Moisture-Induced Non-Equilibrium Phase Segregation in Triple Cation Mixed Halide Perovskite Monitored by In Situ Characterization Techniques and Solid-State NMR

Environmental stability is a major bottleneck of perovskite solar cells.Only a handful of studies are investigating the effect of moisture on the structural degradation of the absorber.They mostly rely on ex situ experiments and on completely degraded samples,which restrict the assessment on initial and final stage.By combining in situ X-ray diffraction under controlled 85%relative humidity,and live observations of the water-induced degradation using liquid-cell transmission electron microscopy,we reveal two competitive degradation paths leading on one hand to the decomposition of state-of-theart mixed cation/anion(Cs_(0.05)(MA_(0.17)FA_(0.83))_(0.95)Pb(Br_(0.17)I_(0.83))_(3)(CsMAFA)into PbI_(2) through a dissolution/recrystallization mechanism and,on the other hand,to a non-equilibrium phase segregation leading to CsPb_(2)Br_(5) and a Cesium-poor/iodide-rich Cs_(0.05)-x(MA_(0.17)FA_(0.83))_(0.95)Pb(Br_(0.17-2y)I_(0.83)+2y)_(3) perovskite.This degradation mechanism is corroborated at atomic-scale resolution through solid-state ^(1)H and ^(133)Cs NMR analysis.Exposure to moisture leads to a film containing important heterogeneities in terms of morphology,photoluminescence intensities,and lifetimes.Our results provide new insights and consensus that complex perovskite compositions,though very performant as champion devices,are comparatively metastable,a trait that limits the chances to achieve long-term stability.

Water induced phase segregation in hydrocarbon proton exchange membranes

Proton exchange membranes （PEMs） are a key material for proton exchange membrane fuel cells （PEM-FCs）, Non-fluorinated hydrocarbon PEMs are low-cost alternatives to Nation, but limited by the low pro-ton conductivity, because of the weak phase segregation structure and narrow ion-transport channels.Various efforts have been taken to improve the performance of hydrocarbon PEMs, but mostly with com-plex methodologies. Here we demonstrate a simple, yet very efficient method to create phase segrega-tion structure inside a typical hydrocarbon PEM, sulfonated poly（ether ether ketone） （SPEEK）. By sim-ply adding appropriate amounts of water into the DMF solvent, the resulting SPEEK membrane exhibitswidened ion-transport channels, with the phase size of 2.7 nm, as indicated by both molecular dynamic（MD） simulations and transmission electron microscope （TEM） observations, and the proton conductivityis thus improved by 200%. These findings not only further our fundamental understanding of hydrocarbonPEMs, but are also valuable to the development of low-cost and practical fuel cell technologies.

Suppressed light-induced phase transition of CsPbBr_(2)I: Strategies, progress and applications in the photovoltaic field

The rapid rise in the power conversion efficiency(PCE)of CsPbBr_(2)I-based perovskite solar cells(PSCs),from 4.7%in 2016 to 11.08%in 2020,render it a promising material for use in photovoltaic devices.However,the phase stability and current hysteresis caused by photo-induced phase segregation in CsPbBr_(2)I represent major obstacles to further improvements in the PCE for such devices.In this review,we describe the basic structure and optical properties of CsPbBr_(2)I,and systematically elaborate on the mechanism of the phase transition.We then discuss the strategies in progress to suppress phase transition in CsPbBr_(2)I,and their potential application in the photovoltaic field.Finally,challenges and application prospects for CsPbBr2I PSCs are summarized in the final section of this article.

Preventing inhomogeneous elemental distribution and phase segregation in mixed Pb-Sn inorganic perovskites via incorporating PbS quantum dots

Inhomogeneous Pb/Sn elemental distribution and the resulted phase segregation in mixed Pb-Sn halide perovskites would result in energy disorder(band structure and phase distribution disorder),which greatly limits their photovoltaic performance.Here,Pb S quantum dot has been synthesized and demonstrated as seeds for modulation crystallization dynamics of the mixed Pb-Sn inorganic perovskites,allowing an enhanced film quality and significantly suppressing phase segregation.With this additive power conversion efficiency of 8%and 6%is obtained under irradiation of full sunlight in planar and mesoporous structured solar cells in combination with CsPb_(0.5) Sn_(0.5)I_(2)Br inorganic perovskite,respectively.Our finding reveals exploring the actual Pb/Sn atoms location in perovskite structure and its influence on developing efficient and stable low-bandgap perovskite solar cells.

