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.

Deep decalcification of factory-provided freezing acidolysis solution to achieveα-high-strength gypsum

The freezing acidolysis solution of the nitric acid-phosphate fertilizer process has a high calcium content,which makes it difficult to produce fine phosphate and high water-soluble phosphate fertilizer products.Here,based on the potential crystallization principle of calcium sulfate in NH_(4)NO_(3)-H_(3)PO_(4)-H_(2)O,the deep decalcification(i.e.calcium removal)technology to achieveα-high-strength gypsum originated from freezing acidolysis-solutions has been firstly proposed and investigated.Typically,calcium can be removed from the factory-provided freezing acidolysis-solution by neutralizing it with ammonia,followed by the addition of ammonium sulfate solution.As a result,the formation of calcium sulfate in the reaction system undergoes the nucleation and growth of CaSO_(4)·2H_(2)O(DH),as well as its dissolution and crystallization into short columnarα-CaSO_(4)·0.5H_(2)O(α-HH).Remarkably,with the molar ratio of SO_(4)^(2-)/Ca^(2+)at 1.8,the degree of neutralization(NH_(3)/HNO_(3) molar ratio)at 1.7,the reaction temperature of 94℃,and the reaction time of 300 min,the decalcification rate can reach 86.89%,of which the high-strengthα-CaSO_(4)·0.5H_(2)O(α-HH)will be obtained.Noteworthy,the deep decalcification product meets the standards for the production of fine phosphates and highly water-soluble phosphate fertilizers.Consequently,the 2 h flexural strength ofα-HH is 5.3 MPa and the dry compressive strength is 36.8 MPa,which is up to the standard of commercialα-HH.

Recent Developments in the Crystallization Process： Toward the Pharmaceutical Industry

Crystallization is one of the oldest separation and purification unit operations, and has recently contributed to significant improvements in producing higher-value products with specific properties and in building efficient manufacturing processes. In this paper, we review recent developments in crystal engineering and crystallization process design and control in the pharmaceutical industry. We systematically summarize recent methods for understanding and developing new types of crystals such as co-crystals, polymorphs, and solvates, and include several milestones such as the launch of the first co-crystal drug, Entresto （No- vartis）, and the continuous manufacture of Orkambi （Vertex）. Conventional batch and continuous processes, which are becoming increasingly mature, are being coupled with various control strategies and the recently developed crystallizers are thus adapting to the needs of the pharmaceutical industry. The development of crystallization process design and control has led to the appearance of several new and innovative crystal- lizer geometries for continuous operation and improved performance. This paper also reviews major recent orogress in the area of process analytical technology.

Ultrasound assisted crystallization of cephalexin monohydrate:Nucleation mechanism and crystal habit control

With the high-quality requirements for cephalexin monohydrate,developing a robust and practical crystallization process to produce cephalexin monohydrate with good crystal habit,appropriate aspect ratio and high bulk density as well as suitable flowability is urgently needed.This research has explored the influence of ultrasound on crystallization of cephalexin monohydrate in terms of nucleation mechanism and crystal habit control.The results of metastable zone width and induction time measurement showed the presence of ultrasound irradiation can narrow the metastable zone and shorten induction time.Cavitation phenomena generated by ultrasound were used to qualitatively explain the mechanism of ultrasound promoting nucleation of cephalexin monohydrate.Furthermore,on the basis of classical nucleation theory and induction time data,a series of nucleation-related parameters(such as crystalliquid interfacial tension,radius of the critical nucleus and etc.)were calculated and showed a decreasing trend under ultrasound irradiation.The diffusion coefficient of the studied system was also determined to increase by 72.73%under ultrasound.The changes in these parameters have quantitatively confirmed the mechanism of ultrasound influence on the nucleation process.In further,the calculated surface entropy factor has confirmed that the growth of cephalexin monohydrate follows continuous growth mechanism under the research conditions of this work.Through the exploration of crystallization conditions,it is found that suitable ultrasonic treatment,seeding,supersaturation control and removal of fine crystals are conducive to improving the quality of cephalexin monohydrate product.Optimizing the crystallization process coupled continuous ultrasound irradiation with fine-crystal dissolution policy has achieved the controllable production of monodisperse cephalexin monohydrate crystal with good performance.

