Growth and Characterization of a New Semi-Organic Nonlinear Optical Crystal: Thiosemicarbazide Cadmium Acetate

A new semi-organic nonlinear optical thiosemicarbazide cadmium acetate (TSCA) material has been synthesized. TSCA single crystals were grown from aqueous solution by slow evaporation method. The solubility of TSCA has been determined for various temperatures. The grown crystals were characterized by single crystal X-ray diffraction (XRD), FTIR, UV-Vis., thermal and second harmonic generation (SHG) analysis. Single crystal XRD study has been carried out to identify the lattice parameters. FTIR studies confirm the functional groups present in the grown crystal. Optical transmission studies have confirmed that the grown crystal is highly transparent. Thermogravimetric and differential thermal analyses reveal the good thermal stability of the material. The SHG conversion efficiency of TSCA was determined using Kurtz powder technique and found two times that of potassium dihydrogen orthophosphate (KDP).

Role of Crystal Seed in Aluminum Hydroxide Crystallization from Ammonia System with Added NH_(4)Al(SO_(4))_(2)·12H_(2)O

A method to promote aluminum hydroxide crystal growth through pickling Al(OH)_(3)as seed in the ammonia system was proposed to overcome these defects.The experimental results show that,under the conditions of pickling time of 15 min,the acid concentration of 10%,the addition of 70 g/L pickling-Al(OH)_(3)seed,and the coarse granular Al(OH)_(3)products(d0.5=85.667)can be obtained.The characterization results show that the phase of the product is gibbsite,consistent with the seed.Moreover,the steps and ledges can be formed on pickling Al(OH)_(3)seed surface under the ammonia system,effectively promoting crystal growth.During crystal growth,the roughness of the crystal surface was first increased and then decreased,and the lamellar structure was deposited on the crystal seed surface.The final particles are approximately round,the surface is compact and dense.The growth of the product is surface reaction controlled.In addition,the content of the AlO_(6)unit is increased and contributed to Al(OH)_(3)crystal growth.

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).

Effect of Fluoride on the Ion-association of Calcium Phosphate and Crystallization of Hydroxyapatite

Using a titration setup to accurately control the reaction conditions and in situ monitor the reaction,we showed that fluoride exhibited negligible effects on the ion association process of calcium and phosphate and the formation of ACP nanospheres in a buffer solution with constant ionic strength.However,the stability of ACP increased with increasing fluoride concentration,which was ascribed to the inhibitory effect of fluoride on the aggregation of ACP nanospheres and the nucleation of nanocrystals on the surface of ACP nanospheres.Furthermore,fluoride could inhibit the lateral growth of HAP nanosheets and promote the formation of rod-like crystals.These results further improve our understanding of the crystallization pathway of HAP crystals and the regulatory effects of fluoride.

Tunable dispersion relations manipulated by strain in skyrmion-based magnonic crystals

We theoretically investigate the propagation characteristics of spin waves in skyrmion-based magnonic crystals. It is found that the dispersion relation can be manipulated by strains through magneto-elastic coupling. Especially, the allowed bands and forbidden bands in dispersion relations shift to higher frequency with strain changing from compressive to tensile,while shifting to lower frequency with strain changing from tensile to compressive. We also confirm that the spin wave with specific frequency can pass the magnonic crystal or be blocked by tuning the strains. The result provides an advanced platform for studying the tunable skyrmion-based spin wave devices.

Synthesis of NaY zeolite from a submolten depolymerized perlite:Alkalinity effect and crystallization kinetics

