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Crystals
Special Issues
Crystal Nucleation and Growth Kinetics
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Crystal Nucleation and Growth Kinetics

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Crystal Engineering".

Deadline for manuscript submissions: closed (15 June 2021) | Viewed by 38440

Special Issue Editors

Dr. Sendhil Poornachary

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Guest Editor
A*STAR Institute of Chemical and Engineering Sciences, Singapore
Interests: crystallization science; molecular modeling; particle technology; structure-property relationships in lubricant additives
Prof. Sameer Dalvi

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Guest Editor
Chemical Engineering, Indian Institute of Technology Gandhinagar, Ahmedabad, India
Interests: crystallization, polymorphism, colloidal suspensions
Dr. Sébastien Teychené

E-Mail Website
Guest Editor
Laboratoire de Génie Chimique, Université de Toulouse, CNRS, INP, UPS Toulouse, France
Interests: crystal nucleation; precipitation; industrial crystallization; non classical crystallization; microfluidics; phase transition
Dr. Damir Kralj

E-Mail Website
Guest Editor
Division of Materials Chemistry, Ruder Boskovic Institute, 10000 Zagreb, Croatia
Interests: precipitation kinetic and mechanism; crystallization; slightly soluble salts; precursors; calcium carbonates; vaterite; calcite; aragonite; calcium oxalates; biomineralization; industrial crystallization
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Crystallization continues to attract research efforts from industry and academia alike despite the plethora of information available in the literature. Competition between nucleation and growth kinetics during the crystallization process significantly affects the characteristics of product crystals such as size distribution, morphology, and polymorphic form. Moreover, the stochastic nature of crystal nucleation from the solution and formation of transient intermediate states (liquid-liquid phase separation, amorphous solid and metastable crystal forms) make control of the crystallization process difficult.

This Special Issue is committed to encouraging the dissemination/exchange of scientific knowledge and innovative ideas among researchers working on diverse themes ranging from crystallization fundamentals to crystal engineering and crystallization process design and development. Studies focused on investigating and establishing the mechanisms underlying crystal nucleation and growth processes that can be exploited to alter the crystallization kinetics are welcome. Scientific contributions on the measurement and modelling of crystal nucleation and growth rates, providing new insights into the following aspects of crystallization are highly encouraged:

  • Particle engineering and polymorphism;
  • Nucleation pathways (Classical and non-classical nucleation mechanisms) and their relevance for industrial crystallization;
  • Use of additives, heterogeneous templates, confinement (droplets, microfluidics and nanofluidics), and external fields (ultrasound, laser, electric and magnetic) to control crystallization;
  • The effect of impurities on crystal quality attributes and chemical purity;
  • Intermolecular interactions that govern the formation of multicomponent crystals such as co-crystals, solvates, hydrates and salts;
  • Preferential crystallization of chiral compounds.

Case studies or reviews on crystallization of small organic molecules, proteins and peptides, inorganic compounds and advanced functional materials will be considered. Modelling and theoretical approaches of crystal nucleation and growth kinetics at both process-scale (using population balance equations) and molecular-scale (molecular dynamics and Monte Carlo simulations) are of topical interest.

Dr. Sendhil Poornachary
Prof. Sameer Dalvi
Dr. Sébastien Teychené
Dr. Damir Kralj
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Crystals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Nucleation theory
  • Supersaturation
  • Impurities
  • Particle size
  • Crystal habit
  • Solubility
  • Phase transformation
  • Precipitation

Published Papers (11 papers)

