Regulation of the order-disorder phase transition in a Cs_(2)NaFeCl_(6) double perovskite towards reversible thermochromic application

Multifunctional lead-free double perovskites demonstrate remarkable potential towards applications in various fields.Herein,an environmentally-friendly,low-cost,high-throughput Cs_(2)NaFeCl_(6) single crystal with exceedingly high thermal stability is designed and grown.It obtains a cubic lattice system in the temperature range of 80-500 K,accompanied by a completely reversible chromatic variation ranging from yellow to black.Importantly,the intriguing thermochromism is proved to own extremely high reproducibility(over 1000 cycles)without a hysteretic effect,originating from its structural flexibility that including(i)the noteworthy distortion/deformation of[NaCl_(6)]5−and[FeCl_(6)]3−octahedra;(ii)order-disorder arrangement transition of[NaCl_(6)]5−and[FeCl6]3−octahedra as the function of temperature.This study paves the way towards a new class of smart windows and camouflage coatings with an unprecedented colour range based on a Cs_(2)NaFeCl_(6) perovskite.

Order-disorder Transformation for TiAl with L1_0 Structure at Stoichiometrical Composition

The embedded atom method （EAM） was used to study the order-disorder transformation in γ-TiAl alloy with L10 structure at stoichiometrical composition, and the effect of lattice constants was also investigated. It was found that the γ-TiAl alloy at stoichiometrical composition exhibits a second-order transition, and the relations between lattice con- stants a, c and the long-range order σ are not linear. The lattice constant a decreases whereas c increases with the increase of the long-range order parameter. In this case the ordering induces the transformation from cubic to tetragonal. The change of the lattice constant during the ordering processes can be interprated in terms of bond length.

Order-Disorder Transition of Carboxyl Terminated Chains in Polydiacetylenes Vesicles Probed by Second Harmonic Generation and Two-Photon Fluorescence

To understand and control the interfacial properties of polydiacetylenes(PDAs)vesicles withπ-conjugated backbone is very important for their colorimetric sensing of chemical and biological targets.In this work,we adopted 10,12-pentacosadiynoic acid(PCDA)as the model molecule to prepare PDAs vesicles in aqueous solution with different forms(from monomer to blue-to-purple-to-red phase)by controlling the UV irradiation dose.The variations of the interfacial conformation of PDAs vesicles during chromatic transitions were inspected by the adsorption behaviors of probe molecules(4-(4-diethylaminostyry)-1-methylpyridinium iodide,D289)on vesicle surface with surface-specific second harmonic generation(SHG)and zeta potential measurements.Resonant SHG signal from D289 adsorbed on vesicle surface attenuated sharply,and the adsorption free energy as well as the corresponding two-photon fluorescence signal decreased slightly in chromatic transitions.While,the change in the surface density of the adsorbed D289 molecules for PDAs vesicles with different forms was relatively small as estimated from zeta potential measurements.The attenuation of the SHG intensity was thus attributed to the overall order-disorder transition and the changed orientation of D289 molecules caused by the gradual distortion of carboxyl head group driven by backbone perturbation.

Theoretic Diffraction Research on the Order-Disorder Effect of Transition Metal in Li(Ni1/3 Co1/3 Mn1/3)O2

After describing research status of super-structure for Li (Ni_(1/3)Co_(1/3)Mn_(1/3)) O_2,diffraction patterns of Li (Ni_(1/3)Co_(1/3)Mn_(1/3)) O_2 in different order parameters have been researched by Powder-cell program,including crystal structure,X-ray and neutron diffraction pattern,anomalous diffraction pattern and comparison of NiCoMn in different positions. The influence of order parameters on intensity of matrix and super-lattice diffraction lines has also been analyzed and the summarization and prospect have been made lastly.

EAM Analysis of the Lattice Parameter Effect in Order-Disorder Transformation

The embedded atom method (EAM) was used to theoretically analyze the effect of the lattice parameter variation on the order-disorder transformation in binary alloys. Based on EAM, it is found that only one kind of order-disorder transition (second- order transition) exists for AB alloy. Three groups of order-disorder transformation can be observed for the A3B or AB3 compounds. For group I, the order-disorder is a completely first-order transition. For group II, the order-disorder transformation is a classical first-order transition. For group III, the order-disorder transformation is found to be a second-order transition. The lattice parameter variations have a significant effect on E2 coefficient, which is related to the ordering energy. These results are in good agreement with experiments.

