The equilibrium crystallisation process of non-crystalline Cu3Au

The equilibrium crystallisation of non-crystalline Cu₃Au has been studied by molecular dynamics method. The results of structure analysis show that the crystallisation kinetics of non-crystalline Cu₃Au in the isothermal process is in agreement with the Avrami equation in the temperature range between 400 and 850 K. The time–temperature transformation diagram of crystallisation process presents a typical C-curve with nose temperature about 650 K. In the crystallisation process, there are also many metastable clusters produced in the disordered structure. The metastable polyhedron structure can promote the nucleation and growth process of crystal.     

Direct in situ observation of increasing structural dimensionality during the hydrothermal formation of open-framework zinc phosphates

The first time-resolved in situ X-ray diffraction studies of the hydrothermal crystallisation of open-framework zinc phosphates reveal a pathway of sequential crystallisation involving formation of a metastable low dimensional chain phase before the growth of three-dimensional zeolitic architectures.     

Inhibition of solute crystallisation in aqueous H(+)-NH(4)(+)-SO4(2-)-H2O droplets

Ice clouds in the Earth's upper troposphere can form via homogeneous nucleation of ice in aqueous droplets. In this study we investigate the crystallisation, or lack of crystallisation, of the solute phase and ice in aqueous (NH(4))(3)H(SO(4))(2)/H(2)O and NH(4)HSO(4)/H(2)O droplets. This is done using in situ X-ray diffraction of emulsified solution droplets mounted on a cold stage. From the diffraction patterns we are able to identify the phases of crystalline solute and ice that form after homogeneous freezing in micrometer sized droplets. An important finding from this study is that crystallisation of the solute does not always occur, even when crystallisation is strongly thermodynamically favoured. The nucleation and growth of solute phase crystals becomes inhibited since the viscosity of the aqueous brine most likely increases dramatically as the brine concentration increases and temperature decreases. If ice nucleates below a threshold freezing temperature, the brine appears to rapidly become so viscous that solute crystallisation is inhibited. This threshold temperature is 192 K and 180 K, in (NH(4))(3)H(SO(4))(2) and NH(4)HSO(4), respectively. We also speculate that the formation of cubic ice within a highly viscous brine blocks the solvent mediated cubic to hexagonal phase transformation, thus stabilising the metastable cubic ice in the most concentrated solution droplets.     

Role of thermal history on the thermal behavior of poly(<Emphasis Type="Italic">L</Emphasis>-lactic acid) studied by DSC and optical microscopy

Summary The thermal behavior of poly(L-lactic acid) (PLLA) was studied with differential scanning calorimetry (DSC) and polarized optical microscopy. For amorphous PLLA samples, double cold crystallisation peaks were observed in the DSC traces during heating process, being strongly dependent on heating rates. The observation was discussed based on the assumption that the quenched PLLA sample presented some remaining metastable or a precrystalline phase. A small exothermal peak was observed before the main melting peak at low heating rates. The probable reason was discussed through melt-recrystallisation mechanism. Influence of thermal history on the cold crystallisation and melting behavior was also performed on heating process for PLLA samples.     

Polymer crystallisation: Role of metastability and the confluence of thermodynamic and kinetic factors

Consideration is given to the effect of size on the thermodynamic stability in situations where two or more phase variants compete in the course of a phase transformation. It is found that, pending on material parameters, a situation can arise where the stabilities of the competing phases invert with size. Such a size induced stability inversion can have a profound influence on phase development in general connecting also with the kinetics of the phase transformation. Specifically, this newly considered combination of interrelated thermodynamic (stability) and kinetic (rates) factors can provide an explanation for the frequently experienced dominance of metastable phases (the century old Ostwald Stage Rule). When applied to polymers, as in the example of polyethylene, it provides a new outlook for polymer crystallisation. Amongst others it creates a unified approach for the two, so far largely disconnected areas of chain folded and extended chain type crystallisation incorporating (not contradicting!) existing approaches within a widened framework.     

