Experiments and model development of p-nitrochlorobenzene and naphthalene purification in a continuous tower melting crystallizer

With the increasing demand for high-purity products,the industrial application of melt crystallization technology has been highly concerned.In this study,the purification process of nitrochlorobenzene binary eutectic system(NBES)and naphthalene–benzothiophene solid solution system(NBSSS)in tower melting crystallizer is analyzed,and a mathematical model of crystallization process is established.The key parameters in terms of feed concentration,crystal bed height,reflux ratio and stirring speed effi-ciency on purification effects were discussed by the established model.The results show that the concentration of p-nitrochlorobenzene was purified from 90.85%to 99.99%,when the crystal bed height is 600 mm,the reflux ratio is 2.5,and the stirring speed is 12 rmin^(-1).The naphthalene concentration is purified from 95.89%to 99.99%,when the crystal bed height is 400 mm,the reflux ratio is 1.43,and the stirring speed is 16 rmin^(-1).The quality of the model is evaluated by the ARD(average relative deviation).The minimum ARD values of the NBES and NBSSS are 2.39%and 5.22%,respectively,indicating the model satisfactorily explains the purification process.

Continuous Reaction Crystallization of Struvite in a DTM Type Crystallizer With Jet Pump of Ascending Suspension Flow in a Mixing Chamber–Kinetic Approach of the Process

Reaction crystallization of struvite in water solutions containing 0.20 mass % of phosphate(V) ions by magnesium and ammonium ions addition was investigated experimentally. Process was carried out in DTM type crystallizer with liquid jet pump device in 298 K assuming stoichiometric conditions. Struvite crystals of mean size Lm 5.2-23.0 μm were produced depending on pH (9-11) and mean residence time of suspension in a crystallizer τ (900-3600 s). Under these conditions linear growth rate of struvite crystals (SIG MSMPR kinetic model) decreased 2-time with the increase in pH and 3-time with the elongation of mean residence time of crystal suspension from 7.11×10-9 m/s (pH 9, τ900 s) to 1.65×10-9 m/s (pH 11, τ3600 s). Nucleation rate varied within the 7.9×108-1.8×1010 1/(sm3) limits. Struvite product of maximal linear size exceeded 100 μm with 10 vol. % of < 3 μm fraction corresponded to pH 9 and τ3600 s.

FINITE ELEMENT SIMULATION OF THICKNESS OF EXIT SLAB SHELL IN CRYSTALLIZER

An enthalpy finite element analysing software is developed. The software can trace the growing process of the slab shell of the crystallizer in the continuous casting and can calculate the surface temperature distribution. By this, the operator can know the solidifying state and the exit thickness of the cast slab's each section in the crystallizer. The software has great significance in production and practice.

Modeling and Estimation of the Kinetics of Seeded Solvent-mediated Phase Transformation in a Batch Crystallizer

Modeling the kinetics of the preparing process is necessary to produce a product with the appropriate particle properties and minimum production cost.Owing to the lackness of crystal size distributor （CSD） information,however,solvent-mediated phase transformation encounters difficulty in modeling the kinetics as compared to solution crystallization.Consequently,a model was established by making the product CSD to move along by horizontal translation to obtain the CSDs of the stable phase in the process of transformation.Then the moment method was used to solve the popular balance equation,and the least square nonlinear regression method was applied to estimate the kinetics parameters.The model has been successfully used to simulate the transformation of CaSO4？2H2O to α-CaSO4？1/2H2O in an isothermal seeded batch crystallizer with different stirring speeds,and it is beneficial to producing high performance α-CaSO4？1/2H2O crystals which have the right particle characteristics.

Estimation of secondary nucleation kinetics of benzoic acid in batch crystallizer

The nucleation and growth kinetics of benzoic acid were determined in a population balance model,describing the seeded batch antisolvent crystallization process.The process analytical technologies(PATs)were utilized to record the evolution of chord length distributions(CLDs)in solid phase together with the concentration decay in liquid phase,which provided essential experimental information for parameter estimation.The model was solved using standard method of moments based on the moments calculated from CLDs and solute concentration.A developed model,incorporating the nucleation and crystal growth as functions of both supersaturation and solvent composition,has been constructed by fitting the zeroth moment of particles and concentration trends.The determined kinetic parameters were consequently validated against a new experiment with a different flow rate,indicating that the developed model predicted crystallization process reasonably well.This work illustrates the strategy in construct a population balance model for further simulation,model-based optimization and control studies of benzoic acid in antisolvent crystallization.

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).

Perception of fundamental science to boost lithium metal anodes toward practical application

As a key material for lithium metal batteries(LMBs),lithium metal is one of the most promising anode materials to break the bottleneck of battery energy density and a commonly used active material for reference electrodes.Although lithium anodes are regarded as the holy grail of lithium batteries,decades of exploration have not led to the successful commercialization of LMBs,due mainly to the challenges related to the inherent properties of lithium metal.To pave the way for further investigation,herein,a comprehensive review focusing on the fundamental science of lithium are provided.Firstly,the natures of lithium atoms and their isotopes,lithium clusters and lithium crystals are revisited,especially their structural and energetic properties.Subsequently,the electrochemical properties of lithium metal are reviewed.Numerous important concepts and scientific questions,including the electronic structure of lithium,influence of high pressure and low temperature on the properties of lithium,factors influencing lithium deposition,generation of lithium dendrites,and electrode potential of lithium in different electrolytes,are explained and analyzed in detail.Approaches to improve the performance of lithium anodes and thoughtfulness about the electrode potential in lithium battery research are proposed.