Phase-field simulation of solidification dendritic segregation in Ti-45Al alloy

The microstructures and mechanical properties of Ti Al alloys are directly linked to micro-segregation which cannot be avoided during solidification. So a thorough understanding of the micro-segregation should be a great help to further enhance the mechanical properties of the cast products. Theoretical analysis and experiments have been used to predict the micro-segregation, but it is very difficult to observe and determine the dendritic segregation in the micro region. Phase-field method has been employed for the simulation of dendritic growth. However, due to the complicated quasi-sub regular solution model for Ti-45Al(at.%) alloy, the classic phase-field models have difficulty to deal with the free energy. In this work, a phase-field model by linking thermodynamic calculation was used to simulate solidification dendritic segregation of Ti-45 Al alloy for Liquid→Liquid+β(Ti). The free energies of solid phase and liquid phase for Ti-45 Al alloy were calculated by Thermo-Calc and then coupled with the phase-field equations. The simulation results show the dendritic morphology and Al content variations between liquid and growing solid phase for Ti-45 Al alloy. With the growth of the β(Ti), dendritic segregation is formed in the liquid and solid phases due to the solute partitioning and rejection into the liquid. As a result, the dendrite arms are depleted of Al element, while the inter-dendrites are enriched. The dendritic tip growth velocity decreases with the progress of solidification, whereas the segregation ratio increases.

PHASE INTERFACE SEGREGATION OF Mg IN A Ni-BASE SUPERALLOY IN100

The segregation of Mg to phase interfaces in a nickel base superalloy IN 100 has been investi- gated using EPT(Electron Microprobe Technique).AES(Auger Electron Spectroscopy) and EDS analyses on thin TEM film.The results show that Mg segregates to the phase inter- faces of MC/γ and γ′/γ.The segregation concentration and layer thickness of Mg on MC/γ phase interface are larger than that on γ′/γ phase interface.Mg is not only a grain boundary segregation element,but also a phase interface segregation one.

Phase Behaviors in Bi-phase Simulation of Powder Segregation in Metal Injection Molding

Powder segregation induced by mold filling is an important phenomenon that affects the final quality of metal injection molding （MIM）. The prediction of segregation in MIM requires a bi-phase flow model to describe distinctly the flows of metallic powder and polymer binder. Viscous behaviors for the flows of each phase should hence be determined. The coefficient of interaction between the flows of two phases should also be evaluated. However, only viscosity of the mixed feedstock is measurable by capillary tests. Wall sticking is supposed in the traditional model for capillary tests, while the wall slip is important to be taken into account in MIM injection. Objective of the present paper is to introduce the slip effect in bi-phase simulation, and search the suitable way to determine the viscous behaviors for each phase with the consideration of wall slip in capillary tests. Analytical and numerical methods were proposed to realize such a specific purpose. The proposed method is based on the mass conservation between the capillary flows in mono-phase model for the mixed feedstock and in bi-phase model for the flows of two phases. Examples of the bi-phase simulation in MIM were realized with the software developed by research team. The results show evident segregation, which is valuable for improving the mould designs.

A-site phase segregation in mixed cation perovskite

Mixed cation strategy greatly benefits the enhancement of device performance and chemical stability.However,adverse impact also accompanies the mixed cation system simultaneously.It brings the compositional instability,wherein the homogeneous film is likely to segregate into multi-phases during the fabrication and ageing process,thus resulting in the efficiency reduction of perovskite solar cells(PSCs)devices.This review focuses on the cation induced phase segregation,and elucidates the segregation mechanisms from the perspectives of film formation and ageing process,respectively.Furthermore,the influence of cation segregation on device performance and operational stability are discussed.And based on these understandings,viable strategies are proposed for the design of phase-stable mixed composition halide perovskites and for suppressing segregation to benefit its development towards commercial applications.