An approach to phase behaviour in polymers

Aspects of phase transition will be surveyed such as are direct consequences of straightforward thermodynamic considerations yet are not normally taken count of in traditional treatments of phase behaviour even if, as is here shown, they can assume special significance in polymers. The central theme will be the common experience that in most materials, but especially in polymers, the state of ultimate thermodynamic stability is hardly ever attained, consequently that we are dealing with metastable states, the issue of metastability thus becoming the main theme of the present treatise. This metastability can manifest itself either through the phase transformation, even in the thermodynamically stable phase, not reaching completion and/or that phases other than those of ultimate stability appear first often taking on a dominant role. The above two strands are being followed through first separately and finally, with the example of polymer crystallisation, in combination. In the course of it all a variety of phase transformations and numerous potentially intriguing consequences are being touched upon. These are encompassing aspects of liquid-liquid phase separation, liquid-crystal formation and crystallisation, the intervention of glass transition, the significance of supercooling, the effect on and influence of the morphology and the connection and interrelation between thermodynamic stability (including metastability) and the rates of the phase transformation, with passing comments on gels and also on some aspects of chain conformation in solution. In the case of the most extensively covered item of crystallisation attention is being drawn to the possibility of stability inversion with phase (here crystal) size. The latter, in terms of ‘Phase Stability Diagrams’, offers a new approach to crystal growth, which in the case of polymers, creates both new perspectives and opens up the possibility of treating so far largely disconnected aspects of the subject within a unifying framework. The survey ends with reference to recent work on amorphisation through pressure pointing to new aspects of material behaviour and to some new and possibly surprising variants of otherwise familiar phase diagrams.     

Conformational dimorphism of 1,1,3,3,5,5-hexachloro-1,3,5-trigermacyclohexane: solvent-induced crystallization of a metastable polymorph containing boat-shaped molecules

Two crystalline modifications of 1,1,3,3,5,5-hexachloro-1,3,5-trigermacyclohexane have been experimentally obtained as phase pure products and studied by single-crystal X-ray diffraction. The six-membered heterocycles adopt a chair conformation in the alpha-phase; this polymorph is accessible by crystallisation from solution and from the melt. In contrast, the beta-form is built up from boat-shaped molecules; it can exclusively be crystallised from n-hexane. At the molecular level, formation energies of the 1,1,3,3,5,5-hexachloro-1,3,5-trigermacyclohexane conformers have been compared by using molecular mechanics, semiempirical and ab-initio quantum mechanical calculations. Possible reasons for the selective formation of the alpha- or beta-phase in specific solvents have been considered. Formation of the metastable phase is suggested to occur via a hypothetical intermediate of composition [(GeCl2CH2)3].0.5C6H14. For such an in-silico solvate, a crystal structure of favourable lattice energy, closely related to the experimentally observed beta-modification, has been found through global energy minimisation. Elimination of the n-hexane molecules from this computer-generated solid and subsequent simulated annealing resulted in a crystal structure that corresponds to the experimentally observed beta-phase within the limits of the force field calculations. This scenario implies solvent directed crystallisation of a metastable polymorphic molecular crystal.     

In situ spectroscopic study of the oxidation and reduction of Pd(111)

Using a photoemission spectroscometer that operates close to ambient conditions of pressure and temperature we have determined the Pd-O phase diagram and the kinetic parameters of phase transformations. We found that on the (111) surface oxidation proceeds by formation of stable and metastable structures. As the chemical potential of O2 increases chemisorbed oxygen forms followed by a thin surface oxide. Bulk oxidation is a two-step process that starts with the metastable growth of the surface oxide into the bulk, followed by a first-order transformation to PdO.     

Polymorphism and melt crystallisation of racemic betaxolol, a β-adrenergic antagonist drug

We report the polymorphic behaviour, in melt cooling experiments, of racemic betaxolol, a low aqueous solubility selective β₁-adrenergic antagonist drug with a flexible molecular structure. A multidisciplinary approach is employed, using thermal analysis (differential scanning calorimetry, polarised light thermomicroscopy), spectroscopic methods (infrared spectroscopy, magic angle spinning ¹H NMR) and X-ray powder diffraction. A glass phase is obtained, T _g ~ ?10 °C, on cooling the melt, unless the cooling rate is ≤0.5 °C min^?1, while a new metastable form, polymorph II, T _fus = 33 °C, is generated in subsequent heating runs in a two step process. Although either partial crystallisation from the melt in the first step or the formation of an intermediate, metastable, low ordered phase may explain these observations, our results favour the second hypothesis. The stable polymorph I, T _fus = 69 °C, which crystallizes on further heating after form II melting, has also been obtained either from polymorph II or from the molten phase, on standing at 25 °C. The racemic betaxolol crystalline phases are found to exhibit some degree of disorder.     