Geochemistry and mineral chemistry of the armoor granitoids,eastern dharwar craton: implications for the redox conditions and tectono-magmatic environment

The mineralogical and geochemical characteristics of the K-rich granites from the Armoor granitic rocks in the northeastern portion of the Eastern Dharwar Craton(EDC) are presented.In order to understand its physicochemical conditions,the petrogenesis of the granitoid was explained from biotite chemistry and geochemical systematics.Studies of mineral chemistry expose that compositionally,K-feldspar and plagioclase in Armoor granite rocks range from An0,Ab_(3-5.9),Or_(94-96.9) and An_(5-29,-Ab71.9-94.9),Or_(0-1.5),respectively.The mineral chemistry of biotite crystals exhibits composition that varies from primary to re-equilibrated primary biotites.Although biotites from the Armoor granites generally exhibit an I-type trend,with calc-alkaline parental magma in a subduction setting.Biotite chemistry of granites displays magnetite(oxidized)series nature,which has oxygen fugacity(fO_(2))=-15.1 to-16.7(log_(10) bar),under high oxidizing conditions.Temperature and pressure estimates for the crystallization of Armoor granites based on biotite composition are T=612-716 ℃ and 1.0-0.4 kbar,respectively.Geochemically,these rocks are metaluminous to slightly peraluminous and magnesian,with calc-alkaline potassiumrich granite.On the chondrite normalized REE diagram,the granites have positive europium anomalies;rich Sr/Y,(Dy/Yb)_(N) ratios and reduced Mg#,Rb/Sr,Rb,Sr indicate that the melting of earlier rocks,crystal accumulation and residual garnet source formed at high pressures.The examined granites show that they are produced from the melting of crustal sources.Thus,the extensive analyses of the described Armoor granite suggest that they were produced by crust sources and developed under oxidizing conditions in subduction setting.

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.

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.

Microstructure and forming mechanism of metals subjected to ultrasonic vibration plastic forming: A mini review

Compared with traditional plastic forming,ultrasonic vibration plastic forming has the advantages of reducing the forming force and improving the surface quality of the workpiece.This technology has a very broad application prospect in industrial manufactur-ing.Researchers have conducted extensive research on the ultrasonic vibration plastic forming of metals and laid a deep foundation for the development of this field.In this review,metals were classified according to their crystal structures.The effects of ultrasonic vibration on the microstructure of face-centered cubic,body-centered cubic,and hexagonal close-packed metals during plastic forming and the mech-anism underlying ultrasonic vibration forming were reviewed.The main challenges and future research direction of the ultrasonic vibra-tion plastic forming of metals were also discussed.

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.

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.

Biomineralization and mineralization using microfluidics:A comparison study

Biomineralization through microbial process has attracted great attention in the field of geotechnical engineering due to its ability to bind granular materials,clog pores,and seal fractures.Although minerals formed by biomineralization are generally the same as that by mineralization,their mechanical behaviors show a significant discrepancy.This study aims to figure out the differences between biomineralization and mineralization processes by visualizing and tracking the formation of minerals using microfluidics.Both biomineralization and mineralization processes occurred in the Y-shaped sandcontaining microchip that mimics the underground sand layers.Images from different areas in the reaction microchannel of microchips were captured to directly compare the distribution of minerals.Crystal size and numbers from different reaction times were measured to quantify the differences between biomineralization and mineralization processes in terms of crystal kinetics.Results showed that the crystals were precipitated in a faster and more uncontrollable manner in the mineralization process than that in the biomineralization process,given that those two processes presented similar precipitation stages.In addition,a more heterogeneous distribution of crystals was observed during the biomineralization process.The precipitation behaviors were further explained by the classical nucleation crystal growth theory.The present microfluidic tests could advance the understanding of biomineralization and provide new insight into the optimization of biocementation technology.

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.

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.

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.

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.

Stability analysis of a liquid crystal elastomer self-oscillator under a linear temperature field

Self-oscillating systems abound in the natural world and offer substantial potential for applications in controllers,micro-motors,medical equipments,and so on.Currently,numerical methods have been widely utilized for obtaining the characteristics of self-oscillation including amplitude and frequency.However,numerical methods are burdened by intricate computations and limited precision,hindering comprehensive investigations into self-oscillating systems.In this paper,the stability of a liquid crystal elastomer fiber self-oscillating system under a linear temperature field is studied,and analytical solutions for the amplitude and frequency are determined.Initially,we establish the governing equations of self-oscillation,elucidate two motion regimes,and reveal the underlying mechanism.Subsequently,we conduct a stability analysis and employ a multi-scale method to obtain the analytical solutions for the amplitude and frequency.The results show agreement between the multi-scale and numerical methods.This research contributes to the examination of diverse self-oscillating systems and advances the theoretical analysis of self-oscillating systems rooted in active materials.