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Research

Jump to: Review

7 pages, 1815 KiB  
Article
As-Grown Domain Structure in Calcium Orthovanadate Crystals
by Ekaterina Shishkina, Vladimir Yuzhakov, Maksim Nebogatikov, Elena Pelegova, Eduard Linker, Lyudmila Ivleva and Vladimir Shur
Crystals 2021, 11(12), 1508; https://doi.org/10.3390/cryst11121508 - 03 Dec 2021
Cited by 3 | Viewed by 1525
Abstract
An as-grown domain structure in nominally pure and Mn-doped calcium orthovanadate (CVO) crystals was studied by several methods of domain imaging: optical microscopy, piezoelectric force microscopy, and Cherenkov-type second harmonic generation. The combination of imaging methods provided an opportunity for comprehensive study of [...] Read more.
An as-grown domain structure in nominally pure and Mn-doped calcium orthovanadate (CVO) crystals was studied by several methods of domain imaging: optical microscopy, piezoelectric force microscopy, and Cherenkov-type second harmonic generation. The combination of imaging methods provided an opportunity for comprehensive study of the domain structure on the polar surface and in the bulk of the samples. It was shown that, in nominally pure CVO crystals, an irregular 3D maze of rounded domains, with charged walls, essentially tilted from the polar direction, was present. It was proposed that the domain structure was formed just below the phase transition temperature and persisted during subsequent cooling. Such behavior is due to effective bulk screening of the depolarization field and a low value of the pyroelectric field which appears during cooling. The revealed formation of triangular domains and flat fragments of domain walls in Mn-doped CVO was attributed to polarization reversal under the action of the polar component of the pyroelectric field, above the threshold value for domain switching. This fact represents the first observation of the domain switching in CVO crystals. Full article
(This article belongs to the Special Issue Crystal Nucleation and Growth Kinetics)
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13 pages, 6799 KiB  
Article
Impact of a Partial Solid Solution and Water Molecules on the Formation of Fibrous Crystals and Fluid Inclusions
by Laureline Marc, Chrystal Lopes, Jean-Marie Schneider, Morgane Sanselme and Gérard Coquerel
Crystals 2021, 11(10), 1188; https://doi.org/10.3390/cryst11101188 - 29 Sep 2021
Cited by 5 | Viewed by 2396
Abstract
Resolution of (±)ibuprofen using S-α-Methylbenzylamine in pure ethanol leads to the enriched S-IBU/S-αMBA diastereomeric salt which crystallizes as very fine needles. In order to improve the filterability and processability of the solid phase, water can be added to the medium and lead to [...] Read more.
Resolution of (±)ibuprofen using S-α-Methylbenzylamine in pure ethanol leads to the enriched S-IBU/S-αMBA diastereomeric salt which crystallizes as very fine needles. In order to improve the filterability and processability of the solid phase, water can be added to the medium and lead to more equant particles that are still elongated. A high fraction of the resulting platelets display on both ends a fluid inclusion containing both liquid and a large bubble of gas. A detailed analysis of the particles reveals that they are not really single crystals but more an ordered association of fibers defined as fibrous crystal. A domain of partial solid solution is evidenced near the pure less soluble diastereomer and its impact on the formation of fibrous crystals is demonstrated. When pure S-IBU/S-αMBA diastereomeric salt is recrystallized in the same medium (e.g., ethanol–water) the crystallinity is improved, but fluid inclusions can still be observed. Full article
(This article belongs to the Special Issue Crystal Nucleation and Growth Kinetics)
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13 pages, 1587 KiB  
Article
Determination of the Metastable Zone Width and Nucleation Parameters of Succinic Acid for Electrochemically Induced Crystallization
by Christian Kocks, Christina Maria Krekel, Marcel Gausmann and Andreas Jupke
Crystals 2021, 11(9), 1090; https://doi.org/10.3390/cryst11091090 - 07 Sep 2021
Cited by 9 | Viewed by 3878
Abstract
Electrified downstream processes for biotechnologically produced carboxylic acids reduce waste salt generation significantly and make biotechnological production ecologically and economically more attractive. In order to design, optimize, scale-up and control electrochemically induced crystallization processes, knowledge of the metastable zone width (MSZW) is essential. [...] Read more.
