weak alkaline electrolyte containing NaOH, Na2SiO3 and NaCl. Centered on the correlation of composition and structure, analyses by means of X-ray diffration （XRD）, scanning electron microscope （SEM） and energy dispersive spectrometry （EDS） are conducted on the specimens, which have been PEO-treated under hybrid voltages of different direct current （DC） values （140-280 V） with constant alternate current （AC） amplitude （200 V）. Attention is paid to the composition, properties and growth mechanism of oxide layers formed with hybrid voltages. Moreover, the main effects of DC value are discussed. Ceramic layers with a double-layer structure which combines hard outer and soft inner layers are found to be consist of α-Al2O3,γ-Al2O3 and mullite. With the DC values increasing, the growth of the ceramic layers tends to have increasingly obvious three-stage feature.
基金supported by the National Natural Science Foundation of China under Grant No.51975152.
文摘The oxide layer on the surface has always been a key obstacle to achieving the diffusion bonding of Al alloys.It is a challenge for performing diffusion bonding without removing oxide layers.Herein,diffusion bonding of Al alloy retaining continuous oxide layers was successfully achieved in the air by a low-temperature and low-pressure diffusion bonding mothed using a Zn interlayer.During the bonding processes,conducted at 360℃ and 3 MPa,Zn diffused into Al through cracks of thin oxide layers to form the joint composed Al/(diffusion layer)/(oxide layer)/(Zn)/(oxide layer)/(diffusion layer)/Al.The diffusion layers were composed of Zn-Al eutectoid,and the oxide layer included nanocrystals and amorphous Al_(2)O_(3).The shear strength of joints containing continuous oxide layers was about 30 MPa.Interestingly,the migration behavior toward the joint center of the interfacial oxide layers was observed with consuming of the Zn interlayer.The cracking phenomenon,the“subcutaneous diffusion”and the migration behavior of oxide layers were verified and analyzed by the diffusion bonding of anodized 6063Al-6063Al.Subsequently,the dynamic migration mechanism of oxide layers with elements diffusion and bonding interface strengths were discussed in detail.The ability to join Al alloys in the air at low temperatures and low pressure suggests a highly practical and economic method for diffusion bonding.
基金financially supported by the National Key R&D Program of China(No.2021YFB3700401)Shandong Provincial Natural Science Foundation for Youths(No.ZR2022QE234)+1 种基金Zhejiang Provincial Natural Science Foundation(No.LQ21E030002)the Youth Innovation team Project of Higher Education Institutions in Shandong Province(No.2022KJ272)。
文摘Revealing the oxidation behavior of superalloys is crucial for optimizing material properties and extending service life.This study investigated the oxidation behavior of superalloy GH4738 under stress states at 850℃.High-throughput specimens were fabricated to withstand different stresses at the same time.Isothermal oxidation s amples were analyzed using the mass gain method to obtain oxidation kinetic curves.The results show that the external stress below 200 MPa could improve the oxidation resistance of the GH4738.With tensile stress increasing,the oxide layer becomes thinner,denser and more complete,while internal oxidation decreases.The tensile stress alters the structure of the external oxide layer from a two-layer to a threelayer configuration.The Cr_(2)O_(3) oxide layer inhibits the outward diffusion of Ti,leading to Ti enrichment at the oxide-matrix interface and altering the oxidation mechanism of GH4738.
基金supported by the National Natural Science Foundation of China (Nos.51901113 and 51775300)the State Key Laboratory of Tribology in Tsinghua University, and the State Key Lab of Advanced Welding and Joining in Harbin Institute of Technology (No.AWJ-21M03)。
文摘For steam tubes used in thermal power plant,the inner and outer walls were operated in high-temperature steam and flue gas environments respectively.In this study,structure,microstructure and chemical composition of oxide films on inner and outer walls of exservice low Cr ferritic steel G102 tube and exservice high Cr ferritic steel T91 tube were analyzed.The oxide film was composed of outer oxide layer,inner oxide layer and internal oxidation zone.The outer oxide layer on the original surface of tube had a porous structure containing Fe oxides formed by diffusion and oxidation of Fe.More specially,the outer oxide layer formed in flue gas environment would mix with coal combustion products during the growth process.The inner oxide layer below the original surface of tube was made of Fe–Cr spinel.The internal oxidation zone was believed to be the precursor stage of inner oxide layer.The formation of internal oxidation zone was due to O diffusing along grain boundaries to form oxide.There were Fe–Cr–Si oxides discontinuously distributed along grain boundaries in the internal oxidation zone of G102,while there were Fe–Cr oxides continuously distributed along grain boundaries in that of T91.
