Fabrication of ZIF-8 membranes on dual-layer ZnO-PES/PES organic hollow fibers by in-situ crystallization

Compared to inorganic supports, polymeric supports can offer additional benefits, e.g., easier processing and cheaper. However, the organic surface has weak adhesion to the zeolitic imidazolate frameworks(ZIFs) membrane layer, which usually requires complex surface modification or seeding. Herein, we demonstrate that a dual-layer asymmetric polymer support prepared by a simple spinning process is a good candidate for the preparation of ZIF-8 membrane. The inner layer of the support is an organic hollow fiber(PES) with finger-like pores, and the outer layer is a ZnO-PES composite layer with finger-like pores also. The ZnO-PES composite layer is expected to contain uniform ZnO crystals in the polymer matrix, i.e., the ZnO particles in the skin layer of the support are not easy to fall off. Under the induction of ZnO particles in the outer layers, continuous ZIF-8 membranes can be prepared by single in-situ crystallization, showing good adhesion to the supports. The obtained ZIF-8 membranes show a H_(2) permeance of 8.7 × 10^(-8)mol·m^(-2)·s^(-1)·Pa^(-1) with a H_(2)/N_(2) ideal separation selectivity of 18.0. The design and preparation of this dual-layer polymer support is expected to promote the large-scale application of MOF membranes on polymer supports.

Adsorption Thermodynamics and Diffusion Kinetics of PX over Na Y Zeolite Synthesized by In-Situ Crystallization from Kaolin Microsphere

Para-xylene was chosen as the probe molecule to study adsorption thermodynamics and diffusion kinetics on NaY zeolite and composite structured NaY zeolite synthesized by in-situ crystallization from kaolin microsphere(designated as Na Y/kaolin composites) separately, using a high precision intelligent gravimetric analyzer(IGA). The adsorption isotherms showed normal Langmuir type-Ⅰ behaviors. The increased adsorption heat with an increasing p-xylene coverage supported a mechanism of phase transition, diffusion and re-arrangement of p-xylene molecules during the adsorption process. The rearrangement seemed to be most pronounced at an adsorption loading of 2.13 and 2.29 mmol/g for Na Y zeolite and Na Y/kaolin composites respectively. Compared with Na Y zeolite, a 2—3 times higher in the diffusion coefficient of p-xylene was observed on Na Y/kaolin composites when the pressure was more than 50 Pa. Temperature-programmed desorption(TPD) of p-xylene on two samples from room temperature to 450 ℃ at a special loading has also been investigated by IGA. Results showed only single desorption peak appeared for Na Y zeolite, indicating that adsorption can only occur in the super-cage structure. Comparably, there were two different peaks for in-situ synthesized Na Y zeolite, corresponding to the two thermo desorption processes in both super-cage structure and the channels provided by kaolin, respectively.Key words:

An in-situ study of static recrystallization in Mg using high temperature EBSD

It has been a common method to improve the mechanical properties of metals by manipulating their microstructures via static recrystallization,i.e.,through heat treatment.Therefore,the knowledge of recrystallization and grain growth is critical to the success of the technique.In the present work,by using in-situ high temperature EBSD,the mechanisms that control recrystallization and grain growth of an extruded pure Mg were studied.The experimental results revealed that the grains of priority for dynamic recrystallization exhibit fading competitiveness under static recrystallization.It is also found that grain boundary movement or grain growth is likely to show an inverse energy gradient effect,i.e.,low energy grains tend to swallow or grow into high energy grains,and grain boundaries of close to 30°exhibit superior growth advantage to others.Another finding is that{10-12}tensile twin boundaries are sites of hardly observed for recrystallization,and are finally swallowed by adjacent recrystallized grains.The above findings may give comprehensive insights of static recrystallization and grain growth of Mg,and may guide the design of advanced materials processing in microstructural engineering.

