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Nucleation and Crystal Growth. Metastability of Solutions and Melts

  • ID: 4460853
  • Book
  • September 2018
  • 512 Pages
  • John Wiley and Sons Ltd
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A unique text presenting practical information on the topic of nucleation and crystal growth processes from metastable solutions and melts

Nucleation and Crystal Growth is a groundbreaking text that offers an overview and description of the processes and phenomena associated with metastability of solutions and melts. The author a noted expert in the field puts the emphasis on low–temperature solutions that are typically involved in crystallization in a wide range of industries. The text begins with a review of the basic knowledge of solutions and the fundamentals of crystallization processes. The author then explores topics related to the metastable state of solutions and melts from the standpoint of three–dimensional nucleation and crystal growth.

Nucleation and Crystal Growth is the first text that contains a unified description and discussion of the many processes and phenomena occurring in the metastable zone of solutions and melts from the consideration of basic concepts of structure of crystallization.  This important text:

  • Outlines an interdisciplinary approach to the topic and offers an essential guide for crystal growth practitioners in materials science, physics, and chemical engineering
  • Contains a comprehensive content that details the crystallization processes starting from the initial solutions and melts, all the way through nucleation, to the final crystal products
  • Presents a unique focus and is the first book on understanding, and exploiting, metastability of solutions and melts in crystallization processes

Written for specialists and researchers in the fields of materials science, condensed matter physics, and chemical engineering. Nucleation and Crystal Growth is a practical resource filled with hands–on knowledge of nucleation and crystal growth processes from metastable solutions and melts.

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Frequently used symbols
1. Structure and properties of liquids
1.1. Different states of matter
1.2. Models of liquid structure
1.3. Water and other common solvents
1.4. Properties of solutions The solvation process The concentration of solutions Density and thermal expansivity of solutions Viscosity of solutions
1.5. Saturated solutions
1.6. High–temperature solvents and solutions
2.  Three–dimensional nucleation of crystals and solute solubility
2.1. Driving force for phase transition
2.2. Three–dimensional nucleation of crystals
2.2.1. Nucleation barrier
2.2.2. Nucleation rate
2.2.3. Three–dimensional heterogeneous nucleation
2.3. Ideal and real solubility
2.3.1. Basic concepts
2.3.2. Examples of experimental data
2.3.3. Mathematical representation of solute solubility in solvent mixtures
2.4. Solute solubility as a function of solvent mixture composition
2.4.1. A simple practical approach
2.4.2. Physical interpretation of the Ô nfactor and solvent activity
2.4.3. Preferential solvation of solute by solvents
2.5. Solid–solvent interfacial energy
2.6. Solubility and supersolubility
3. Kinetics and mechanism of crystallization
3.1. Crystal growth as a kinetic process
3.2. Types of crystal–medium interfaces
3.3. Thermodynamic and kinetic roughening of surfaces
3.4. Growth kinetics of rough faces
3.5. Growth kinetcs of perfect smooth faces
3.6. Growth kinetics of imperfect smooth faces
3.6.1. Surface diffusion and direct integration models
3.6.2. Bulk diffusion models
3.6.3. Growth at edge dislocations
3.7. Simultaneous bulk–diffusion and surface–reaction controlled growth
3.8. Effect of impurities on growth kinetics
3.9. Overall crystallization
3.9.1. Basic theoretical equations
3.9.2. Polynuclear crystallization
3.9,2.1. Instantaneous nucleation mode Progressive nucleation mode Trends of overall crystallization curves Some comments on the KJMA theory
3.9.3. Mononuclear crystallization
3.9,4. Effect of additives on overall crystallization
4.  Phase transformation and isothermal crystallization kinetics
4.1. Nucleation and transformation of metastable phases
4.1.1. Thermodynamics of crystallization of metastable phases
4.1.2. Transformation kinetics of metastable phases
4.1.3. Transformation of metastable phases according to KJMA theory
4.1.4. Effect of solvent on transformation of metastable phases
4.2. Some non–KJMA models of isothermal crystallization kinetics
4.2.1. Approach involving formation of amorphous precursor
4.2.2. Model of Mazzanti, Marangoni and Idziak
4.2.3. Gompertz s model
4.2.4. Model of Foubert, Dewettinck, Jansen and Vanrolleghem
4.3. Comparison of different models of isothermal crystallization kinetics
5.  Nonisothermal crystallization kinetics and the metastable zone width
5.1. Theoretical interpretations of MSZW
5.1.1. Nývlt s approach
5.1.2. Kubota s approach
5.1.3. Self–consistent Nývlt–like equation of MSZW
5.1.4. Approach based on the classical theory of 3D nucleation
5.1.5. Approach based on progressive 3D nucleation
5.1.6. Approach based on instantaneous 3D nucleation
5.2.  Experimental results on MSZW of solute solvent systems
5.2.1. Dependence of dimensionless supercooling on cooling rate
5.2.2. Effect of detection technique on MSZW
5.2.3. Relationship between Ò and Z and between ¶ and F
5.2.4. Relationship between dimensionless F1 and crystallization temperature
5.2.5. Dependence of parameters ¶ and F on saturation temperature T0
5.2.6. Physical significance of Esat and its relationship with ´Hs
5.2.7. The nucleation order m 