Phase Regulation and Defect Passivation Enabled by Phosphoryl Chloride Molecules for Efficient Quasi‑2D Perovskite Light‑Emitting Diodes

Quasi-2D perovskites have attracted tremendous interest for application as lightemission layers in light-emitting diodes(LEDs).However,the heterogeneous n phase and non-uniform distribution still severely limit the further development of quasi-2D perovskite LEDs(Pero-LEDs).Meanwhile,the increased defect density caused by the reduced dimension and grain size induces non-radiative recombination and further deteriorates the device performance.Here,we found that a series of molecules containing phosphoryl chloride functional groups have noticeable enhancement effects on the device performance of quasi-2D Pero-LEDs.Then,we studied the modification mechanism by focusing on the bis(2-oxo-3-oxazolidinyl)phosphinic chloride(BOPCl).It is concluded that the BOPCl can not only regulate the phase distribution by decreasing the crystallization rate but also remain in the grain boundaries and passivate the defects.As a result,the corresponding quasi-2D Pero-LEDs obtained a maximum external quantum efficiency(EQE_(max))of 20.82%and an average EQE(EQE_(ave))of around 20%on the optimal 50 devices,proving excellent reproducibility.Our work provides a new selection of molecular types for regulating the crystallization and passivating the defects of quasi-2D perovskite films.

Crystal Facet Engineering of TiO_(2) Nanostructures for Enhancing Photoelectrochemical Water Splitting with BiVO_(4) Nanodots

Although bismuth vanadate(BiVO4)has been promising as photoanode material for photoelectrochemical water splitting,its charge recombination issue by short charge diffusion length has led to various studies about heterostructure photoanodes.As a hole blocking layer of BiVO4,titanium dioxide(TiO_(2)) has been considered unsuitable because of its relatively positive valence band edge and low electrical conductivity.Herein,a crystal facet engineering of TiO_(2) nanostructures is proposed to control band structures for the hole blocking layer of BiVO4 nanodots.We design two types of TiO_(2) nanostructures,which are nanorods(NRs)and nanoflowers(NFs)with different(001)and(110)crystal facets,respectively,and fabricate BiVO4/TiO_(2) heterostructure photoanodes.The BiVO4/TiO_(2) NFs showed 4.8 times higher photocurrent density than the BiVO4/TiO_(2) NRs.Transient decay time analysis and time-resolved photoluminescence reveal the enhancement is attributed to the reduced charge recombination,which is originated from the formation of type II band alignment between BiVO4 nanodots and TiO_(2) NFs.This work provides not only new insights into the interplay between crystal facets and band structures but also important steps for the design of highly efficient photoelectrodes.

Synthesis of LiFePO_4 using FeSO_4·7H_2O byproduct from TiO_2 production as raw material

As the byproduct of TiO2 industrial production, impure FeSO4.7H2O was used for the synthesis of LiFePO4. With the purified solution of FeSO4-7H2O, FePO4.xH2O was prepared by a normal titration method and a controlled crystallization method, respectively. Then LiFePO4 materials were synthesized by calcining the mixture of FePO4,xH2O, LizCO3, and glucose at 700℃ for 10 h in flowing Ar. The results indicate that the elimination of FeSO4.TH2O impurities reached over 95%, and using FePO4-xH2O prepared by the controlled crystallization method, the obtained LiFePO4 material has fine and sphere-like particles. The material delivers a higher initial discharge specific capacity of 149 mAh.g^-1 at a current density of 0.1C rate （1C = 170 mA.g^-0）; the discharge specific capacity also maintains above 120 rnAh.g^-1 after 100 cycles even at 2C rate. Thus, the employed processing is promising for easy control, low cost of raw material, and high electrochemical performance of the prepared material.

