CRYSTAL RESEARCH AND TECHNOLOGY
·
2024
·Vol. 59
·期 2
·2300264
·
IF 1.5
Hongyan Cui,Liangcheng Song,Sheng Lv,Chongqiang Zhu,Chunhui Yang
Seeding metastable zone of itaconic acid in water is determined using a laser dynamic detecting technique, based on which feedback supersaturation control is performed for the crystallization process. The crystallization is strictly confined within the metastable zone throughout the whole process to effectively inhibit the secondary nucleation and the strategy of seed loading is employed to avoid the burst of primary nucleation, resulting in the uniform particle size distribution. With the aid of solution information, continuous feedback control is conducted to keep the supersaturation at a high level accelerating the crystal growth, which significantly shortens the time consumption, and also the effect of seed amount is discussed in this work.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CRYSTENGCOMM
·
2024
·Vol. 26
·期 9
·1303-1311
·
IF 2.6
Shuyue Miao,Fangbao Jiao,Ying Wang,Qi Zhang,Suming Jing,Hongzhen Li,Xin Zhou
Compared with jagged and rod-like raw products, the spherulitic 3-nitro-1,2,4-triazol-5-one (NTO) crystalline powder is generally superior in the formulation. However, the growth mechanism and corresponding influential factors for NTO spherulites remain to be deeply explored. Herein, the morphological evolutions of NTO crystals in alcohol solvents under a range of maximum supersaturation (Smax) are systematically investigated. It was found that differences in solvent-crystal interface interactions determine the primary morphology of the growing crystals while the magnitude of Smax determines the subsequent polycrystalline evolution. The cooling rate, initial concentration and stirring rate all could affect the crystal morphology by changing the Smax. It is demonstrated that there exists a critical Smax range (1.75–1.88) above which the formation of spherulites is kinetically favorable. Face indexing tests suggest that the (0 0 1) plane of NTO is mostly prone to twinning at low supersaturation, which is because that the molecular layers on the (0 0 1) surface are prone to twisting and the energy difference before and after is only 8.77 kJ mol−1. Then, the interfacial growth theory is employed to explain how a growing crystal plane develops from smooth to rough with non-crystallographic sub-individuals as the crystallization driving force increases. The change of morphology has a positive consequence in improving the safety performance of NTO crystalline powder under drop-weight impact. These findings would forward the understanding of the spherulitic crystallization process for energetic crystals.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
CRYSTENGCOMM
·
2025
·
IF 2.6
Fujian Li,Min Li,Zhibo Zhu,Yuan Liu,Dandan Han
L-tryptophan, an essential amino acid for protein synthesis and neurotransmitter regulation, tends to crystallize in flake crystals in the crystallization process, resulting in difficulty in processability and poor product quality. Faced with this challenge, in this work, the approach of spherulite growth induced by the polymeric additive was applied to form spherulites of L-tryptophan with effectively improved powder properties. In detail, L-tryptophan spherulites were fabricated through cooling crystallization under the effect of hydroxypropyl methylcellulose (HPMC). Then, the formation mechanism of L-tryptophan spherulites was analyzed based on the results of experiments and molecular simulations. Besides, the effect of supersaturation coupling additive concentration on the morphology of L-tryptophan spherulites was investigated. It turns out that the formation of L-tryptophan spherulites follows the classical non-crystallographic branching for spherulitic growth, in which HPMC preferentially adsorbs on the (001) face of L-tryptophan to introduce stress triggering the branching. Furthermore, the tap density of the prepared L-tryptophan spherulites was improved and nearly 4 times that of the L-tryptophan flake crystals, and the angle of repose of the L-tryptophan flake crystals was 46°, while the angle of repose of L-tryptophan spherulites was 29°, exhibiting the improved flowability for the post-processing. To sum up, this study provides a feasible method for the manufacture of L-tryptophan crystals with good product quality, as well as making efforts to reveal the mechanism of spherulitic growth, which may provide new insight into the structure design of organic crystals.