Metastable phases in kinetics of phase transformations in the frozen liquid crystal 4-ethoxybenzylidene-4'-n-butylaniline

The nematogen 4-ethoxybenzylidene-4'-n-butylaniline gives by fast cooling a frozen phase called C₁ different from a glassy nematic state. The X-ray diffraction spectra of a non-aligned sample and a sample aligned by a magnetic field show that the C₁ phase is a monolayer smectic phase: molecules are inclined to the normal of the smectic planes by an angle of 35° ± 5°. On reheating we obtain metastable phases more and more ordered; those phases C₂ and C₃ are crystalline. The kinetics for the metastable phases correspond to a nucleation growth process of the same type (n = 2) for the two transformations C₁→C₂→C₂. If we assume a thermal process the growth is monodimensional.     

Glass Transition Dynamics of Poly(L‐lactic acid) during Isothermal Crystallisation Monitored by Real‐Time Dielectric Relaxation Spectroscopy Measurements

Summary: Dielectric relaxation spectroscopy was used to monitor the development of crystallinity in poly(L ‐lactic acid) (PLLA) at 80 °C. The continuous shifting of the main loss peak towards lower frequencies was modelled considering the evolution of three relaxation processes: the α‐process of the bulk‐like (non‐restricted) amorphous phase, the α‐process of the amorphous fraction influenced by the crystalline structure and the β‐relaxation. It was found that the shape parameters and the position of the loss peaks are essentially constants during crystallisation, just with their dielectric strengths varying. This indicates that (i) the two segmental dynamics process develops independently and (ii) the dynamics features of the (slower) confined amorphous phase do not change during crystallisation. Optical microscopy results showed that a correlation exists between the evolution of the spherulitic morphology and the dielectric strength of the α‐processes.

Dielectric loss in the frequency domain for PLLA during crystallisation at 80 °C and polarised optical micrographs showing the spherulitic morphology in PLLA after 45 min during isothermal crystallisation.     

Coupling of simulated moving bed chromatography and fractional crystallisation for efficient enantioseparation

An optimised coupling of liquid chromatography and fractional crystallisation is suggested for efficient enantioseparation. As a first stage, a chromatographic separation, preferably simulated moving bed (SMB) chromatography, is applied to achieve an enantiomeric enrichment sufficient for a subsequent crystallisation. First results of the experimental and modelling work for the model system (+)-/(-)-mandelic acid in an aqueous solution are described. Chromatographic investigations involve the estimation of adsorption isotherms on a suitable chiral stationary phase and the simulation and optimisation of a corresponding SMB process. From the ternary phase diagram measured for the (+)-/(-)-enantiomer/ solvent system, the conditions required to crystallise a pure enantiomer from an asymmetric mixture can be derived. The productivity gains achievable from the combined process compared to the application of chromatography alone are discussed.     

Metastable Self‐Assembly of Theta‐Shaped Colloids and Twinning of Their Crystal Phases

Anisotropic colloids self‐assemble into different crystal structures compared to spherical colloids. Exploring and understanding their self‐assembly behavior could lead to creation of new materials with hierarchical structures through a bottom‐up process. Herein, we report metastable self‐assembly of theta‐shaped SiO₂ colloids interacting with a depletion force in a quasi‐two‐dimensional space and we demonstrate that both a metastable “prone” crystal phase and a stable “standing” crystal phase can be formed, depending on the self‐assembly path. Path selection stems from an interplay between particle–particle interactions and particle–wall interactions. In particular, a twinning of the metastable crystals was observed and two twinning mirror axes were found. A variety of complex twinned crystals were formed by each individual mirror axis or their combinations.     

Crystallisation, melting, recrystallisation and polymorphism of n-eicosane for application as a phase change material

Phase change materials (PCM) provide thermoregulation originating from the latent heat exchanged during melting or crystallisation. Linear hydrocarbons have weak interactions, but high symmetry, providing an effective quantity of latent heat over the most acceptable temperature range for applications. The ability to both melt and crystallise over a narrow range is made complex by nucleation, polymorphism and the kinetic nature of these changes. Differential scanning calorimetry (DSC), optical microscopy and temperature modulated DSC (TMDSC) was used to study the melting of n-eicosane. This PCM has a low degree of supercooling and conversion to the most stable crystalline state (triclinic) that occurs rapidly from a metastable phase (rotator) state on cooling. TMDSC revealed a small, yet similar degree of thermodynamic reversibility in the melting of each of the crystalline phases.     