Preparation, Crystallization and Mechanical Properties of Potassium Aluminosilicate Glass-ceramics

In this study,transparent K_(2)O-Al_(2)O_(3)-SiO_(2)(KAS)glass-ceramics with leucite as the main crystalline phase were prepared by melting-quench method and two-step heat treatment.The effects of SiO_(2)/Al_(2)O_(3) ratio and heat treatment on crystallization and mechanical properties were studied.The crystallization kinetics and X-Ray Diffraction(XRD)results showed that SiO_(2)/Al_(2)O_(3) ratio and heat treatment system had a direct impact on the crystallization behavior of potassium aluminosilicate glass-ceramics.When heat-treated at 680℃/2 h and 780℃/1 h,cracks generated on the surface of the sample with the addition of SiO_(2)/Al_(2)O_(3)=4.8(in mol)due to the huge difference in the coefficient of thermal expansion between glass matrix and surface.When the addition of SiO_(2)/Al_(2)O_(3)(in mol)was 4,the sample with leucite as the main crystalline phase showed an excellent fracture toughness(1.46 MPa·m^(0.5))after the heat treatment of 680℃/2 h and 780℃/5 h.And there was a phase transformation from kaliophilite to leucite.The crystalline phases of the sample heat-treated at 680℃/8 h and 780℃/1 h were leucite and kaliophilite,which resulted in the visible light transmittance of 63%and the fracture toughness of 0.91 MPa·m^(0.5).Furthermore,after the heat treatment of 680℃/2 h and 780℃/5 h,the main crystalline phase of the sample with SiO_(2)/Al_(2)O_(3)=3.2(in mol)was still kaliophilite.Because leucite only grows on the surface of the sample and is hard to grow inward,it is hard to achieve the bulk crystallization of leucite in the sample with SiO_(2)/Al_(2)O_(3)=3.2(in mol).

Purification of copper foils driven by single crystallization

High-purity copper(Cu) with excellent thermal and electrical conductivity, is crucial in modern technological applications, including heat exchangers, integrated circuits, and superconducting magnets. The current purification process is mainly based on the zone/electrolytic refining or anion exchange, however, which excessively relies on specific integrated equipment with ultra-high vacuum or chemical solution environment, and is also bothered by external contaminants and energy consumption. Here we report a simple approach to purify the Cu foils from 99.9%(3N) to 99.99%(4N) by a temperature-gradient thermal annealing technique, accompanied by the kinetic evolution of single crystallization of Cu.The success of purification mainly relies on(i) the segregation of elements with low effective distribution coefficient driven by grain-boundary movements and(ii) the high-temperature evaporation of elements with high saturated vapor pressure.The purified Cu foils display higher flexibility(elongation of 70%) and electrical conductivity(104% IACS) than that of the original commercial rolled Cu foils(elongation of 10%, electrical conductivity of ~ 100% IACS). Our results provide an effective strategy to optimize the as-produced metal medium, and therefore will facilitate the potential applications of Cu foils in precision electronic products and high-frequency printed circuit boards.

Unveiling the early stage evolution of local atomic structures in the crystallization process of a metallic glass

The early stage evolution of local atomic structures in a multicomponent metallic glass during its crystallization process has been investigated via molecular dynamics simulation.It is found that the initial thermal stability and earliest stage evolution of the local atomic clusters show no strong correlation with their initial short-range orders,and this leads to an observation of a novel symmetry convergence phenomenon,which can be understood as an atomic structure manifestation of the ergodicity.Furthermore,in our system we have quantitatively proved that the crucial factor for the thermal stability against crystallization exhibited by the metallic glass is not the total amount of icosahedral clusters,but the degree of global connectivity among them.

