Atomically Substitutional Engineering of Transition Metal Dichalcogenide Layers for Enhancing Tailored Properties and Superior Applications

Transition metal dichalcogenides(TMDs)are a promising class of layered materials in the post-graphene era,with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior.Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties,providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs.The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable(opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts(0–100%).Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase,band alignment/structure,carrier density,and surface reactive activity,enabling novel and promising applications.This review comprehensively elaborates on atomically substitutional engineering in TMD layers,including theoretical foundations,synthetic strategies,tailored properties,and superior applications.The emerging type of ternary TMDs,Janus TMDs,is presented specifically to highlight their typical compounds,fabrication methods,and potential applications.Finally,opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.

Ductilization of Ni_3Al by Alloying with Substitutional Elements

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

Structural model of substitutional sulfur in diamond

Based on ab initio calculations,it is found that the donor center of substitutional sulfur(S)in diamond with C2v symmetry is more stable than that with C3vsymmetry,which is different from previous reports in literature.The energy difference of C2vand C3vstructures is qualitatively affected by the supercell size,and the 216-atom supercell could be proposed as the minimum to obtain stable configuration of substitutional S in diamond.Using supercells of up to 512 atoms,the donor level of substitutional S with C2vsymmetry is deep.

Antiferromagnetic-ferromagnetic transition in zigzag graphene nanoribbons induced by substitutional doping

Using first-principles calculations based on density functional theory,we show that the ground state of zigzag-edged graphene nanoribbons(ZGNRs)can be transformed from antiferromagnetic(AFM)order to ferromagnetic(FM)order by changing the substitutional sites of N or B dopants.This AFM–FM transition induced by substitutional sites is found to be a consequence of the competition between the edge and bulk states.The energy sequence of the edge and bulk states near the Fermi level is reversed in the AFM and FM configurations.When the dopant is substituted near the edge of the ribbon,the extra charge from the dopant is energetically favorable to occupy the edge states in AFM configuration.When the dopant is substituted near the center,the extra charge is energetically favorable to occupy the bulk states in FM configuration.Proper substrate with weak interaction is necessary to maintain the magnetic properties of the doped ZGNRs.Our study can serve as a guide to synthesize graphene nanostructures with stable FM order for future applications to spintronic devices.

Grain-boundary segregation and grain growth in nanocrystalline substitutional solid solution alloys

A model for describing solute segregation at grain boundaries has been developed for substitutional solid solution alloys,which integrates multiple factors from atomic to microstructural scales.A concept of mo-lar Gibbs free energy of segregation was introduced to evaluate the segregating capability of the solute elements in a closed system,through which the influences of grain boundary structure,grain size,ma-terial composition,and external conditions were described.Based on the evaluation of various energy forms related to solute segregation and grain growth processes,the nature of the thermal stabilization of nanograin structures by solute segregation was disclosed.A criterion for the destabilization of nanostruc-tures,which is determined by the competition of the change rates between the molar Gibbs free energy of segregation and the total energy of grain boundaries with grain size,has been proposed.This study provided guideline to achieve high-temperature stability of nanograin structures of solid solution alloys even for the weakly segregating nanocrystalline systems.

Controllable substitutional vanadium doping in wafer-scale molybdenum disulfide films

Substitutional atomic doping of transition metal dichalcogenides(TMDs)in the chemical vapor deposition(CVD)process is a promising and effective strategy for modifying their physicochemical properties.However,the conventional CVD method only allows narrow-range modulation of the dopant concentration owing to the low reactivity of the precursors.Moreover,the growth of wafer-scale monolayer TMD films with high dopant concentrations is much more challenging.Herein,we report a facile doping approach based on liquid precursor-mediated CVD process for achieving high vanadium(V)doping in the MoS_(2)lattice with excellent doping uniformity and stability.The lateral growth of the host MoS_(2)lattice and the reactivity of the V precursor were simultaneously improved by introducing an alkali metal halide as a reaction promoter.The metal halide promoter enabled the wafer-scale synthesis of V-incorporated MoS_(2)monolayer film with excessively high doping concentrations.The excellent wafer-scale uniformity of the highly V-doped MoS_(2)film was confirmed through a series of microscopic,spectroscopic,and electrical analyses.