NaY zeolites are synthesized using submolten salt depolymerized natural perlite mineral as the main silica and alumina sources in a 0.94 L stirred crystallizer.Effects of alkalinity ranging from 0.38 to 0.55(n(Na2O)/n(SiO_(2)))on the relative crystallinity,textural properties and crystallization kinetics were investigated.The results show that alkalinity exerts a nonmonotonic influence on the relative crystallinity and textural properties,which exhibit a maximum at the alkalinity of 0.43.The nucleation kinetics are studied by fitting the experimental data of relative crystallinity with the Gualtieri model.It is shown that the nucleation rate constant increases with increasing alkalinity,while the duration period of nucleation decreases with increasing alkalinity.For n(Na2O)/n(SiO_(2))ratios ranging from 0.38 to 0.55,the as-synthesized NaY zeolites exhibit narrower crystal size distributions with the increase in alkalinity.The growth rates determined from the variations of average crystal size with time are 51.09,157.50,46.17 and 24.75 nm·h^(-1),respectively.It is found that the larger average crystal sizes at the alkalinity of 0.38 and 0.43 are attributed to the dominant role of crystal growth over nucleation.Furthermore,the combined action of prominent crystal growth and the longer duration periods of nucleation at the alkalinity of 0.38 and 0.43 results in broader crystal size distributions.The findings demonstrate that control of the properties of NaY zeolite and the crystallization kinetics can be achieved by conducting the crystallization process in an appropriate range of alkalinity of the reaction mixture.

Simultaneous guidance of electromagnetic and elastic waves via glide symmetry phoxonic crystal waveguides

A phoxonic crystal waveguide with the glide symmetry is designed,in which both electromagnetic and elastic waves can propagate along the glide plane at the same time.Due to the glide symmetry,the bands of the phoxonic crystal super-cell degenerate in pairs at the boundary of the Brillouin zone.This is the so-called band-sticking effect and it causes the appearance of gapless guided-modes.By adjusting the magnitude of the glide dislocation the edge bandgaps,the bandgap of the guided-modes at the boundary of the Brillouin zone,can be further adjusted.The photonic and phononic guided-modes can then possess only one mode for a certain frequency with relatively low group velocities,achieving single-mode guided-bands with relatively flat dispersion relationship.In addition,there exists acousto-optic interaction in the cavity constructed by the glide plane.The proposed waveguide has potential applications in the design of novel optomechanical devices.

CDBS:基于CRYSTALS-Dilithium算法的盲签名方案

为了应对传统盲签名方案在用户端、签名方和验证者交互过程中无法抵御量子计算攻击的这一难题,以NIST选定的后量子数字签名算法CRYSTALS-Dilithium为基础框架,设计了一种新型抗量子计算攻击的盲签名方案CDBS。整体方案采用Fiat-Shamir签名结构,包括密钥生成、盲化、签名、去盲和验证5个阶段,方案内部结合拒绝采样技术防止密钥泄露,使用NTT算法优化多项式计算以提高签名和验证效率。分析表明,所提方案安全性依赖于模误差学习(MLWE)问题和小整数解(SIS)问题,同时满足正确性、盲性和不可伪造性。与其他基于格的盲签名方案相比,所提方案具有较高的安全性,且签名生成过程更高效,占用开销更小。在相同样本参数设置下,所提方案整体开销仅为MBS方案的67.1%。经软件测试验证,实现一次完整的盲签名和验证过程平均仅需657.65μs。所提方案为CRYSTALS-Dilithium数字签名算法的拓展应用提供了参考。

High-efficiency ultra-fast all-optical photonic crystal diode based on the lateral-coupled nonlinear elliptical defect

An all-optical Fano-like diode featuring a nonlinear lateral elliptical micro-cavity and a reflecting column in the photonic crystal waveguide is proposed.The asymmetric micro-cavity is constructed by removing one rod and changing the shape of the lateral rod from a circle to an ellipse.A reflecting pillar is also introduced into the waveguide to construct an F-P cavity with the elliptical defect and enhance the asymmetric transmission for the incident light wave transmitting rightwards and leftwards,respectively.By designing the size of the ellipse and optimizing a reflecting rod at a suitable position,a maximum forward light transmittance of-1.14 dB and a minimum backward transmittance of-57.66 dB are achieved at the working wavelength of 1550.47 nm.The corresponding response time is about 10 ps when the intensity of the pump light beam resonant at 637 nm is 3.97 W/μm2.