Formation and Properties of Organic Long Persistent Luminescence Crystals Containing Benzidine Derivatives by Melt Crystallization

Organic molecules that exhibit long persistent luminescence (LPL) are rapidly gaining attention for a variety of applications. In this study, organic molecules with simple structures were selected and organic long persistent luminescence (OLPL) crystals were prepared. The crystal structure of the prepared OLPL crystal was elucidated and the guideline for the design of OLPL crystal was clarified. LPL was observed in OLPL crystals prepared with TMB as the guest molecule and 1,2-bis(diphenylphosphino)ethane as the host molecule. XRD measurements of the OLPL crystals suggest that the guest molecule is a solid solution substituted in the stable crystal structure of the host molecule in a lattice-shrinking direction.

The reaction mechanism and interfacial crystallization of Al nanoparticle-embedded Ni under shock loading

The shock-induced reaction mechanism and characteristics of Ni/Al system,considering an Al nanoparticle-embedded Ni single crystal,are investigated through molecular dynamics simulation.For the shock melting of Al nanoparticle,interfacial crystallization and dissolution are the main characteristics.The reaction degree of Al particle first increases linearly and then logarithmically with time driven by rapid mechanical mixing and following dissolution.The reaction rate increases with the decrease of particle diameter,however,the reaction is seriously hindered by interfacial crystallization when the diameter is lower than 9 nm in our simulations.Meanwhile,we found a negative exponential growth in the fraction of crystallized Al atoms,and the crystallinity of B2-NiAl(up to 20%)is positively correlated with the specific surface area of Al particle.This can be attributed to the formation mechanism of B2-NiAl by structural evolution of finite mixing layer near the collapsed interface.For shock melting of both Al particle and Ni matrix,the liquid-liquid phase inter-diffusion is the main reaction mechanism that can be enhanced by the formation of internal jet.In addition,the enhanced diffusion is manifested in the logarithmic growth law of mean square displacement,which results in an almost constant reaction rate similar to the mechanical mixing process.

Euler’s First-Order Explicit Method–Peridynamic Differential Operator for Solving Population Balance Equations of the Crystallization Process

Using Euler’s first-order explicit(EE)method and the peridynamic differential operator(PDDO)to discretize the time and internal crystal-size derivatives,respectively,the Euler’s first-order explicit method–peridynamic differential operator(EE–PDDO)was obtained for solving the one-dimensional population balance equation in crystallization.Four different conditions during crystallization were studied:size-independent growth,sizedependent growth in a batch process,nucleation and size-independent growth,and nucleation and size-dependent growth in a continuous process.The high accuracy of the EE–PDDO method was confirmed by comparing it with the numerical results obtained using the second-order upwind and HR-van methods.The method is characterized by non-oscillation and high accuracy,especially in the discontinuous and sharp crystal size distribution.The stability of the EE–PDDO method,choice of weight function in the PDDO method,and optimal time step are also discussed.

In-situ coating and surface partial protonation co-promoting performance of single-crystal nickel-rich cathode in all-solid-state batteries

The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poor crystal structure stability of Ni-rich cathode.Several coating strategies are previously employed to enhance the stability of the cathodic interface and crystal structure for Ni-rich cathode.However,these methods can hardly achieve simplicity and high efficiency simultaneously.In this work,polyacrylic acid(PAA)replaced traditional PVDF as a binder for cathode,which can achieve a uniform PAA-Li(LixPAA(0<x≤1))coating layer on the surface of single-crystal LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)due to H^(+)/Li^(+)exchange reaction during the initial charging-discharging process.The formation of PAA-Li coating layer on cathode can promote interfacial Li^(+)transport and enhance the stability of the cathodic interface.Furthermore,the partially-protonated surface of SC-NCM83 casued by H^(+)/Li^(+)exchange reaction can restrict Ni ions transport to enhance the crystal structure stability.The proposed SC-NCM83-PAA exhibits superior cycling performance with a retention of 92%compared with that(57.3%)of SC-NCM83-polyvinylidene difluoride(PVDF)after 200 cycles.This work provides a practical strategy to construct high-performance cathodes for ASSBs.