研究领域:
晶体工程
·
药学
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材料科学
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高分子科学
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物理化学
✓ 已验证
产品关联
DOI
高影响因子
Particuology
·
2021
·
IF 3.067
Jinbo Ouyang,Xiaohong Xing,Jian Chen,Limin Zhou,Zhirong Liu,Jerry Y.Y. Heng
Swift cooling crystallization of vanillin was investigated in water, ethanol, isopropanol and ethyl acetate. Morphology and polymorph evolution of vanillin were discussed in terms of solvent, supersaturation ratio and silica template. PXRD, DSC, FTIR and microscope were used to identify polymorphs of vanillin. Results showed that the nucleated polymorphs of vanillin depended largely on the solvent, supersaturation ratio and silica template. Low supersaturation ratios favor the nucleation of stable form I in water, and high supersaturation ratio exceeds 7 generating 100% metastable form II. However, if the supersaturation ratio is too high ( S >8), liquid–liquid phase separation will occur, and no crystals could be obtained. In other solvents such as ethanol, isopropanol and ethyl acetate, only form I was obtained. However, it should be noted that the morphology of form I prepared in ethanol, isopropanol and ethyl acetate is distinct from that obtained in water, the former is flake-like and the latter is rod-like. The nucleation of vanillin from different solution was also studied with the presence of SiO 2 , SiO 2 –NH 2 and SiO 2 −COOH templates, which did not change the nucleated polymorph of vanillin, but changed the nucleation and growth rate of stable form I.
研究领域:
化学工程
·
材料科学
·
晶体学
✓ 已验证
DOI
高影响因子
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
·
2017
·Vol. 24
·期 6
·5791-5799
·
IF 2.741
Dai Hongliang,Lu Xiwu,Peng Yonghong,Yang Zixuan,Zhsssu Huaqing
The HAP crystallization for phosphorus removal from wastewater contributes to an environmental friendly production due to the fact that it helps reduce or eliminate the water eutrophication as well as increases the recovery of mineral resources. However, the generated microcrystalline with poor settleability in high levels of supersaturation solution has a negative effect on the phosphorus recovery efficiency. To overcome the drawback, multiple reagent feed ports (four feed ports) and different recirculation ratio (1.0, 1.5, 2.0, 2.5, 3.0) were investigated to control the levels of supersaturation in an air-agitated reactor with calcite as seeds. Results showed that the approach of multiple reagent feed ports could improve the conversion ratio of orthophosphate, but it had a limited effect (∼3% improvement) on phosphorus recovery efficiency (deposition on the seeds). With the increase of the recirculation ratio, the recovery efficiency was increased gradually and reached an optimal value of 85.63% under the recirculation ratio of 2.5 and four feed ports. This is because the adopted strategies could reduce the level of supersaturation by diluting the concentration of the reagents and inhibit large numbers of microcrystalline coinstantaneous occurrence. Meanwhile, the crystallized products were detected and analyzed by scanning electron micrograph (SEM) with energy-dispersive spectrometry (EDS) and X-ray diffraction (XRD), which were proved to be HAP with a high purity. Collectively, these results demonstrated that supersaturation control using conventional approaches had a limited improvement on the phosphorus recovery efficiency in the form of HAP, and the new control strategies for supersaturation dispersion should be developed in the further study.
研究领域:
环境工程
·
化学工程
·
资源回收
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水处理技术
·
结晶过程
✓ 已验证
DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-10
·
IF 14.7
Chen Xue-Guang,Lin Linhan,Huang Guan-Yao,Chen Xiao-Mei,Li Xiao-Ze,Zhou Yun-Ke,Zou Yixuan,Fu Tairan,Li Peng,Li Zhengcao,Sun Hong-Bo
Crystallization is a fundamental phenomenon which describes how the atomic building blocks such as atoms and molecules are arranged into ordered or quasi-ordered structure and form solid-state materials. While numerous studies have focused on the nucleation behavior, the precise and spatiotemporal control of growth kinetics, which dictates the defect density, the micromorphology, as well as the properties of the grown materials, remains elusive so far. Herein, we propose an optical strategy, termed optofluidic crystallithography (OCL), to solve this fundamental problem. Taking halide perovskites as an example, we use a laser beam to manipulate the molecular motion in the native precursor environment and create inhomogeneous spatial distribution of the molecular species. Harnessing the coordinated effect of laser-controlled local supersaturation and interfacial energy, we precisely steer the ionic reaction at the growth interface and directly print arbitrary single crystals of halide perovskites of high surface quality, crystallinity, and uniformity at a high printing speed of 10 2 μm s −1 . The OCL technique can be potentially extended to the fabrication of single-crystal structures beyond halide perovskites, once crystallization can be triggered under the laser-directed local supersaturation.