Nonreciprocal transport in the superconducting state of the chiral crystal NbGe_(2)

Due to the lack of inversion,mirror or other roto-inversion symmetries,chiral crystals possess a well-defined handedness which,when combined with time-reversal symmetry breaking from the application of magnetic fields,can give rise to directional dichroism of the electrical transport phenomena via the magnetochiral anisotropy.In this study,we investigate the nonreciprocal magneto-transport in microdevices of NbGe_(2),a superconductor with structural chirality.A giant nonreciprocal signal from vortex motions is observed during the superconducting transition,with the ratio of nonreciprocal resistance to the normal resistanceγreaching 6×10^(5)T^(-1)·A^(-1).Interestingly,the intensity can be adjusted and even sign-reversed by varying the current,the temperature,and the crystalline orientation.Our findings illustrate intricate vortex dynamics and offer ways of manipulation on the rectification effect in superconductors with structural chirality.

Effect of Fe_(2)O_(3)on the Structure,Physical Properties and Crystallization of CaO-Al_(2)O_(3)-SiO_(2)Glass

The calcium aluminosilicate-based glasses(CaO-Al_(2)O_(3)-SiO_(2),CAS)with different Fe_(2)O_(3)content(0.10wt%,0.50wt%,0.90wt%,and 1.30wt%)were prepared by traditional melt-quenching method.The glass network structure,thermal and mechanical properties,and crystallization behavior changes were investigated by nuclear magnetic resonance spectrometer,Fourier-transform infrared spectro-photometer,X-ray diffractometer,differential scanning calorimetry and field emission scanning electron microscope measurements.The change of Q^(n)in glass structures reveals the glass network connectivity decreases due to the increasing content of Fe_(2)O_(3)addition,resulting in the increasing of non-bridging number in glass structure.The glass densities slightly rise from 2.644 to 2.681 g/cm^(3),while Vickers’s hardness increases at first,from 6.469 to 6.901 GPa,then slightly drops to 6.745 GPa,with Fe_(2)O_(3)content increase.There is almost no thermal expansion coefficient change from different Fe_(2)O_(3)content.The glass transmittance in visible range gradually decreases with higher Fe_(2)O_(3)content,resulting from the strong absorption of Fe^(2+)and Fe^(3+)ions.The calculated activation energy from thermal analysis results first decreases from 282.70 to 231.18 kJ/mol,and then increases to 244.02 kJ/mol,with the Fe_(2)O_(3)content increasing from 0.10wt%to 1.30wt%.Meanwhile,the maximum Avrami constant of 2.33 means the CAS glasses exhibit two-dimensional crystallization.All of the CAS glass-ceramics samples contain main crystal phase of anorthite,the microstructure appears lamellar and columnar crystals.

High-precision X-ray polarimeter based on channel-cut crystals

We report on using synthetic silicon for a high-precision X-ray polarimeter comprising a polarizer and an analyzer,each based on a monolithic channel-cut crystal used at multiple Brewster reflections with a Bragg angle very close to 45°.Experiments were performed at the BL09B bending magnet beamline of the Shanghai Synchrotron Radiation Facility using a Si(800)crystal at an X-ray energy of 12.914 keV.A polarization purity of 8.4×10^(-9)was measured.This result is encouraging,as the measured polarization purity is the best-reported value for the bending magnet source.Notably,this is the firstly systematic study on the hard X-ray polarimeter in China,which is crucial for exploring new physics,such as verifying vacuum birefringence.

Etching of quartz crystals in liquid phase environment:A review

Quartz crystals are the most widely used material in resonant sensors,owing to their excellent piezoelectric and mechanical properties.With the development of portable and wearable devices,higher processing efficiency and geometrical precision are required.Wet etching has been proven to be the most efficient etching method for large-scale production of quartz devices,and many wet etching approaches have been developed over the years.However,until now,there has been no systematic review of quartz crystal etching in liquid phase environments.Therefore,this article provides a comprehensive review of the development of wet etching processes and the achievements of the latest research in thisfield,covering conventional wet etching,additive etching,laser-induced backside wet etching,electrochemical etching,and electrochemical discharge machining.For each technique,a brief overview of its characteristics is provided,associated problems are described,and possible solutions are discussed.This review should provide an essential reference and guidance for the future development of processing strategies for the manufacture of quartz crystal devices.