Fabrication and luminescence of highly transparent C12A7:Tb^(3+)glass-ceramics via in-situ crystallization from aerodynamic levitation processed glasses

Rare earth doped 12CaO·7Al_(2)O_(3)(C12A7)glass-ceramics are one of attractive photonic materials due to their high transparency,high luminescent efficiency and eco-friendly nature.A series of C12A7 glasses with different Tb^(3+)doping concentrations was prepared by aerodynamic levitation method.The C12A7:Tb glass-ceramics were obtained via in-situ growth from the glasses with the identical chemical composition at 800℃.The microstructure observation demonstrates that the elemental distributions of Ca and Al are homogeneous in the glass-ceramics and the grain size of C12A7 is 4-70 nm.The in-line transmittance of glass-ceramics reaches as high as 82%at 1500 nm.The emission spectra of the C12A7:Tb glass-ceramics present characteristic Tb^(3+)emission peaks at 486 nm(^(5)D_(4)→^(7)F_6),541 nm(^(5)D_(4)→^(7)F_(5)),585 nm(^(5)D_(4)→^(7)F_(4))and 621 nm(^(5)D_(4)→^(7)F_(3)).The photolumine scence lifetime of C12A7:0.3%Tb glass-ceramic is 1.9 ms.Compared with the emission intensity of the glasses,that of the glass-ceramics increases due to the reducing in concentration of oxygen vacancy associated with network forming(NWF)cations.The highly transparent C12A7:Tb glass-ceramics may be a promising candidate for green light source in solid state lighting.

Exploring influence of MgO/CaO on crystallization characteristics to understand fluidity of synthetic coal slags

The crystallization has significant influence on fluidity of slag and slag discharge of entrained-flow-bed(EFB) gasifier. The crystallization characteristics and fluidity of five synthetic slags with different MgO/CaO ratios prepared on the basis of the range of oxide contents of Zhundong coal ash were investigated in this study. The results show that with the MgO/CaO ratio increase, the initial crystallization temperature increases, and the main temperature range of crystallization ratio growth moves to higher temperature range gradually which causes Tp25(Tp25is the temperature corresponding to the viscosity of 25 Pa·s)to increase. Mg-rich crystals are formed preferentially than Ca-rich crystals when adding the same amount of MgO and CaO during cooling. The effective slagging operating temperature range decrease from 217 ℃ for the slag with a 0:4 MgO/CaO ratio to 44 ℃ for the slag with a 4:0 MgO/CaO ratio with the MgO/CaO ratio increase. The slags with 2:2 and 1:3 MgO/CaO ratios show similar effective slagging operating temperature range, Tp25and the temperature corresponding to the viscosity of 2 Pa·s.However, compared with the slag with a 1:3 MgO/CaO ratio, the crystallization ratio and rate of slag with a 2:2 MgO/CaO ratio are lower within lower temperature range(1300–1200 ℃), causing its lower critical viscosity temperature and wider actual operating temperature range. Of the five slags, the widest effective slagging operating temperature range and the lowest Tp25of the slag with a 0:4 MgO/CaO ratio due to its low crystallization ratio, and wider actual operating temperature range of the slag with a 2:2 MgO/CaO ratio make the two slags suitable for slag discharge of EFB gasifier.

Inherent relationship between process parameters,crystallization and mechanical properties of continuous carbon fiber reinforced PEEK composites

High-performance thermoplastic composites have been developed as significant structural materials for cutting-edge equipment in the aerospace and defence fields.However,the internal mechanism of processing parameters on mechanical properties in the manufacturing process of thermoplastic composite structures is still a serious challenge.The purpose of this study is to investigate the process/crystallization/property relationships for continuous carbon fiber(CF)reinforced polyether-ether-ketone(PEEK)composites.The composite laminates are fabricated according to orthogonal experiments via the thermoforming method.The mechanical performance is investigated in terms of crystallization properties and fracture morphology characterizations.Experimental results show that the mechanical performance and crystallization properties of thermoplastic composites are significantly affected by the coupling of processing parameters.The increased molding temperature,pressure,and holding time improve the degree of fiber/matrix infiltration and affect the crystallinity and crystalline morphology of the matrix,which further influences the mechanical properties of the composites.This is reflected in the test results that crystallinity has an approximately linear effect on mode-I interlaminar fracture toughness and transverse flexural modulus.As well as the higher molding temperature can destroy the pre-existent crystals to improve the toughness of the matrix,and the well-defined crystalline structures can be observed when fabricated at higher temperatures and longer periods of holding time.