Preparation of spherical cobalt carbonate powder with high tap density

Spherical cobalt carbonate with high tap density, good crystallization and uniform particle size was prepared by controlled chemical crystal method using cobalt chloride and ammonium bicarbonate as cobalt source and precipitator. The effects of pH value and reaction time on crystallization and physical properties of cobalt carbonate were studied. The results show that the key factors influencing the preparation process of spherical cobalt carbonate with high tap density and good crystallization are how to control pH value (7.25±0.05) and keep some reaction time (about 10 h). Co4O3 was prepared by sintering spherical morphology CoCO3 samples at varied temperatures. The results show that as the decomposition temperature increases, the as-obtained Co4O3 products with porous structure transform into polyhedral structure with glazed surface, and simultaneously the cobalt content and tap density increase. However, the specific surface area shows a trend of decrease.

New design of high-precision oven controlled crystal oscillator

Combining oven controlled technique,digital compensation,high-resolution frequency difference measurement and self-calibration technique,a new design method of precise oven controlled crystal oscillator（OCXO） is proposed.Fine compensation is made in the vicinity of the crystal temperature inflection point by using the non-real-time temperature compensation strategy,and self-calibration system is integrated in the crystal.The method improves the digital compensated phase noise,simplifies the traditional OCXO development system,reduces the cost and shortens the developing cycle.Experiment results show that with a standard reference signal and self-calibration updated data,the oscillator can work stable and achieve its best performence.The performance index of crystal oscillator had an improvement with one to two orders of magnitude on the basis of original technical index.The method is widely used in the improvement of high-end crystal oscillator and atomic clock.

Atmospheric stable and fexible Sn-based perovskite solar cells via a bioinspired antioxidative crystal template

Sn-based perovskite solar cells(PSCs)demonstrate a potential development in eco-friendly devices due to their hypotoxicity.However,poor stability and crystalline quality are still the challenges for achieving high-performance and long-term operating devices.In this work,inspired by biological protein,nickelporphyrin(Ni-P)with electron cloud on conjugate ring is applied into Sn-based perovskite to prevent perovskite from being eroded.The synergistic effect of water and oxygen is broken in grain boundaries and surface so that the stability of PSCs can be improved obviously,despite there is hardly any barrier for water to erode.Simultaneously,the electron-rich molecules can passivate the defects of perovskite such as iodine vacancy.Moreover,the ester group in Ni-P molecule can bind with SnI;to form complex and then restrain nucleation.Combining with the template effect of 2D molecular,the crystallization of perovskite films is optimized.Therefore,the Sn-based PSCs with Ni-P achieve a stabilized power conversion efficiency(PCE)of 7.79%with negligible hysteresis in fexible devices,respectively.Moreover,the PSCs can maintain 80%of the pristine PCE after 300 h under air environment.

The Preparation of Ultra-fine Calcium Carbonate and Its properties Study

This article adopts the double decomposition method, select the appropriate experimental conditions and operation process, respectively add appropriate amount of sodium carboxymethyl cellulose （CMC） as crystal control agent to study the influence of crystalline of ultrafine calcium carbonate. The experimental results show that the different concentrations of CMC as crystal control agent on the morphology and crystal structure of calcium carbonate have obvious effect, which emerge morphology change from square to spherical, crystalline transition from calcite to aragonite. Thus, the results provide experimental data and theoretical basis for the use of different additives, and provide experimental basis and feasible solution for this kind of reaction.