Investigation on the homogenization treatment and element segregation on the microstructure of a γ/γ′-cobalt-based superalloy

The aim of the present study was to investigate the effect of element segregation on the microstructure and γ′ phase in a γ/γ′ cobalt-based superalloy. Several samples were prepared from a cast alloy and homogenized at 1300°C for different times, with a maximum of 24 h. A microstructural study of the cast alloy using wavelength-dispersive spectroscopic analysis revealed that elements such as Al, Ti, and Ni segregated mostly within interdendritic regions, whereas W atoms were segregated within dendrite cores. With an increase in homogenization time, segregation decreased and the initial dendritic structure was eliminated. Field-emission scanning electron microscopy micrographs showed that the γ′ phases in the cores and interdendritic regions of the as-cast alloy were 392 and 124 nm, respectively. The size difference of γ′ was found to be due to the different segregation behaviors of constituent elements during solidification. After homogenization, particularly after 16 h, segregation decreased; thus, the size, chemical composition, and hardness of the precipitated γ′ phase was mostly uniform throughout the samples.

Relieving segregation in twin-roll cast Mg-8Al-2Sn-1Zn alloys via controlled rolling

Twin-roll casting(TRC)of Mg alloys with high Al content has unique advantages and broad development prospects.However,the severe segregation of high-alloyed Mg caused by TRC technology is difficult to solve at present,which restricts its practical application.In this work,the homogenization of coarse segregated phases in a twin-roll cast Mg-8Al-2Sn-1Zn(ATZ821)alloy was successfully achieved by a method combining solid-solution heat treatment and controlled rolling,which is suitable for industrial-scale production.In addition,the evolution of the microstructure was studied in detail.It was found that phases dynamically precipitated and dissolved repeatedly during the hot rolling process,and the evolution of entire second phases can be classified into three stages,i.e.,the net dissolution,balancing and net precipitation stages.During the process,the large-size chain-like eutectic phases evolved into a fine and nearly spherical(∼0.4μm)morphology that was uniformly dispersed in the Mg-matrix due to the thermodynamic coupling and the Ostwald ripening effect.Moreover,a fine grain microstructure(∼4μm)was obtained.The formidable segregation problem of twin-roll cast Mg alloys with high Al content was solved,which is an important finding for the industrial application of high-alloyed twin-roll cast sheets.©2020 Published by Elsevier B.V.on behalf of Chongqing University.

Effect of magnetic field on segregation behavior of α-Fe particles in Cu-Fe thin film prepared by magnetron sputtering

The segregation behavior of α-Fe particles in Cu-Fe film prepared by magnetron sputtering was studied by X-ray scattering and X-ray diffraction. The results show that the roughness of the film surface increases with the sputtering time increasing. The as-sputtered films are super saturation solid solution of Cu-Fe. After annealing at 500℃, α-Fe particle can be segregated from the Cu matrix. The orientations α-Fe particles in the annealed film without magnetic field are random. But the clear texture of α-Fe particles in the annealed film with magnetic field is formed, and the 〈001〉 direction of α-Fe particles tends to be parallel to the magnetic field direction.

Premature failure induced by non-equilibrium grain-boundary tantalum segregation in air-plasma sprayed ZrO_(2)-YO_(1.5)-TaO_(2.5)thermal barrier coatings

ZrO_(2)-YO_(1.5)-TaO_(2.5)(ZYTO)is a promising top-coat material for thermal barrier coatings(TBCs).The bulk properties of ZYTO have been reported by several studies,but its performances as TBCs are less-well understood.In this work,ZYTO TBCs were prepared by air plasma spraying(APS)and their thermal cycling performances were investigated at 1150℃.Despite of the good bulk properties,APS ZYTO TBCs present an extremely short thermal fatigue life.This is attributed to the non-equilibrium grain-boundary segregation of TaO_(2.5) induced by limited solubility and rapid quenching during APS process,resulting in a tetragonal(t)to cubic(c)and metastable-tetragonal(tm)phase transformation in ZYTO TBCs.The volume shrinkage(~0.74vol%)of phase transformation leads to many cracks at the c/tm phase boundaries after deposition.On the other hand,the formation of cubic phase with massive grain-boundary Ta segregation induces a large intergranular embrittlement and a weak bonding strength(~5.3 MPa),resulting in the premature failure of the ZYTO TBCs.