Order-Disorder Phase Transition and Dielectric Mechanism in Relaxor Ferroelectrics

An overview is presented on the order-disorder structural transitions and the dielectric mechanism in the complex-perovskite type relaxor ferroelectrics, i.e., the relaxors. Emphasis is put on the theoretical understanding of the structural transitions, the macroscopic dielectric properties, and the relationship between them. The influences of the composition, the temperature, and the atomic interactions on the order-disorder microstructures can be well understood in the cluster-variation-method calculations. The criterion drawn from theoretical analysis is successful in predicting the order-disorder structure of relaxors. Among various physical models about relaxors, the dipole glassy model that described the dielectric response as the thermally activated flips of the local spontaneous polarization under random interactions is discussed in details. The Monte Carlo simulation results of this model are consistent with the linear and nonlinear experiments of relaxors.

Influence of order-disorder transition on the mechanical andthermophysical properties of ABOhigh-entropy ceramicsInfluence of order-disorder transition on the mechanical and thermophysical properties of A_(2)B_(2)O_(7)high-entropy ceramics 1

The order–disorder transition(ODT)of A_(2)B_(2)O_(7)compounds obtained enormous attention owing to the potential application for thermal barrier coating(TBC)design.In this work,the influence of ODT on the mechanical and thermophysical properties of dual-phase A_(2)B_(2)O_(7)high-entropy ceramics was investigated by substituting Ce^(4+)and Hf^(4+)with different ionic radii on B-sites(Zr^(4+)).The X-ray diffraction(XRD),Raman,and transmission electron microscopy(TEM)results show that rA3+/rB^(4+)=1.47 is the critical value of ODT phase boundary with different doping B-site ion contents,and the energy dispersive spectroscopy(EDS)results further indicate the uniform distribution of elements.Interestingly,owing to the high intrinsic disorder derived from high-entropy effect,the A_(2)B_(2)O_(7)high-entropy ceramics exhibit unreduced modulus(E0≈230 GPa)and enhanced mechanical properties(HV≈10 GPa,KIC≈2.3 MPa·m^(0.5)).A_(2)B_(2)O_(7)high-entropy ceramics exhibit excellent thermal stability with relatively high thermal expansion coefficients(TECs)(Hf_(0.25),11.20×10-6 K-1,1000℃).Moreover,the matching calculation implied that the ODT further enhances the phonon scattering coefficient,leading to a relatively lower thermal conductivity of(La_(0.25)Eu_(0.25)Gd_(0.25)Yb_(0.25))2(Zr_(0.85)Ce_(0.15))_(2)O_(7)(1.48–1.51 W/(m·K),100–500℃)compared with other components.This present work provides a novel composition design principle for high-entropy ceramics,as well as a material selection rule for high-temperature insulation applications.

THE INVESTIGATION OF KINETICS OF HIGH-TEMPERATURE STRUCTURE TRANSFORMATION OF HOMOPHASES AND HETEROPHASES MATERIALS

The kinetics of internal boundaries relaxation: antiphase domain boundaries and interphase boundaries-in the conditions of high-temperature annealing and the structure transformations are investigated in homophase and heterophase systems. Homophase systems look like ordered binary alloy and include antiphase domain boundaries of various orientation. Clear components border on ordered alloy in heterophase systems and two processes take place simultaneously here-disordering of binary alloy and solution in ordered phase of clear component. Computer experiment is realized in the sphere of temperatures close to the temperature of order-disorder phase transition in the limits of two-dimensional model of atom diffusion at the vacant knots of crystal lattics.

Influence of Aluminum Content in γ-TiAl with L1_0 Structure during Ordering Processes

Based on EAM (embedded atom method) interatomic potential, the effect of aluminum content on the type of order-disorder transformation (ODT) and the structure properties (lattice constants, volume, c/a ratio and configu- ration energy) during ordering processes was investigated for γ-TiAI based alloys. Results show that for the alloys with lower than 50%Al (all composition is in atom number fraction), the ODT is the first order transition, and the second order transition for the alloys with equal or higher than 50% Al. The increase of aluminum content results in the critical temperature increasing. The aluminum content has a very little effect on the lattice constants, the volume and the c/a ratio, but has a significant effect on the configuration energy. A metastable disordered state was found for the alloys with less than 50%Al.