研究领域:
材料科学
·
光学
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CERAMICS INTERNATIONAL
·
2023
·
IF 5.2
Lu Liu,Shuzhong Wang,Wei Liu,Jinlong Wang,Baoquan Zhang,Jianqiao Yang,Hui Liu,Yanhui Li
In this paper, ZnO particles with the particle size as low as 23 nm were successfully prepared by supercritical hydrothermal synthesis technique. The particle size of nano-ZnO decreased with the increase of temperature and pressure. Nano-ZnO particles in ZnSO 4 system were spherical with smaller particle size. The discrepancy in nano-ZnO produced by different precursor of Zn(NO 3 ) 2 , Zn(CH 3 COO) 2 or ZnSO 4 is attributed to the anion effects and supersaturation . The particles in the KOH system (29 nm) were smaller than those in the NaOH system (44 nm). For precursor concentration, intermediate Zn(OH) 2 was generated at lower concentration, while Zn 4 SO 4 (OH) 6 ·4H 2 O was produced at higher concentration. For alkali concentration, as the gradual increase of KOH concentration, Zn(OH) 2 began to decrease and gradually transformed into Zn(OH) 3 – and [Zn(OH) 4 ] 2− . When the KOH concentration reached a certain value, [Zn(OH) 4 ] 2− occupied the dominance in the mixed solution.
研究领域:
材料科学
·
纳米技术
·
化学工程
✓ 已验证
DOI
高影响因子
DESALINATION
·
2022
·
IF 11.211
Jie Liu,Yewei Wang,Zhuo Li,Xin Liu,Weiyi Li
Scaling of sparingly soluble salts is a challenge standing in the way of enhancing water recovery of desalination via an approach based on membrane distillation (MD). Improvement of anti-scaling strategies is dependent on understanding various mechanisms accounting for evolution of the scaling layer. This study made efforts to address a fundamental concern as to how bulk precipitation is competing with surface growth to form a layer of crystalline particles in the process of MD. When concentrating a feed containing calcium sulfate , scaling was induced in a series of MD processes with a varied transmembrane temperature difference. In addition to the measurements of flux decline and electrical conductivity , optical coherence tomography (OCT) was explored to simultaneously monitor the formation of crystals in the feed bulk and resolve the scaling layer evolving on the membrane surface . Comparison of these characterization results revealed the key role of surface growth in initiating the scaling, while suggesting that the cake development could be gradually dominated by the deposition of crystals formed in the feed bulk. A further analysis of the local growth rates provided deeper insights into the mechanistic transition; effects of varying the degree of supersaturation were also discussed in the context of redistributing the size of deposits and inducing the crystal-membrane interactions. This study refines the picture of developing a scaling layer in MD, which would be of great value in advancing applications of MD-based desalination.
研究领域:
环境科学
·
化学工程
·
水处理
✓ 已验证
产品关联
DOI
高影响因子
CRYSTAL GROWTH & DESIGN
·
2019
·
IF 4.153
Si Li,Weiwei Tang,Mengya Li,Lingyu Wang,Yang Yang,Junbo Gong
The precipitation of calcium oxalate can be either grown into structural support in plants or precipitated as stones in human kidneys. Previously, citrate, an effective inhibitor for oxalate stone formation, was suggested to alter the crystallization pathway of calcium oxalate and enhance the formation of less stable calcium oxalate trihydrate; however, the underlying mechanism is unknown. Herein we investigated the role of citric acid on crystallization pathways of calcium oxalate hydrates and the effect of supersaturation. It was found that the presence of citric acid can modulate the water content of amorphous nucleated precipitates by TEM and XRD and hence promote the formation of different calcium oxalate hydrates. The remaining water content in amorphous precipitates depends upon the amount of citric acid employed. FTIR and XRD analyses further reveal the extreme structural similarities between amorphous precipitates and the resultant hydrates. Additionally, the role of citric acid on crystallization pathways could be completely changed by supersaturation of calcium oxalate. High supersaturation dominated by homogeneous nucleation can diminish or even invalidate citric acid roles. The findings highlight the interplay of roles between additives and supersaturations, and could improve current understandings on the formation mechanism of oxalate stone.