Synthesis of substitutional hexaboride of lanthanum and cerium La_(1-x)Ce_(x)B_(6) via aluminothermic reduction

Rare-earth hexaborides(REB_(6))are vital raw materials for cathode materials and high temperature structural ceramics that are widely applied as high-frequency electron tubes and ceramics adaptive for extreme environment,respectively.In this work,single phase substitutional solid solution REB_(6)(LaB_(6),La_(0.75)Ce_(0.25)B_(6).La_(0.5)Ce_(0.5)B_(6),La_(0.25)Ce_(0.75)B_(6) and CeB_(6))powders were prepared with the raw materials of La_(2)O_(3),CeO_(2),B_(4)C and Al powders,after calcining at 1773 K for 4 h and the following alkaline leaching.All substitutional solid solution products have homogeneous distributions of La and Ce in particles.Through microscopic morphology analysis,it is discovered that the formation of solid solution is beneficial for reducing the particle size of product,relative to LaB_(6) and CeB_(6).Moreover,Al flux plays an important role in decarbonizing reaction,and C contents of all products are below 0.4 wt%.

Manure substitution improves maize yield by promoting soil fertility and mediating the microbial community in lime concretion black soil

Synthetic nitrogen(N)fertilizer has made a great contribution to the improvement of soil fertility and productivity,but excessive application of synthetic N fertilizer may cause agroecosystem risks,such as soil acidification,groundwater contamination and biodiversity reduction.Meanwhile,organic substitution has received increasing attention for its ecologically and environmentally friendly and productivity benefits.However,the linkages between manure substitution,crop yield and the underlying microbial mechanisms remain uncertain.To bridge this gap,a three-year field experiment was conducted with five fertilization regimes:i)Control,non-fertilization;CF,conventional synthetic fertilizer application;CF_(1/2)M_(1/2),1/2 N input via synthetic fertilizer and 1/2 N input via manure;CF_(1/4)M_(3/4),1/4 N input synthetic fertilizer and 3/4 N input via manure;M,manure application.All fertilization treatments were designed to have equal N input.Our results showed that all manure substituted treatments achieved high soil fertility indexes(SFI)and productivities by increasing the soil organic carbon(SOC),total N(TN)and available phosphorus(AP)concentrations,and by altering the bacterial community diversity and composition compared with CF.SOC,AP,and the soil C:N ratio were mainly responsible for microbial community variations.The co-occurrence network revealed that SOC and AP had strong positive associations with Rhodospirillales and Burkholderiales,while TN and C:N ratio had positive and negative associations with Micromonosporaceae,respectively.These specific taxa are implicated in soil macroelement turnover.Random Forest analysis predicted that both biotic(bacterial composition and Micromonosporaceae)and abiotic(AP,SOC,SFI,and TN)factors had significant effects on crop yield.The present work strengthens our understanding of the effects of manure substitution on crop yield and provides theoretical support for optimizing fertilization strategies.

Off-farm employment,agriculture production activities,and household dietary diversity in environmentally and economically vulnerable areas of Asia