Crystal phase control and ignition properties of HNS/CL-20 composite microspheres prepared by microfluidics combined with emulsification techniques

Improved controllability and energy density of ignition agents are of great significance for the devel-opment of energetic composite materials.In this study,droplet microfluidics and emulsification tech-niques were combined to prepare HNS/CL-20 composite microspheres with polyglycidyl azide polymer(GAP)as the binder.The influence of binder content on the morphology of microspheres was investi-gated,and the microspheres were characterized and tested for particle size,crystal structure,thermal decomposition,dispersibility,mechanical sensitivity,combustion behavior and detonation performance.The results showed that microspheres prepared with a binder content of 3%had higher sphericity and particle size uniformity.The microspheres retained the crystal structure of both HNS and CL-20(ε-type).Compared with raw HNS,the microspheres had higher apparent activation energy,better safety per-formance,and good dispersibility.The ignition experiments and detonation performance tests show that HNS/CL-20 composite microspheres have excellent ignition performance,obvious combustion flame,and significant energy release effects,which are expected to achieve high energy and high-speed response of the igniter,thus improving the ignition reliability in special environments or systems.

Applications of the crystallization process in the pharmaceutical industry

The applications of the crystallization technique in the pharmaceutical industry as a purification and separation process for the isolation and synthesis of pure active pharmaceutical ingredients(API),co-crystals,controlled release pulmonary drug delivery,and separation of chiral isomers are briefly discussed using a few case studies.The effect of process variables and solvent on the polymorphism and morphology of stavudine is discussed.The implementation of external control in the form of feedback and real-time optimal control using cooling and antisolvent crystallization of paracetamol in water-isopropyl alcohol is introduced.Two methods to prepare micronsized drug particles,namely,micro-crystallization and polymer-coated API-loaded magnetic nanoparticles for pulmonary drug delivery,are discussed.The significance of co-crystals in drug administration is highlighted using the theophylline-nicotinamide co-crystal system.Resolution of chloromandelic acid derivatives,a racemic compound,is achieved using direct crystallization and diastereomeric salts crystallization.The crystal structures of diastereomeric salts of chloromandelic acid and phenylethylamine are determined.The structure comparison between the less soluble and more soluble salts shows that weak interactions such as CH/πinteractions and van der Waals forces contribute to chiral recognition when the hydrogen bonding patterns are similar.

Crystal phase control in two-dimensional materials

It is the nature of crystals to exist in different polymorphs. The recent emergence of two-dimensional(2 D) materials has evoked the discovery of a number of new crystal phases that are different from their bulk structures at ambient conditions, and revealed novel structure-dependent properties, which deserve in-depth understanding and further exploration. In this contribution, we review the recent development of crystal phase control in 2 D materials, including group V and VI. transition metal dichalcogenides(TMDs), group IVA metal chalcogenides and noble metals. For each group of materials, we begin with introducing the various existing crystal phases and their structure-related properties, followed by a detailed discussion on factors that influence these crystal structures and thus the possible strategies for phase control. Finally, after summarizing the whole paper, we present the challenges and opportunities in this research direction.

Efficient and stable Ruddlesden-Popper layered tin-based perovskite solar cells enabled by ionic liquid-bulky spacers

The crucial component,bulky spacers,in two-dimensional Ruddlesden-Popper(2 DRP)layered tin(Sn)perovskites are highly limited by halide ammonium salts,leading to the insufficient control of complex crystallization process due to the limited interaction between bulky spacers and 2 DRP perovskite frameworks.Here,we report an ionic liquid-bulky spacer,butylammounium acetate(BAAc O),for constructing efficient and stable 2 DRP Sn-based perovskite solar cells(PSCs).In contrast to the traditional halide ammonium bulky spacer,butylammounium iodide(BAI),the Ac O^(-)-functional group in BAAc O has a strong interaction with formamidine ions(FA^(+))and Sn2+.The inter-component interaction allows the formation of controllable intermediates for the favorable growth of smooth,dense,and highly oriented perovskite films.A PSC with power conversion efficiency of 10.36%(7.16%for BAI)is achieved,which is the highest report,along with improved stability with~90%retained after~600 h storage in N_(2) atmosphere without any encapsulation.