Influence ofβ-nucleating Compound Agents on the Mechanical Properties and Crystallization Behavior of Polypropylene Random Copolymer

A novel polypropylene random(PPR)composite materials with optimized properties was developed by addingβ-nucleating compound agents(rare earth complex WBG-2 and aryl amide derivative TMB-5)and ternary compound modifier(TPE/WBG-2/CaCO_(3)).The effects of differentβ-nucleating agents and ternary compound modifier on the mechanical properties and crystallization behavior of PPR were analyzed.The results show that,compared with pure PPR materials,both WBG-2 and TMB-5 could significantly improve the impact strength of PPR.The crystallization temperature of PPR increased with the addition ofβ-nucleating agent.The modified PPR prepared with ternary compound modifier showed the most excellent comprehensive properties.

Crystal plane induced in-situ electrochemical activation of manganese-based cathode enable long-term aqueous zinc-ion batteries

Rapid capacity decay and sluggish reaction kinetics are major barriers hindering the applications of manganese-based cathode materials for aqueous zinc-ion batteries.Herein,the effects of crystal plane on the in-situ transformation behavior and electrochemical performance of manganese-based cathode is discussed.A comprehensive discussion manifests that the exposed(100)crystal plane is beneficial to the phase transformation from tunnel-structured MnO_(2) to layer-structured ZnMn_(3)O_(7)·3H_(2)O,which plays a critical role for the high reactivity,high capacity,fast diffusion kinetics and long cycling stability.Additionally,a two-stage zinc storage mechanism can be demonstrated,involving continuous activation reaction and phase transition reaction.As expected,it exhibits a high capacity of 275 mAh g^(-1)at 100 mA g^(-1),a superior durability over 1000 cycles and good rate capability.This study may open new windows toward developing advanced cathodes for ZIBs,and facilitate the applications of ZIBs in large-scale energy storage system.

Centimeter-sized Cs_(3)Cu_(2)I_(5)single crystals grown by oleic acid assisted inverse temperature crystallization strategy and their films for high-quality X-ray imaging

Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging,yet the issues of the poor chemical stability of hybrid halide perovskite,the high poisonousness of lead halides and the relatively low detectivity of the lead-free halide perovskites which seriously restrain its commercialization.Here,we developed a solution inverse temperature crystal growth(ITCG)method to bring-up high quality Cs_(3)Cu_(2)I_(5)crystals with large size of centimeter order,in which the oleic acid(OA)is introduced as an antioxidative ligand to inhibit the oxidation of cuprous ions effieiently,as well as to decelerate the crystallization rate remarkalby.Based on these fine crystals,the vapor deposition technique is empolyed to prepare high quality Cs_(3)Cu_(2)I_(5)films for efficient X-ray imaging.Smooth surface morphology,high light yields and short decay time endow the Cs_(3)Cu_(2)I_(5)films with strong radioluminescence,high resolution(12 lp/mm),low detection limits(53 nGyair/s)and desirable stability.Subsequently,the Cs_(3)Cu_(2)I_(5)films have been applied to the practical radiography which exhibit superior X-ray imaging performance.Our work provides a paradigm to fabricate nonpoisonous and chemically stable inorganic halide perovskite for X-ray imaging.