Access to off-farm employment has been expected to be a critical approach to ending hunger and all forms of malnutrition,two important targets of achieving Zero Hunger.This study aims to investigate the role of off-farm employment in improving dietary diversity through substitution effect and complementary effect with agricultural production activities and income effect.This study adopts Poisson/Tobit/Probit/OLS regressions and the instrument variable method based on the primary survey data collected among 1,282 households at 12 sites in environmentally and economically vulnerable areas of China,Nepal,Cambodia,Thailand,and Myanmar in 2019.The results show that off-farm employment is positively associated with household dietary diversity and the consumption of flesh meat,fish and other aquatic animals,fruits,and milk and dairy products,which are rich in protein and micronutrients.The results of mechanism analysis show that off-farm employment contributes to household dietary diversity by improving crop diversity,especially for poor households,boosting the probability of livestock raising for households with the middle one-third disposal income,and increasing household income.The positive association between off-farm employment and household dietary diversity is much higher for households with the bottom one-third disposal income,low illiteracy,and from upper-middle income countries.These findings imply that off-farm employment does play a vital role in achieving multiple benefits of poverty alleviation,malnutrition reduction,and agrobiodiversity conservation in environmentally and economically vulnerable areas.However,it may enlarge the gaps in dietary diversity between households with low human capital and from low and lower-middle income countries and those with high human capital and from middle-high countries.

Synthesis and Modulation of Low-Dimensional Transition Metal Chalcogenide Materials via Atomic Substitution

In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterparts.The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications.In this context,the atomic substitution method has emerged as a favorable approach.It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely,crystal structures,and inherent properties of the resulting materials.In this review,we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional,one-dimensional and two-dimensional TMC materials.The effects of substituting elements,substitution ratios,and substitution positions on the structures and morphologies of resulting material are discussed.The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided,emphasizing the role of atomic substitution in achieving these advancements.Finally,challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.

Atom substitution of the solid-state electrolyte Li_(10)GeP_(2)S_(12)for stabilized all-solid-state lithium metal batteries

Solid-state electrolyte Li_(10)GeP_(2)S_(12)(LGPS)has a high lithium ion conductivity of 12 mS cm^(-1)at room temperature,but its inferior chemical stability against lithium metal anode impedes its practical application.Among all solutions,Ge atom substitution of the solid-state electrolyte LGPS stands out as the most promising solution to this interface problem.A systematic screening framework for Ge atom substitution including ionic conductivity,thermodynamic stability,electronic and mechanical properties is utilized to solve it.For fast screening,an enhanced model Dop Net FC using chemical formulas for the dataset is adopted to predict ionic conductivity.Finally,Li_(10)SrP_(2)S_(12)(LSrPS)is screened out,which has high lithium ion conductivity(12.58 mS cm^(-1)).In addition,an enhanced migration of lithium ion across the LSr PS/Li interface is found.Meanwhile,compared to the LGPS/Li interface,LSrPS/Li interface exhibits a larger Schottky barrier(0.134 eV),smaller electron transfer region(3.103?),and enhanced ability to block additional electrons,all of which contribute to the stabilized interface.The applied theoretical atom substitution screening framework with the aid of machine learning can be extended to rapid determination of modified specific material schemes.

Bio-Based Waterborne Poly(Vanillin-Butyl Acrylate)/MXene Coatings for Leather with Desired Warmth Retention and Antibacterial Properties

This study presents a solvent-free,facile synthesis of a bio-based green antibacterial agent and aromatic monomer methacrylated vanillin(MV)using vanillin.The resulting MV not only imparted antibacterial properties to coatings layered on leather,but could also be employed as a green alternative to petroleum-based carcinogen styrene(St).Herein,MV was copolymerized with butyl acrylate(BA)to obtain waterborne bio-based P(MV-BA)miniemulsion via miniemulsion polymerization.Subsequently,MXene nanosheets with excellent photothermal conversion performance and antibacterial properties,were introduced into the P(MV-BA)miniemulsion by ultrasonic dispersion.During the gradual solidification of P(MV-BA)/MXene nanocomposite miniemulsion on the leather surface,MXene gradually migrated to the surface of leather coatings due to the cavitation effect of ultrasonication and amphiphilicity of MXene,which prompted its full exposure to light and bacteria,exerting the maximum photothermal conversion efficiency and significant antibacterial efficacy.In particular,when the dosage of MXene nanosheets was 1.4 wt%,the surface temperature of P(MV-BA)/MXene nanocomposite miniemulsioncoated leather(PML)increased by about 15℃ in an outdoor environment during winter,and the antibacterial rate against Escherichia coli and Staphylococcus aureus was nearly 100%under the simulated sunlight treatment for 30 min.Moreover,the introduction of MXene nanosheets increased the air permeability,water vapor permeability,and thermal stability of these coatings.This study provides a new insight into the preparation of novel,green,and waterborne bio-based nanocomposite coatings for leather,with desired warmth retention and antibacterial properties.It can not only realize zerocarbon heating based on sunlight in winter,reducing the use of fossil fuels and greenhouse gas emissions,but also improve ability to fight off invasion by harmful bacteria,viruses,and other microorganisms.