5.3. Isothermal crystallization
5.4. Effect of additives on MSZW of solutions
5.4.1. Some general features
5.4.2. Theoretical considerations Approach based on classical nucleation theory Final expressions for analysis of experimental data
5.4.3. Some examples of effect of impurities on MSZW Boric acid aqueous solutions KDP aqueous solutions POP–acetone solutions containing PPP additive
5.4.4. Dependence of maximum supersaturation ratio Smax on impurity concentration ci
5.4.5. Solute–additive binding energies and MSZW of systems
5.5. Effects of some other factors on MSZW of solutions
5.5.1. Effect of stirring and ultrasound on MSZW
5.5.2. Effect of solution volume on MSZW
5.6. Nonisothermal crystallization kinetics in melts
6.  Antisolvent and combined antisolvent/cooling crystallization and the metastable zone width
6.1. Observation techniques for antisolvent crystallization
6.2. Light intensity measurements
6.2.1. Some experimental data
6.2.2. Processes involved in antisolvent crystallization
6.3. Temperature measurements
6.3.1. Some experimental data
6.3.2. Kinetics of temperature increase
6.3.3. Physical interpretation of temperature changes of ADP solutions with antisolvent feeding time at different rates
6.3.4. Origin of two minima and maximum in temperature change T during antisolvent crystallization
6.3.5. Relationship between different temperature changes, antisolvent feeding rate and antisolvent content
6.3.6. Comparison of light–intensity and temperature measurements
6.4. Effect of antisolvent composition on nucleation rate
6.5. Different approaches of MSZW
6.5.1. Modified Nývlt–like approach
6.5.2. Kubota s approach
6.5.3. Another derivation of Nývlt–like equation
6.5.4. Approach based on classical theory of 3D nucleation
6.6. Experimental data of MSZW in antisolvent crystallization
6.6.1. Analysis of experimental ´xmax(RA) data  

6.6.2. Effect of detection technique on MSZW
6.6.3. Effect of stirring on MSZW
6.6.4. Threshold and limiting antisolvent addition rates
6.7. Combined antisolvent/cooling crystallization
6.7.1. Theoretical considerations
6.7.2. Some experimental data
7.  Induction period for crystallization
7.1. Theoretical background
7.1.1. Theoretical interpretation of induction period
7.1.2. Some other relations
7.1.3. Basic equations
7.2. Induction period for isothermal crystallization
7.2.1. Crystallization from solutions
7.2.2. Crystallization from the melt
7.3. Induction period in antisolvent crystallization
7.4.  Induction perod for nonisothermal crystallization
7.4.1. Crystallization from solutions
7.4.2. Effect of impurities on crystallization from solutions
7.4.3. Crystallization from the melt
8. Ostwald ripening, crystal size distribution and polymorph selection
8.1. Supersaturation decay during antisolvent crystallization
8.1.1. General trends
8.1.2. Kinetics of supersaturation decay
8.1.3. Relationship between constant K and antisolvent feeding rate RA
8.2. Solvation and desolvation processes
8.2.1. Origin of minima in ´Tsw(t) plots
8.2.2. Kinetics of evolution of minima in ´Tsw(t) plots
8.3. Evolution of desupersaturation curves
8.4. Crystal morphology
8.5. Growth rate dispersion
8.6. Ostwald ripening
8.7. Crystal size distribution
8.8. Control of phase and size of crystallizing particles
9. Glass formation and crystallization processes
9.1. Glass formation by cooling of melts
9.2. Temperature dependence of viscosity and the glass transition temperature
9.3. Composition dependence of glass transition temperature
9.4. Relationship between glass transition temperature and metastable zone width of solutions
9.5. Metastable zone width of melts and glass formation
9.5.1. Derivation of basic equations
9.5.2. Effect of melt viscosity and additives on Z and F parameters
9.5.3. Calculations of RLlim, Z, F and TN for molten elements and electrolytes
9.5.4. Relationship between Tg and Tm for various substances
9.5.5. Comparison of cooling behavior of melts and electrolyte solutions
A. Volumetric thermal expanson coefficient of melts
B. Relationship between ÑV and other physical properties
B.1. Molten elements
B.2. Molten electrolytes
C. Relationship between densities dm of molten metals and electrolytes and their atomic mass
Subject index
Author index


Volumetric thermal expanson coefficient of melts
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Keshra Sangwal
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