Electrified downstream processes for biotechnologically produced carboxylic acids reduce waste salt generation significantly and make biotechnological production ecologically and economically more attractive. In order to design, optimize, scale-up and control electrochemically induced crystallization processes, knowledge of the metastable zone width (MSZW) is essential. An optical observation approach of nucleation processes close to the electrode and determination of the MSZW is presented. This work presents a method for MSZW measurements for electrochemically induced pH-shift crystallization processes by monitoring the nucleation, the saturation pH value and saturation concentration for different current densities. The measured MSZWs for electrochemically induced pH-shift crystallization are narrow due to the foreign surface, gas bubbles and electrode surface, and rising current densities lead to even smaller MSZW. Nucleation parameters are estimated from MSWZ data, adapting the classical approach of Nývlt to electrochemically induced crystallization. Full article
(This article belongs to the Special Issue Crystal Nucleation and Growth Kinetics)
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25 pages, 3280 KiB  
Article
First-Principles Elastic and Anisotropic Characteristics of Structure-H Gas Hydrate under Pressure
by Shaden M. Daghash, Phillip Servio and Alejandro D. Rey
Crystals 2021, 11(5), 477; https://doi.org/10.3390/cryst11050477 - 24 Apr 2021
Cited by 7 | Viewed by 2488
Abstract
Evaluating gas hydrates properties contributes valuably to their large-scale management and utilization in fundamental science and applications. Noteworthy, structure-H (sH) gas hydrate lacks a comprehensive characterization of its structural, mechanical, and anisotropic properties. Anisotropic and pressure dependent properties are crucial for gas hydrates’ [...] Read more.
Evaluating gas hydrates properties contributes valuably to their large-scale management and utilization in fundamental science and applications. Noteworthy, structure-H (sH) gas hydrate lacks a comprehensive characterization of its structural, mechanical, and anisotropic properties. Anisotropic and pressure dependent properties are crucial for gas hydrates’ detection and recovery studies. The objective of this work is the determination of pressure-dependent elastic constants and mechanical properties and the direction-dependent moduli of sH gas hydrates as a function of guest composition. First-principles DFT computations are used to evaluate the mechanical properties, anisotropy, and angular moduli of different sH gas hydrates under pressure. Some elastic constants and moduli increase more significantly with pressure than others. This introduces variations in sH gas hydrate’s incompressibility, elastic and shear resistance, and moduli anisotropy. Young’s modulus of sH gas hydrate is more anisotropic than its shear modulus. The anisotropy of sH gas hydrates is characterized using the unit cell elastic constants, anisotropy factors, and the angular dependent moduli. Structure-properties composition correlations are established as a function of pressure. It is found that compressing filled sH gas hydrates increases their moduli anisotropy. Differences in atomic bonding across a crystal’s planes can be expected in anisotropic structures. Taken together the DFT-based structure–properties–composition relations for sH gas hydrates provide novel and significant material physics results for technological applications. Full article
(This article belongs to the Special Issue Crystal Nucleation and Growth Kinetics)
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15 pages, 6104 KiB  
Article
Effects of Synthesis Parameters on the Crystallization Profile and Morphological Properties of SAPO-5 Templated by 1-Benzyl-2,3-Dimethylimidazolium Hydroxide
by Ismail Alhassan Auwal, Fitri Khoerunnisa, Florent Dubray, Svetlana Mintova, Tau Chuan Ling, Ka-Lun Wong and Eng-Poh Ng
Crystals 2021, 11(3), 279; https://doi.org/10.3390/cryst11030279 - 12 Mar 2021
Cited by 1 | Viewed by 2648
Abstract
The formation of SAPO-5 molecular sieves is studied under hydrothermal conditions in the presence of a new templating agent, 1-benzyl-2,3-dimethylimidazolium hydroxide ([bzmIm]OH). The syntheses were carried out by varying the synthesis parameters, viz. crystallization temperature, heating time and reactants molar composition (SiO2 [...] Read more.
The formation of SAPO-5 molecular sieves is studied under hydrothermal conditions in the presence of a new templating agent, 1-benzyl-2,3-dimethylimidazolium hydroxide ([bzmIm]OH). The syntheses were carried out by varying the synthesis parameters, viz. crystallization temperature, heating time and reactants molar composition (SiO2, Al2O3, P2O5, [bzmIm]+, H2O) in order to investigate the role of each synthesis parameter on the formation of SAPO-5. The results showed that these synthesis parameters had significant influences on the entire crystallization process (induction, nucleation, crystal growth, and Ostwald ripening) and physicochemical properties of SAPO-5 (morphology and crystal size). Moreover, this study also demonstrated a fast hydrothermal synthesis approach where a SAPO-5 molecular sieve with hexagonal prism morphology could be crystallized within 10 h instead of days using a novel [bzmIm]OH heterocyclic template, thus offering an alternative route for synthesizing zeolite-like materials for advanced applications. Full article
(This article belongs to the Special Issue Crystal Nucleation and Growth Kinetics)