Boron-doped high-entropy oxide toward high-rate and long-cycle layered cathodes for wide-temperature sodium-ion batteries

03-type layered metal oxides hold great promise for sodium-ion batteries cathodes owing to their energy density advantage.However,the severe irreversible phase transition and sluggish Na^(+)diffusion kinetics pose significant challenges to achieve high-performance layered cathodes.Herein,a boron-doped03-type high entropy oxide Na(Fe_(0.2)Co_(0.15)Cu_(0.05)Ni_(0.2)Mn_(0.2)Ti_(0.2))B_(0.02)O_(2)(NFCCNMT-B_(0.02))is designed and the covalent B-O bonds with high entropy configuration ensure a robust layered structure.The obtained cathode NFCCNMT-B_(0.02)exhibits impressive cycling performance(capacity retention of 95%and 82%after100 cycles and 300 cycles at 1 and 10 C,respectively)and outstanding rate capability(capacity of 83 mAh g^(-1)at 10 C).Furthermore,the NFCCNMT-B_(0.02)demonstrates a superior wide-temperature performance,maintaining the same capacity level(113,4 mAh g^(-1)@-20℃,121 mAh g^(-1)@25℃,and 119 mAh g^(-1)@60℃)and superior cycle stability(90%capacity retention after 100 cycles at 1 C at-20℃).The high-entropy configuration design with boron doping strategy contributes to the excellent sodium-ion storage performance.The high-entropy configuration design effectively suppresses irreversible phase transitions accompanied by small volume changes(ΔV=0.65 A3).B ions doping expands the Na layer distance and enlarges the P3 phase region,thereby enhancing Na^(+)diffusion kinetics.This work offers valuable insights into design of high-performance layered cathodes for sodium-ion batteries operating across a wide temperature.

Substitutional doping in 2D transition metal dichalcogenides

Two-dimensional(2D)van der Waals transition metal dichalcogenides(TMDs)are a new class of electronic materials offering tremendous opportunities for advanced technologies and fundamental studies.Similar to conventional semiconductors,substitutional doping is key to tailoring their electronic properties and enabling their device applications.Here,we review recent progress in doping methods and understanding of doping effects in group 6 TMDs(MX2,M=Mo,W;X=S,Se,Te),which are the most widely studied model 2D semiconductor system.Experimental and theoretical studies have shown that a number of different elements can substitute either M or X atoms in these materials and act as n-or p-type dopants.This review will survey the impact of substitutional doping on the electrical and optical properties of these materials,discuss open questions,and provide an outlook for further studies.