Coarsening Behavior of Gamma Prime Precipitates in a Nickel Based Single Crystal Superalloy

The γ/γ＇ microstructural evolution in a nickel based single crystal superalloy during load-free thermal exposure at 900 ℃ has been further investigated in this paper. The growth characteristics of γ＇ precipitates were discussed in detail. The generation of interfacial dislocations would accelerate the rate of coalescence in the dendrite arms. The average sizes of precipitates were used to compare interface with diffusion controlled growth mechanism and no mechanism seems obviously dominant, although the square rate law gives slightly better fit. The coarsening behavior may be controlled by diffusion through the ragged interface between the γ＇ precipitate and the y matrix.

Diffusion-reaction compromise the polymorphs of precipitated calcium carbonate

Diffusion is seldom considered by chemists and materialists in the preparation of materials while it plays an important role in the field of chemical engineering. If we look at crystallization at the atomic level, crystal growth in a solution starts from the diffusion of ions to the growing surface followed by the incorporation of ions into its lattice. Diffusion can be a rate determining step for the growth of crystals. In this paper, we take the crystallization of calcium carbonate as an example to illustrate the microscopic processes of diffusion and reaction and their compromising influence on the morphology of the crystals produced. The diffusion effect is studied in a specially designed three-cell reactor. Experiments show that a decrease of diffusion leads to retardation of supersaturation and the formation of a continuous concen- tration gradient in the reaction cell, thus promoting the formation of cubic calcite particles. The reaction rate is regulated by temperature. Increase of reaction rate favors the formation of needle-like aragonite particles. When diffusion and reaction play joint roles in the reaction system, their compromise dominates the formation of products, leading to a mixture of cubic and needle-like particles with a controllable ratio. Since diffusion and reaction are universal factors in the preparation of materials, the finding of this paper could be helpful in the controlled synthesis of other materials.

Measurement, modelling, and closed-loop control of crystal shape distribution： Literature review and future perspectives

Crystal morphology is known to be of great importance to the end-use properties of crystal products, and to affect down-stream processing such as filtration and drying. However, it has been previously regarded as too challenging to achieve automatic closed-loop control. Previous work has focused on controlling the crystal size distribution, where the size of a crystal is often defined as the diameter of a sphere that has the same volume as the crystal. This paper reviews the new advances in morphological population balance models for modelling and simulating the crystal shape distribution （CShD）, measuring and estimating crystal facet growth kinetics, and two- and three-dimensional imaging for on-line characterisation of the crystal morphology and CShD. A framework is presented that integrates the various components to achieve the ultimate objective of model-based closed-loop control of the CShD. The knowledge gaps and challenges that require further research are also identified.

Analysis and Design of an Improved Servo System for Rubidium Atomic Frequency Standard

In this paper, we analyze and design a new type of servo system with noninteger voltage controlled crystal oscillator （VCXO） for rubidium atomic frequency standard （RAFS）, which does not require fractional frequency synthesizer. By the estab- lishment of the loop equations with noises and drifts, we prove that all the components of the loop can affect its performance in- dex, and in which, RAFS long-term frequency stability is mainly determined by frequency multiplier, quantum system, and servo amplifier; the short-term one is mostly decided by VCXO. Owing to the elimination of the frequency synthesizer and its additive mixing unit, we can reduce phase noise and stray of the servo sys- tem, and it is favorable for miniaturizing the RAFS system. In addition, we adopt some targeted optimization measures to im- prove the frequency stability index. The good short-term fre- quency stability index is also validated by the test results.

Temperature Insensitive Open Loop Attenuation Control of a Liquid Crystal Based VOA

A patent pending open-loop liquid crystal based variable optical attenuator is introduced. The temperature dependent performance is compensated through electric monitoring and adjustment utilizing liquid crystal's opto-electronic properties.