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15 pages, 3591 KiB  
Article
Role of Hydrodynamics, Li+ Addition and Transformation Kinetics on the Formation of Plate-Like {001} Calcite Crystals
by Nives Matijaković Mlinarić, Jasminka Kontrec, Branka Njegić Džakula, Giuseppe Falini and Damir Kralj
Crystals 2021, 11(3), 250; https://doi.org/10.3390/cryst11030250 - 28 Feb 2021
Cited by 6 | Viewed by 1709
Abstract
Plate-like calcite crystals with expressed unstable {001} planes are interesting research model for investigations of interfacial interactions of different additive molecules, but also the crystal growth mechanisms. The aim of this study is to reproducibly prepare a significant amount of well-defined plate-like calcite [...] Read more.
Plate-like calcite crystals with expressed unstable {001} planes are interesting research model for investigations of interfacial interactions of different additive molecules, but also the crystal growth mechanisms. The aim of this study is to reproducibly prepare a significant amount of well-defined plate-like calcite crystals and to investigate the critical experimental parameters. Thus, in precipitation system c(NaHCO3) = c(CaCl2) = 0.1 mol dm−3, the influence of hydrodynamic parameters (mode of mixing of the reaction components) and a presence of lithium ions Li+ within a wide range of concentrations, 0.0 mol dm−3 < c(Li+) < 1.0 mol dm−3, have been studied. In addition, the kinetics of the solution mediated transformation of the initially formed metastable polymorph, vaterite, were followed in order to reproducibly describe the formation of stable calcite with expressed unstable morphology. The results indicate that the plate-like calcite is formed predominantly when the ultrasound irradiation is applied at c(Li+) ≥ 0.3 mol dm−3. On the other hand, when the magnetic and mechanical stirring are applied at higher Li+ concentrations, truncated rhombohedral crystals in a mixture with plate-like crystals are obtained. It was also found that the Li+ addition significantly prolonged the transformation, mainly by inhibiting the crystal growth of calcite. Full article
(This article belongs to the Special Issue Crystal Nucleation and Growth Kinetics)
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15 pages, 3913 KiB  
Article
Biocementation of Calcareous Beach Sand Using Enzymatic Calcium Carbonate Precipitation
by Ahmed Miftah, Hamed Khodadadi Tirkolaei and Huriye Bilsel
Crystals 2020, 10(10), 888; https://doi.org/10.3390/cryst10100888 - 01 Oct 2020
Cited by 19 | Viewed by 3169
Abstract
Beach sands are composed of a variety of minerals including quartz and different carbonate minerals. Seawater in beach sand contains several ions such as sodium, magnesium, calcium, chloride, sulfate, and potassium. These variations in mineralogy and the presence of salts in beach sand [...] Read more.
Beach sands are composed of a variety of minerals including quartz and different carbonate minerals. Seawater in beach sand contains several ions such as sodium, magnesium, calcium, chloride, sulfate, and potassium. These variations in mineralogy and the presence of salts in beach sand may affect the treatment via enzyme-induced carbonate precipitation (EICP). In this study, set test tube experiments were conducted to evaluate the precipitation kinetics and mineral phase of the precipitates in the presence of zero, five, and ten percent seawater (v/v). The kinetics were studied by measuring electrical conductivity (EC), pH, ammonium concentration, and carbonate precipitation mass in EICP solution at different time intervals. A beach sand was also treated using EICP solution containing zero and ten percent seawater at one, two, and three cycles of treatment. Unconfined compressive strength (UCS), carbonate content, and mineralogy of the precipitates in the treated specimens were evaluated. The kinetics study showed that the rate of urea hydrolysis and the rate of precipitation for zero, five, and ten percent seawater were similar within the first 16 h of the reaction. After 16 h, it was observed that the rates dropped in the solution containing seawater, which might be attributed to the faster decay rate of urease enzyme when seawater is present. All the precipitates from the test tube experiments contained calcite and vaterite, with an increase in vaterite content by increasing the amount of seawater. The presence of ten percent seawater was found to not significantly affect the UCS, carbonate content, and mineralogy of the precipitates of the treated beach sand. Full article
(This article belongs to the Special Issue Crystal Nucleation and Growth Kinetics)
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17 pages, 3634 KiB  
Article
Parameter Estimation of the Stochastic Primary Nucleation Kinetics by Stochastic Integrals Using Focused-Beam Reflectance Measurements
by Joi Unno and Izumi Hirasawa
Crystals 2020, 10(5), 380; https://doi.org/10.3390/cryst10050380 - 07 May 2020
Cited by 9 | Viewed by 3492
Abstract