Crystallization thermodynamics of 2,4(5)-dinitroimidazole in binary solvents

2,4(5)-Dinitroimidazole(2,4(5)-DNI)is an important organic intermediate,and itself can also be used for energetic material.In this work,the solubility of 2,4(5)-DNI in(methanol+water,acetonitrile+water,acetone+water)binary solvents were measured by using a dynamic test method from 278.15 K to 323.15 K under 101.1 k Pa.The Jouyban–Acree model,van't Hoff–Jouyban–Acree model,Apelblat–Jouyb an–Acree model,Ma model,and Sun model were used to correlate the experimental data.The values of relative average deviation(RAD)and root-mean-square deviation(RMSD)were very small,indicating that the error between the experimental value and the correlated value was very small.The thermodynamic parameters such as dissolution enthalpy,dissolution entropy and Gibbs energy were calculated based on solubility data.High-purity of 2,4(5)-DNI was efficiently obtained by using cooling and dilution crystallization method.

Crystalline Morphology and Crystallization Characteristics of In-situ Blends of Anionic Polyamide 6 with Noncrystallizable Semiaromatic Polyamide Copolymer

A noncrystallizable semiaromatic polyamide copolymer（NSAP） was dissolved in molten caprolactam, and PA6/ NSAP blends were produced in-situ via the anionic ring-opening polymerization of caprolactam. The presence of a single loss tangent（tanS） peak measured by means of dynamic mechanical analysis（DMA） proves the miscibility between PA6 and NSAP in the blends. It was found that there existed drastic changes in the crystallographic form and crystallization kinetics for the in-situ blends, e.g. , when 20% NSAP was added, nearly all crystallites existed in the ,y form and the crystallization could hardly occur upon cooling even at a rate of 2.5 ℃/min. Moreover, cold crystallization appears during the subsequent heating, and its melting point is 40 ℃ lower than that of the virgin system. On the other hand, the size of the spherulites only decreases modestly. It is suggested that the introduction of irregular stiff segments originated from NSAP into PA6 macromolecule chain, which resulted from transamidation during the polymerization play a dominant role in the drastic change of crystallization kinetics and the resultant morphology of the in-situ blends.

IN-SITU AFM OF POLYMER CRYSTALLIZATION

Atomic force microscopy images taken during the crystallization of polyethylene both from processed andquiescent melts are presented. Crystallization from processed melts provides further evidence of a region in front of agrowing lamella that is influenced by the crystallization process, but extending only 40 nm into the melt. High-resolutionimages of the growing crystal tip, taken during crystallization, show no direct evidence of the existence of intermediatephases. The growing tip is shown to be slightly rounded. In-filling crystallization, occurring after the initial flush of growth,is imaged in polyethylene for the first time, and shown to continue to a temperature 8℃ below the initial crystallizationtemperature.

Crystallization and Orientation Modulation Enable Highly Efficient Doctor-Bladed Perovskite Solar Cells

With the rapid rise in perovskite solar cells(PSCs)performance,it is imperative to develop scalable fabrication techniques to accelerate potential commercialization.However,the power conversion efficiencies(PCEs)of PSCs fabricated via scalable two-step sequential deposition lag far behind the state-of-the-art spin-coated ones.Herein,the additive methylammonium chloride(MACl)is introduced to modulate the crystallization and orientation of a two-step sequential doctorbladed perovskite film in ambient conditions.MACl can significantly improve perovskite film quality and increase grain size and crystallinity,thus decreasing trap density and suppressing nonradiative recombination.Meanwhile,MACl also promotes the preferred face-up orientation of the(100)plane of perovskite film,which is more conducive to the transport and collection of carriers,thereby significantly improving the fill factor.As a result,a champion PCE of 23.14%and excellent longterm stability are achieved for PSCs based on the structure of ITO/SnO_(2)/FA_(1-x)MA_xPb(I_(1-y)Br_y)_3/Spiro-OMeTAD/Ag.The superior PCEs of 21.20%and 17.54%are achieved for 1.03 cm~2 PSC and 10.93 cm~2 mini-module,respectively.These results represent substantial progress in large-scale two-step sequential deposition of high-performance PSCs for practical applications.