Raman Scattering in Ga_xIn_(1-x)P and (Al_xGa_(1-x) )_0.51 In_0.49 P Alloys

Raman scattering spectroscopy is applied to investigate the phonon modes in Ga x In 1- x P ( x =0.52) and (Al x Ga 1- x ) 0.51 In 0.49 P ( x =0.29) alloys. Two mode behavior in Ga x In 1- x P and three mode behavior in (Al x Ga 1- x ) 0.51 In 0.49 P are observed. In ordered Ga x In 1- x P, we clearly distinguish the TO 1(GaP like) mode and the splitting of LO 1(GaP like) and LO 2 (InP like) modes, which is believed to be the result of superlattice effect of ordering, and the LO 1+LO 2 mode, which is observed for the first time. In addition to the b/a ratio, it’s found that the relative intensity of the FLA and the LO 1+LO 2 modes also corresponds to the degree of order. The TO 1 and the splitting of LO 1 and LO 2 devote together to the reduction of the "valley depth". In (Al x Ga 1- x ) 0.51 In 0.49 P, the doubling of FLA is observed. Due to the influence of Al composition, the GaP like LO mode becomes a shoulder of the InP like LO mode. The unresolved Raman spectra indicate the existence of ordered structure in (Al x Ga 1- x ) 0.51 In 0.49 P alloys.

Microphase Separation of Semiflexible Ring Diblock Copolymers

Aiming at the difficult problem of solving the conformation statistics of complex polymers, this study presents a novel and concise conformation statistics theoretical approach based on Monte Carlo and Neural Network method. This method offers a new research idea for investigating the conformation statistics of complex polymers, characterized by its simplicity and practicality. It can be applied to more complex topological structure, more higher degree of freedom polymer systems with higher dimensions, theory research on dynamic self-consistent field theory and polymer field theory, as well as the analysis of scattering experimental data. The conformation statistics of complex polymers determine the structure and response properties of the system. Using the new method proposed in this study, taking the semiflexible ring diblock copolymer as an example, Monte Carlo simulation is used to sample this ring conformation to construct the dataset of polymer. The structure factor describing conformation statistics are expressed as continuous functions of structure parameters by neural network supervised learning. This is the innovation of this work. As an application, the structure factors represented by neural networks were introduced into the random phase approximation theory to study the microphase separation of semiflexible ring diblock copolymers. The influence of the ring's topological properties on the phase transition behavior was pointed out.

Synthesis and characterization of Dy-Eu-Tm co-doped cubic phase stabilized bismuth oxide based electrolytes in terms of intermediate temperature-solid oxide fuel cells(IT-SOFCs)

In this study,a new Dy-Eu-Tm co-doped cubic phase stabilized bismuth oxide solid electrolyte system was synthesized by using solid-state reaction method in atmospheric conditions.Before conductivity measurements,X-ray diffraction(XRD)pro files of the annealed samples show that created mixtures have heterogeneous phase,but after conductivity measurements,the face-centered cubic(FCC)crystal structure is stabilized for all samples.Also,the increase in total dopant rate causes an increase in full width half maxima(FWHM)of main peak(111)on the XRD pattern while average crystal size decreases with it.On the other hand,the highest conductivity value was obtained for the sample having 15%total dopant rate with 0.62 S/cm at 750℃,whose dopants are evenly distributed in mole percent.Differential thermal analysis(DTA)results of the samples having 1:1:1 and 1:2:1 dopant content ratios show that endothermic peak occurs on their DTA curve,indicating crystal structure transformation such as phase transition or order-disorder transition.Also,thermo-gravimetric analysis(TGA)depending on temperature was evaluated in terms of mass loss.According to TGA curves,mass loss for both heating and cooling process can be negligible due to the small fluctuations(2%)on their TGA curves.

NH_(+)^(4)/K^(+)-substitution-induced C–F–K coordination bonds for designing the highest-temperature hybrid halide double perovskite ferroelastic

Ferroelastic materials with switchable spontaneous strain possess widely potential applications in the field of energy and information conversion.Recently,organic-inorganic hybrid halide double perovskites (OIHHDPs) have become a charming new platform for developing various functional materials,such as ferroelectrics,fluorescence and X–ray detection.Nevertheless,OIHHDP ferroelastic materials,especially high-temperature ones,are rare.Herein,we initially synthesized an OIHHDP ferroelastic,(2,2-difluoroethanamine)_(2)[(NH_(4))InCl_6](1),which possesses a ferroelastic phase transition at 407 K.Moreover,thanks to the flexible B-site for OIHHDPs,we replaced the NH_(4)^(+) ions within[(NH_(4))InCl_6]_n^(2n–)formworks with K^(+)ions,which endows with coordination bonds between 2,2-difluoroethanamine organic cations and[KInCl_6]_n^(2n–)formworks.Due to the existence of coordination bonds,the phase transition temperature of (2,2-difluoroethanamine)_(2)[KInCl_6](2) can reach 458 K.As far as we know,this value is the highest reported in OIHHDP ferroelastics.This work offers inspiration for the design of high-temperature OIHHDP phase transition materials including ferroelectrics and ferroelastics.