The kinetic parameters of stochastic primary nucleation were estimated for the batch-cooling crystallization of L-arginine. It is difficult for process analytical tools to detect the first nucleus. In this study, the latent period for the total number of crystals to be increased to [...] Read more.
The kinetic parameters of stochastic primary nucleation were estimated for the batch-cooling crystallization of L-arginine. It is difficult for process analytical tools to detect the first nucleus. In this study, the latent period for the total number of crystals to be increased to a predetermined threshold was repeatedly measured with focused-beam reflectance measurements. Consequently, the latent periods were different in each measurement due to the stochastic behavior of both primary and secondary nucleation. Therefore, at first, the distribution of the latent periods was estimated by a Monte Carlo simulation for some combinations of the kinetic parameters of primary nucleation. In the simulation, stochastic integrals of the population and mass balance equations were solved. Then, the parameters of the distribution of latent periods were estimated and correlated with the kinetic parameters of primary nucleation. The resulting correlation was represented by a mapping. Finally, the parameters of the actual distribution were input into the inverse mapping, and the kinetic parameters were estimated as the outputs. The estimated kinetic parameters were validated using statistical techniques, which implied that the observed distribution function of the latent periods for the thresholds used in the estimation coincided reasonably with the simulated one based on the estimated parameters. Full article
(This article belongs to the Special Issue Crystal Nucleation and Growth Kinetics)
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11 pages, 2719 KiB  
Article
Effects of Various Inhibitors on the Nucleation of Calcium Oxalate in Synthetic Urine
by Yu-Chao Hsu, Yi-Hsuan Lin and Lie-Ding Shiau
Crystals 2020, 10(4), 333; https://doi.org/10.3390/cryst10040333 - 23 Apr 2020
Cited by 11 | Viewed by 4660
Abstract
A new synthetic urine was adopted in this work to study the nucleation kinetics of calcium oxalate using a batch crystallizer for various supersaturations at 37 °C. In the studied new synthetic urine, three additional components (urea, uric acid and creatinine) within the [...] Read more.
A new synthetic urine was adopted in this work to study the nucleation kinetics of calcium oxalate using a batch crystallizer for various supersaturations at 37 °C. In the studied new synthetic urine, three additional components (urea, uric acid and creatinine) within the normal physiological ranges were added to the commonly-used synthetic urine to simulate human urine more closely. The interfacial energy for the nucleation of calcium oxalate was determined based on classical nucleation theory using the turbidity induction time measurements. The effects of various inhibitors, including magnesium, citrate, hydroxycitrate, chondroitin sulfate, and phytate, on the nucleation of calcium oxalate were investigated in detail. Scanning electron microscopy was used to examine the influences of these inhibitors on the preferential nucleation of the different hydrates of calcium oxalate crystals. Full article
(This article belongs to the Special Issue Crystal Nucleation and Growth Kinetics)
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9 pages, 2297 KiB  
Article
Skull Melting Growth and Characterization of (ZrO2)0.89(Sc2O3)0.1(CeO2)0.01 Crystals
by Dmitrii Agarkov, Mikhail Borik, Galina Eliseeva, Alexey Kulebyakin, Elena Lomonova, Filipp Milovich, Valentina Myzina, Yuriy Parkhomenko, Elena Skryleva and Nataliya Tabachkova
Crystals 2020, 10(1), 49; https://doi.org/10.3390/cryst10010049 - 19 Jan 2020
Cited by 2 | Viewed by 2642
Abstract
(ZrO2)0.89(Sc2O3)0.1(CeO2)0.01 crystals have been grown by directional melt crystallization in a cold crucible. The chemical and phase compositions of the crystals have been characterized using energy dispersion X-ray spectroscopy (EDX), [...] Read more.
(ZrO2)0.89(Sc2O3)0.1(CeO2)0.01 crystals have been grown by directional melt crystallization in a cold crucible. The chemical and phase compositions of the crystals have been characterized using energy dispersion X-ray spectroscopy (EDX), Raman scattering spectroscopy and transmission electron microscopy (TEM). The X-ray photoelectron emission method has been used for determining the valence state of the Ce ions. We show that directional melt crystallization produces an inhomogeneous ceria distribution along the crystal length. The as-grown crystals are mixtures of cubic and rhombohedral zirconia modifications. The rhombohedral phase has an inhomogeneous distribution along crystal length. Melt crystallization does not produce single-phase cubic (ZrO2)0.89(Sc2O3)0.1(CeO2)0.01 crystals. The formation of the phase structure in the crystals for different synthesis methods has been discussed. Full article
(This article belongs to the Special Issue Crystal Nucleation and Growth Kinetics)
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Review