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.

Manipulating Crystal Growth and Secondary Phase PbI_(2)to Enable Efficient and Stable Perovskite Solar Cells with Natural Additives

In perovskite solar cells(PSCs),the inherent defects of perovskite film and the random distribution of excess lead iodide(PbI_(2))prevent the improvement of efficiency and stability.Herein,natural cellulose is used as the raw material to design a series of cellulose derivatives for perovskite crystallization engineering.The cationic cellulose derivative C-Im-CN with cyano-imidazolium(Im-CN)cation and chloride anion prominently promotes the crystallization process,grain growth,and directional orientation of perovskite.Meanwhile,excess PbI_(2)is transferred to the surface of perovskite grains or formed plate-like crystallites in local domains.These effects result in suppressing defect formation,decreasing grain boundaries,enhancing carrier extraction,inhibiting non-radiative recombination,and dramatically prolonging carrier lifetimes.Thus,the PSCs exhibit a high power conversion efficiency of 24.71%.Moreover,C-Im-CN has multiple interaction sites and polymer skeleton,so the unencapsulated PSCs maintain above 91.3%of their initial efficiencies after 3000 h of continuous operation in a conventional air atmosphere and have good stability under high humidity conditions.The utilization of biopolymers with excellent structure-designability to manage the perovskite opens a state-of-the-art avenue for manufacturing and improving PSCs.

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.

Boosting kinetic separation of ethylene and ethane on microporous materials via crystal size control

The adsorptive separation of C_(2)H_(4)and C_(2)H_(6),as an alternative to distillation units consuming high energy,is a promising yet challenging research.The great similarity in the molecular size of C_(2)H_(4)and C_(2)H_(6)brings challenges to the regulation of adsorbents to realize efficient dynamic separation.Herein,we reported the enhancement of the kinetic separation of C_(2)H_(4)/C_(2)H_(6)by controlling the crystal size of ZnAtzPO_(4)(Atz=3-amino-1,2,4-triazole)to amplify the diffusion difference of C_(2)H_(4)and C_(2)H_(6).Through adjusting the synthesis temperature,reactant concentration,and ligands/metal ions molar ratio,ZnAtzPO4 crystals with different sizes were obtained.Both single-component kinetic adsorption tests and binary-component dynamic breakthrough experiments confirmed the enhancement of the dynamic separation of C_(2)H_(4)/C_(2)H_(6)with the increase in the crystal size of ZnAtzPO_(4).The separation selectivity of C_(2)H_(4)/C_(2)H_(6)increased from 1.3 to 98.5 with the increase in the crystal size of ZnAtzPO_(4).This work demonstrated the role of morphology and size control of adsorbent crystals in the improvement of the C_(2)H_(4)/C_(2)H_(6)kinetic separation performance.

Volume-averaged modeling of multiphase solidification with equiaxed crystal sedimentation in a steel ingot

Macrosegregation is a critical factor that limits the mechanical properties of materials.The impact of equiaxed crystal sedimentation on macrosegregation has been extensively studied,as it plays a significant role in determining the distribution of alloying elements and impurities within a material.To improve macrosegregation in steel connecting shafts,a multiphase solidification model that couples melt flow,heat transfer,microstructure evolution,and solute transport was established based on the volume-averaged Eulerian-Eulerian approach.In this model,the effects of liquid phase,equiaxed crystals,columnar dendrites,and columnar-to-equiaxed transition(CET)during solidification and evolution of microstructure can be considered simultaneously.The sedimentation of equiaxed crystals contributes to negative macrosegregation,where regions between columnar dendrites and equiaxed crystals undergo significant A-type positive macrosegregation due to the CET.Additionally,noticeable positive macrosegregation occurs in the area of final solidification in the ingot.The improvement in macrosegregation is beneficial for enhancing the mechanical properties of connecting shafts.To mitigate the thermal convection of molten steel resulting from excessive superheating,reducing the superheating during casting without employing external fields or altering the design of the ingot mold is indeed an effective approach to control macrosegregation.

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.