Sintering characteristics, phase transitions, and microwave dielectric properties of low-firing [(Na_(0.5)Bi_(0.5))_(x)Bi_(1-x)](W_(x)V_(1-x))O_(4) solid solutionceramics

A series of high-k[(Na_(0.5)Bi_(0.5))_(x)Bi_(1-x)](W_(x)V_(1-x))O_(4)(abbreviated as NBWV(x value))solid solution ceramics with a scheelite-like structure are synthesized by a modified solid-state reaction method at the temperature range of 680-760 C.A monoclinic(0≤x<0.09)to tetragonal scheelite(0.09≤x≤1.0)structural phase transition is confirmed by X-ray difraction(XRD),Raman,and infrared(IR)analyses.The effect of structural deformation and order-disorder caused by Na^(+)/Bi^(3+)/W^(6+) complex substitution on microwave dielectric properties is investigated in deail.The compositional series possess a wide range of variable relative permittivity(er=24.8-80)and temperature coefficient of resonant frequency(TCF value,-271.9-188.9 ppm/℃).The maximum permittivity of 80 and a high Qxf value of~10,000 GHz are obtained near the phase boundary at x=0.09.Furthermore,the temperature-stable dielectric ceramics sintered at 680 C with excellent microwave dielectric properties of ε_(r)=80.7,Qxf=9400 GHz(at 4.1 GHz),and TCF value=-3.8 ppm/℃ are designed by mixing the components of x=0.07 and 0.08.In summary,similar sinterability and structural compatibility of scheelite-like solid solution systems make it potential for low-temperature co-fired ceramic(LTCC)applications.

Disordering and reordering of an Al_3Ti-Mn-Nb alloy

Due to their attractive characteristics such as low density （3,4g/cm3）, relatively high melting point （1613 K）, good high-temperature strength and oxidation resistance, the Al3Tibase alloys have been considered good candidates for high-temperature structural purpose. The stoichiometric Al3Ti intermetallic compound has a tetragonal DO22 crystal structure. By replacing a certain amount of At with Fe, Mn, Cr, or Ni, etc., the DO22 structure

Experimental study of phase equilibria on Co-Fe-rich side of Co-Al-Fe system

Despite various studies on Co-Al-Fe ternary system, its phase equilibria are still in doubt. Phase equilibria, magnetic transition and bcc_A2/bcc_B2 order-disorder transformation at the Co-Fe-rich side of the Co-Al-Fe alloys were carefully investigated by means of electron probe microanalysis (EPMA), X-ray diffraction (XRD) and differential scanning calo-rimetry. The equilibrium phases and their compositions were determined by 18 alloy samples annealed at 900, 1000, 1100 and 1200℃ for 528, 336, 168 and 96h, respectively, followed by quenching. However, by adopting the above traditional method, bcc_A2 and fcc_A1 phases are difficult to be distinguished through XRD analysis at room temperature due to the martensitic transformation of fcc_A1 phase during quenching. For this reason, high-temperature insitu XRD technique was utilized to correctly establish the phase relationships among bcc_A2, bcc_B2 and fcc_A1 phases. The phase transformation between bcc_A2 and B2 phases was determined to be second order instead of first order at temperatures higher than 900℃. The equilibrium phases and compositions were further confirmed by fabricating 16 diffusion couples together with EPMA. Meanwhile, using three-dimensional differential scanning calorimetry method, bcc_A2/B2 and ferro-/paramagnetic transi-tions were determined with high accuracy.

Experimental evidence of coupling interaction between charge ordering and spin ordering

In order to experimentally probe into the complicated interaction between charge ordering and spin ordering in manganites,two sets of samples Nd0.5Sr0.5Mn1-xGaxO3(NSMGO) and Nd 0.5Sr0.5Mn1-y CryO3(NSMCO)(0.0 x,y 0.075),have been studied by means of electrical transport,magnetization,electron spin resonance and transmission electron microscopy analysis.By comparing the influence of Cr-doping and Ga-doping in the Nd0.5Sr0.5MnO3(NSMO) system,large difference between the evolution of charge ordering temperature T co in the Cr-doping and the Ga-doping cases is found.In the NSMCO system,the CE-type antiferromagnetic(AFM)/charge ordering(CO) phase disappears with only 2.5 percent Cr doping;but in the NSMGO system,the CE-type AFM/CO phase always exists.This phenomenon indicates that the charge ordering formation is dominated by the spin ordering.As a result,it is experimentally proved that there is strong coupling interaction between charge ordering and spin ordering in NSMO system.