Thermo-Calc based multi-component micro-segregation model and solidification paths calculations

On the basis of a multi-length scale modeling, a mixture-averaged multi-component /multiphase micro-segregation model was proposed without pre-set function for the micro-scale solute profile. The model explains the effect of morphologies of solidifying phases and solid back diffusion (SBD) on segregation, and covers the two limiting solidification cases of Scheil and Lever-rule models. A commercial Thermo-Calc software package/database was linked to the algorithms via its TQ6-interface for instantaneous determination of the related thermodynamic data of the multi-component alloys. The influences of cooling rate and other parameters on the solidification path and micro-segregation behavior were numerically investigated by sample calculation of the ternary Al-Cu-Mg alloys. A parallel experimental investigation on Al-Cu-Si alloys solidified under different cooling conditions was conducted to validate the theoretical model. Reasonable agreements were gained between the predicted solidification paths and the measured results.

Integral PVA-PES Composite Membranes by Surface Segregation Method for Pervaporation Dehydration of Ethanol

一个灵巧的表面分离方法被利用 poly 制作(乙烯基白酒)-polyethersulfone (PVA 足) 合成的膜。PVA 和足首先在 dimethyl sulfoxide (DMSO ) 被溶解，然后一个玻璃盘子上的 casted 并且在凝结洗澡沉浸。在在凝结洗澡的阶段倒置进程期间， PVA 自发地分离了到聚合物答案 / 凝结洗澡接口。表面上的充实的 PVA 是由 glutaraldehyde 的进一步的 crosslinked。扫描电子显微镜学(SEM ) ， X 光检查光电子光谱学(XPS ) 和散分光计(版本) 证实了的精力有稠密的充实 PVA 的表面和多孔的充实足的支持的不可分、不对称的膜结构，以及 PVA 的表面丰富。当在膜配方的 PVA 内容是 16.7% 时，由 PVA 的膜表面的范围部分到达了多达 86.8%( 由质量) 。水接触角度随 PVA 内容的增加减少了。膜结构上的凝结洗澡类型的效果被分析。膜 pervaporation 表演被改变 PVA 内容评估，退火的温度，喂集中和操作温度。膜展出了一个相当好的乙醇脱水能力和长期的运作的稳定性。

铜基偏晶合金的研究现状

铜基偏晶合金(Cu-Co、Cu-Fe、Cu-Cr等)具有优异的电、磁、力学等特性,受到国内外材料科学领域学者的广泛关注。在制备过程中,铜基偏晶合金由于发生液相分离行为并形成严重的偏析组织现象,被称为不混溶合金。过去的研究主要集中于寻求使铜基偏晶合金组织均匀的制备方法,然而近期研究表明,偏析组织异质结构的强度-韧性协同作用有利于提高材料的韧性,这为铜基偏晶合金的进一步发展提供了新思路。本文综述了目前国内外对铜基偏晶合金的液相分离和偏析组织形成机理的理论研究成果(包括液相分离组织结构演变、液相分离热力学以及第二相液滴形核生长动力学研究),归纳了目前主流的改善偏析组织方法(包括微合金化法、快速凝固法和激光成形法),阐述了铜基偏晶合金因液相分离特性产生的双相复合微观组织结构的强度-韧性协同作用,最后对铜基偏晶合金未来的研究发展方向进行了展望。