Train post‑derailment behaviours and containment methods:a review

Railway accidents,particularly serious derailments,can lead to catastrophic consequences.Therefore,it is essential to prevent derailment escalation to reduce the likelihood of severe derailments.Train post-derailment behaviours and containment methods play a critical role in preventing derailment escalation and providing passive safety protection and accident prevention in the event of a derailment.However,despite the increasing attention on this field from academia and industry in recent years,there is a lack of systematic exploration and summarization of emerging applications and containment methods in train post-derailment research.For this reason,this paper presents a comprehensive review of existing studies on train post-derailment behaviours,encompassing various topics such as post-derailment contact-impact models,dynamic modelling and simulation techniques,and the primary factors influencing post-derailment behaviours.Significantly,this review introduces and elucidates substitute guidance mechanisms(SGMs),which serve as railway-specific passive safety protection and accident prevention measures.The various types of SGMs are depicted,and their ongoing developments and applications are explored in depth.The review additionally points out several unresolved challenges including the adverse effects of SGMs,and proposes future research directions to advance the theoretical understanding and practical application of train post-derailment behaviours and containment methods.This review seeks to be a valuable reference for railway industry professionals in preventing catastrophic derailment consequences through post-derailment containment methods.

In-situ neutron-transmutation for substitutional doping in 2D layered indium selenide based phototransistor

Neutron-transmutation doping(NTD)has been demonstrated for the first time in this work for substitutional introduction of tin(Sn)shallow donors into two-dimensional(2D)layered indium selenide(InSe)to manipulate electron transfer and charge carrier dynamics.Multidisciplinary study including density functional theory,transient optical absorption,and FET devices have been carried out to reveal that the field effect electron mobility of the fabricated phototransistor is increased 100-fold due to the smaller electron effective mass and longer electron life time in the Sn-doped InSe.The responsivity of the Sn-doped InSe based phototransistor is accordingly enhanced by about 50 times,being as high as 397 A/W.The results show that NTD is a highly effective and controllable doping method,possessing good compatibility with the semiconductor manufacturing process,even after device fabrication,and can be carried out without introducing any contamination,which is radically different from traditional doping methods.

Spray pyrolysis feasibility of tungsten substitution for cobalt in nickel-rich cathode materials

Cobalt(Co)serves as a stabilizer in the lattice structure of high-capacity nickel(Ni)-rich cathode materials.However,its high cost and toxicity still limit its development.In general,it is possible to perform transition metal substitution to reduce the Co content.However,the traditional coprecipitation method cannot satisfy the requirements of multielement coprecipitation and uniform distribution of elements due to the differences between element concentration and deposition rate.In this work,spray pyrolysis was used to prepare LiNi_(0.9)Co_(0.1-x)W_(x)O_(2)(LNCW).In this regard,the pyrolysis behavior of ammonium metatungstate was analyzed,together with the substitu-tion of W for Co.With the possibility of spray pyrolysis,the Ni-Co-W-containing oxide precursor presents a homogeneous distribution of metal elements,which is beneficial for the uniform substitution of W in the final materials.It was observed that with W substitution,the size of primary particles decreased from 338.06 to 71.76 nm,and cation disordering was as low as 3.34%.As a consequence,the pre-pared LNCW exhibited significantly improved electrochemical performance.Under optimal conditions,the lithium-ion battery assembled with LiNi_(0.9)Co_(0.0925)W_(0.0075)O_(2)(LNCW-0.75mol%)had an improved capacity retention of 82.7%after 200 cycles,which provides insight in-to the development of Ni-rich low-Co materials.This work presents that W can compensate for the loss caused by Co deficiency to a cer-tain extent.

Trace element compositions of pyrite and stibnite:implications for the genesis of antimony mineralization in the Yangla Cu skarn deposit,Northwestern Yunnan,China