Jump to: Research

18 pages, 986 KiB  
Review
Solution Cocrystallization: A Scalable Approach for Cocrystal Production
by Nitin Pawar, Anindita Saha, Neelesh Nandan and Jose V. Parambil
Crystals 2021, 11(3), 303; https://doi.org/10.3390/cryst11030303 - 18 Mar 2021
Cited by 33 | Viewed by 8424
Abstract
With an increasing interest in cocrystals due to various advantages, demand for large-scale cocrystallization techniques is rising. Solution cocrystallization is a solvent-based approach that utilizes several single-component crystallization concepts as well as equipment for generating cocrystals. Solution-based techniques can produce cocrystals with reasonable [...] Read more.
With an increasing interest in cocrystals due to various advantages, demand for large-scale cocrystallization techniques is rising. Solution cocrystallization is a solvent-based approach that utilizes several single-component crystallization concepts as well as equipment for generating cocrystals. Solution-based techniques can produce cocrystals with reasonable control on purity, size distribution, morphology, and polymorphic form. Many of them also offer a scalable solution for the industrial production of cocrystals. However, the complexity of the thermodynamic landscape and the kinetics of cocrystallization offers fresh challenges which are not encountered in single component crystallization. This review focuses on the recent developments in different solution cocrystallization techniques for the production of pharmaceutically relevant cocrystals. The review consists of two sections. The first section describes the various solution cocrystallization methods, highlighting their benefits and limitations. The second section emphasizes the challenges in developing these techniques to an industrial scale and identifies the major thrust areas where further research is required. Full article
(This article belongs to the Special Issue Crystal Nucleation and Growth Kinetics)
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