阳极氧化后某2A12铝合金零件表面缺陷的成因

阳极氧化后某2A12铝合金零件膜层异常发亮、存在表面缺陷。采用光学显微镜、扫描电子显微镜、能谱仪、X射线衍射仪等分析技术,研究了阳极氧化后零件膜层颜色异常,显现出线条状缺陷的原因。结果表明:该铝合金基体存在富铜偏析相和夹杂相,在阳极氧化过程中,基体中的偏析相优先溶解,杂质相不被氧化,导致阳极氧化膜不均匀,膜层局部区域出现孔洞和夹杂物。

低Nb含量的CoCrFeNiNb_x合金退火后的组织演变和性能

在FCC型CoCrFeNi合金中添加少量Nb可起到固溶强化和第二相强化效果,但目前对Nb在FCC相中的溶解度及其对合金组织和性能的影响还不够了解。为此,本文基于热力学计算相图,实验研究了含1%~5%Nb(摩尔分数)的铸态CoCrFeNiNb_x合金在800~1200℃真空退火前后的显微组织和显微硬度。结果表明:即使添加1%Nb,铸态CoCrFeNiNb_x合金中仍存在约3%的FCC+C14共晶组织。后凝固的FCC相中Nb含量可高达2.4%~3.1%,在800℃退火后可析出针状纳米级Mg_(3)Cd型τ相,使合金硬度提高约30HV。经1000℃或1200℃退火后,FCC相的成分均匀,Nb含量分别为1.6%和3.1%,与热力学计算结果一致。退火后,共晶组织中的C14 Laves相球化长大,层片组织消失,合金硬度降低。因此,添加少于3.1%Nb后再进行固溶及时效处理以析出τ相是提高FCC型CoCrFeNi合金强度的有效途径。

(Ti_(35)Zr_(40)Nb_(25))_(100-x)Al_(x)(x=0,5,10,15,20)高熵合金相组成、组织和力学性能

难熔高熵合金主要由难熔金属元素组成,其熔点通常高于1800℃,且具有高热稳定性和优异抗高温软化能力,在高温领域具有巨大的应用潜力,但是高密度导致的比强度不足和室温脆性等缺点成为其应用的阻碍。本文设计并制备了系列新型非等原子比(Ti_(35)Zr_(40)Nb_(25))_(100-x)Al_(x)(x=0,5,10,15,20)轻质难熔高熵合金,研究了Al含量对相组成、组织和力学性能的影响。X射线衍射分析表明,随着Al含量的增加,合金的相结构由无序BCC转变为有序B2。五种铸态合金具有类似的组织形貌,铸锭边缘存在一个沿着冷却方向生长的细长枝晶区域,铸锭中心区域则主要为等轴枝晶。能谱分析表明Nb元素在枝晶干偏聚,Al和Zr元素则富集在枝晶间,这是由Nb的高熔点以及Al和Zr的强键合共同决定的。室温压缩实验发现Al含量的增加导致合金的屈服强度和抗压强度均逐渐提升,但没有降低室温塑性,所有合金的室温压缩断裂应变均超过50%。

温度梯度下Cu/Sn-58Bi/Cu微焊点热迁移及界面反应行为

探究了焊点平均温度为110℃(时效)及180℃(回流)时,Cu/Sn-58Bi/Cu微焊点在温度梯度作用下的原子热迁移行为及界面反应行为.结果表明,在时效过程中,因Bi相的网状结构,Cu/Sn-58Bi/Cu微焊点冷、热两端界面金属间化合物(intermetallic compound,IMC)呈现对称性生长.在温度梯度为1000℃/cm时,未发生明显的Bi原子迁移现象,但当温度梯度达到或超过1300℃/cm时,Bi原子会由热端向冷端界面迁移,并在冷端界面处偏聚.在回流过程中,温度梯度驱动Cu原子由微焊点热端向冷端界面迁移,导致两端界面IMC呈非对称性生长,而并未发现Bi原子的热迁移行为.因此,当Cu/Sn-58Bi/Cu微焊点中钎料呈液态时,温度梯度仅驱动了Cu原子的热迁移,并未致使Bi原子发生热迁移;当钎料呈固态时,在较低温度梯度下Cu和Bi原子均不发生明显的热迁移,但较高的温度梯度会引发Bi原子的热迁移.