The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are strictly controlled by the stratum,structure,and lithology,which are lenticular and vein-like within the marble fracture zone,which can provide a window into multistage miner-alization and ore genesis at Yangla.Mineralization can be divided into three types,Cu–Pb–Zn(skarn)pyrite,galena,and sphalerite,Cu(porphyry)chalcopyrite and pyrite,and Sb(hydrothermal)stibnite and pyrite.The mineral assem-blages were stibnite+pyrite+calcite+quartz±minor scheelite in antimony ores.This study presents quantitative measurements of the trace element compositions of pyrite and stibnite from the Yangla antimony ores.Analysis of pyrite with electron probe microanalysis(EPMA)showed enrichment in Co,Ni,Sb,As,and Mo,and deficit in its S and Fe contents when compared to the stoichiometric con-centrations of S and Fe in pyrite.The Sb-related pyrite may belong to sedimentary-reworked genesis and may be modi-fied by hydrothermalfluids,thereby presenting a certain dif-ference(i.e.,crystal morphology,texture,and chemical com-position)compared to the skarn and porphyry Cu-related pyrite in the Yangla Cu skarn deposit.Analysis of stibnite with EPMA and inductively coupled plasma-mass spectrom-etry showed enrichment in As,Pb,Sn,Pb,Cu,and Zn,and presented much higher Sb contents and slightly lower S con-tents when compared to the stoichiometric concentrations of Sb and S in stibnite.Statistical analysis of the stibnite trace elements showed correlations for the elemental pairs Cu–Pb,As–Sb,and Sn–Pb,and the coupled substitution equations Sb^(3+)↔Cu^(+)+Pb^(2+),Sb^(3+)↔As^(3+),and Sn^(2+)↔Pb^(2+)may be the major factors governed the incorporating Cu,Pb,As and Sn within the stibnite.Moreover,this study preliminary shows that the antimony mineralization may belong to a car-bonate replacement hydrothermal genesis at Yangla.

Enhancing wood efficiency through comprehensive wood flow analysis:Methodology and strategic insights

Wood,an essential natural resource in human civilization,remains widely used despite advances in technology and material substitution.The surge in greenhouse gas emissions and environmental concerns accentuates the need for optimizing wood utilization.Material flow analysis is a powerful tool for tracking material flows and stocks,aiding resource management and environmental decision-making.However,the full extent of its methodological dimensions,particularly within the context of the wood supply chain,remains relatively unexplored.In this study,we delve into the existing literature on wood flow analysis,discussing its primary objectives,materials involved,temporal and spatial scales,data sources,units,and conversion factors.Additionally,data uncertainty,data reconciliation and crucial assumptions in material flow analysis are highlighted in this paper.Key findings reveal the significance of wood cascading and substitution effects by replacing non-wood materials,where they can reduce greenhouse gas emissions more than the natural carbon sink of forests and wood products.The immediate impact of short-term wood cascading might not be as robust as the substitution effect,with energy substitution showcasing better results than material substitution.However,it's crucial to note that these conclusions could experience significant reversal from a long-term and global perspective.Strategies for improving wood efficiency involve maximizing material use,advancing construction technologies,extending product lifespans,promoting cascade use,and optimizing energy recovery processes.The study underscores the need for standardized approaches in wood flow analysis and emphasizes the potential of wood efficiency strategies in addressing environmental challenges.

Impact of Co^(2+)substitution on structure and magnetic properties of M-type strontium ferrite with different Fe/Sr ratios

Ion substitution has significantly improved the performance of ferrite magnets,and cobalt remains a key area of research.Studies on the mechanism of Co^(2+)in strontium ferrite,especially SrFe_(2n-x)Co_(x)O_(19-d)(n=6.1-5.4;x=0.05-0.20)synthesized using the ceramic method,showed that Co^(2+)preferentially enters the lattice as the Fe/Sr ratio decreases.This results in a decrease in the lattice constants a and c due to oxygen vacancies and iron ion deficiency.The impact of Co substitution on morphology is minor compared to the effect of the Fe/Sr ratio.As the Fe/Sr ratio decreases and the Co content increases,the saturation magnetization decreases.The magnetic anisotropy field exhibits a nonlinear change,generally increasing with higher Fe/Sr ratios and Co content.These changes in the performance of permanent magnets are attributed to the absence of Fe^(3+)ions at the 12k+2a and 2b sites and the substitution of Co^(2+)at the 2b site.This suggests that by adjusting the Fe/Sr ratio and appropriate Co substitution,the magnetic anisotropy field of M-type strontium ferrite can be effectively optimized.