研究领域:
化学
·
材料科学
·
生物矿化
·
泌尿学
✓ 已验证
产品关联
DOI
高影响因子
CRYSTAL GROWTH & DESIGN
·
2021
·
IF 4.076
Qingyang Zhang,Min Su,Linjing Yu,Yang Zhang
Bulk protein crystallization used in biopharming as an alternative method of protein-based biotherapeutics purification has been researched with a noticeable focus because of its advantages of low cost and high purification efficiency. We proposed a method to prepare magnetic protein crystals with targeting function using nanomagnetic spheres as the core and polymers as the medium. Lysozyme was used as a model protein, and polymers with different structural characteristics were selected to assist the molecular self-assembly of magnetic lysozyme crystals. Polymer C with free carboxyl groups provoked the largest increase in the effective supersaturation (S = 9.57), which enhanced the shortest induction time (T = 5.5 h). UV spectrum, fluorescence, molecular docking, and molecular dynamics (MD) methods were conducted to investigate the interaction law in the interface between polymers and lysozyme. Polymer C had the strongest interaction with lysozyme and promoted the most suitable change in the conformation of lysozyme, which all resulted in optimum crystallization propensities. This article provides insight into the mechanism of the interface-assisted self-assembly of magnetic lysozyme crystals, which can provide a method for selecting polymers to assist the self-assembly of functional crystals.
研究领域:
生物化学
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材料科学
·
生物技术
·
药学
✓ 已验证
产品关联
DOI
高影响因子
CRYSTENGCOMM
·
2021
·Vol. 23
·期 12
·2367-2375
·
IF 3.545
Yuntian Xiao,Wenchao Yang,Ling Zhou,Hongxun Hao,Ying Bao,Qiuxiang Yin,Chuang Xie
As an emerging technology that can simultaneously improve the powder performance and bioavailability of drugs, spherulitic cocrystallization has increasingly shown its unique advantages. In this study, we reported a new case of a propylthiouracil/kaempferol (PTU–KA) spherulitic cocrystal and explored its growth mechanism. The morphological evolution process and growth kinetics of spherulites were studied using an in situ stereomicroscope and scanning electron microscope. The growth of the PTU–KA spherulitic cocrystal was discovered to have three stages: single crystal growth, non-crystallographic branching, and surface nucleation. It was found that increasing temperature can strengthen the surface nucleation process, and the increasing degree of supersaturation is beneficial to the formation of dense spherulites. An appropriate kinetic model has been established, which has demonstrated that the growth rate curve is not monotonical but has a maximum. Subsequent modeling analysis shows that different stages involve different control steps. Specifically, the non-crystallographic branching process is mainly dominated by interface control, while the surface nucleation process is mainly determined by diffusion control. The results of this work may provide a useful reference for the design and manufacture of spherulitic cocrystals.
研究领域:
药学
·
晶体学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energetic Materials
·
2022
·
IF 2.421
Yi-Fan Zhang,Song Zhang,Le-Wu Zhan,Wan-Ying Tang,Jing Hou,Bin-Dong Li
Current methods, including ball milling and spray drying, are subject to some restrictions in application for preparing nano 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105), such as too large volume of dangerous goods, unstable temperature as well as discontinuous industrial production. In this study, continuous and safe preparation of nano-LLM-105 was achieved using microfluidic technology. Several influence factors had been studied on the particle size of LLM-105 including supersaturation, microreactor structure, solvent/non-solvent ratio, the total flow rate, reactor temperature, as well as the number of plates. Results showed that supersaturation of solution and structure of the microreactor played a critical role in the formation of nano-scale LLM-105. Further analysis on these nano-particles revealed its D50 was 124.95 nm with a spherical-like narrow shape through scanning electron microscopy and particle size distribution curve. X-ray diffraction results show that the crystal structure of nano-LLM-105 has not changed, and the differential scanning calorimeter test results show that nano-LLM-105 still maintains good thermal stability compared to raw-LLM-105. In short, this protocol provides a new route for continuous and safe preparation of nano-level LLM-105, which could be potentially applied to other nano-energetic materials, such as HMX and CL-20.
研究领域:
化学工程
·
材料科学
·
纳米技术
·
炸药
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）