Clathrate thermodynamics for the unstable host framework

We have introduced the concept of clathrates whose empty host framework is unstable. In contrast to the Van der Waals theory, according to which the empty host framework is metastable, we believe it to become metastable when, in the cellular clathrates, certain type of cavities are fully occupied or, in the channel clathrates, the guest molecules are closely packed. The free energy of the channel and cellular types of clathrates has been determined using statistical thermodynamics methods. The obtained chemical potentials allowed us to describe the equilibrium of the clathrate with the stable host -phase and the gaseous guest phase. For the cellular clathrates the equations have been obtained determining the dependence of the degree of filling of small cavities upon temperature and the gaseous phase pressure. In the case of the channel clathrates the set of equations on the composition and parameter of the orientational ordering is found. These equations enable us to describe quantitatively compressed state of the guest molecules in the channel and to find temperatures of orientational ordering.     

Crystallisation from a Water‐in‐Oil Emulsion as a Route to Enantiomer Separation: The Case of dl‐Threonine

The use of crystalliation as a means of separating enantiomers is well known. The utility of commonly applied seeding approaches is limited by the ultimate crystallisation of the antipode. Here we demonstrate how the combination of colloid science and crystal chemistry can lead to an emulsion based process yielding robust separation of a purified solid and impure liquid phases with ultimate product ee of up to 90 %. Threonine is used as a model to demonstrate the viability of the method but it is clear that extension to include, for example, simultaneous racemisation within the disperse phase is easily possible and would transform this from a separation to a preparation process.     

Ab initio probing of the aromatic oxygen cluster O4(2+)

The structure of the O(4)(2+) dication has been studied theoretically using a few conventional theoretical methods. We found the O(4)(2+) dication to be a metastable species with a perfect square structure. The molecular orbital analysis reveals that this dication is the first all-oxygen aromatic system with 6pi electrons. Although the O(4)(2+) dication is highly thermodynamically unstable, we believe that appropriate counteranions with very high electron detachment energy (superhalogens) can be found to form a solid-state compound containing O(4)(2+). Another way to probe the planar aromatic tetra oxygen dication could be a double-photoionization process of the (O(2))(2) dimer.     

Mechanism of CIT-6 and VPI-8 crystallization from zincosilicate gels

The crystallisation of CIT-6, a large-pore zincosilicate with the framework topology of zeolite Beta and synthesised from clear hydrogels that contain, tetraethylammonium (TEA+), Li+ and Zn2+ cations, proceeds initially through the formation of an amorphous solid that incorporates all the initial Zn species. Nucleation of the *BEA phase is effected by reorganisation of the amorphous phase, whereas crystal growth involves the incorporation of soluble species also. A highly crystalline CIT-6 material is obtained after 164 h of synthesis at 140 degrees C. Scanning electron microscopy (SEM) shows that this sample exhibits two different types of crystals: well-defined pseudo-cubic crystals and rounded crystals. The latter has a broad crystal-size distribution. If crystallisation is continued with longer synthesis times, the VPI-8 crystalline phase appears, and a new population of needle-shaped crystals is detected in the SEM images. This new crystalline phase is nucleated on the surface of the rounded CIT-6 crystals, which disappear as the crystallisation progresses, while no changes are observed in the population of pseudo-cubic CIT-6 crystals. At higher crystallisation temperatures these phase transformations are accelerated, and the formation of VPI-8 is favoured over that of CIT-6.     

Crystal growth in framework materials

Crystal-growth phenomena in open-framework microporous materials are explored using a combination of atomic force microscopy, high-resolution electron microscopy and modelling. Analogies are drawn between these open-framework systems and dense phase structures. In particular we discuss the role of organic structure-directing agents, commonly known as templates and suggest a new philosophy for predicting suitable molecules. We also discuss the role of defects in the crystallisation of open-framework materials and the effect of crystallisation processes on the incorporation of defects and intergrowths.     

Interactions and phase transitions in protein solutions

Understanding interactions and phase transitions in protein solutions is essential in order to develop systematic protein crystallisation strategies. Recent studies show that proteins near crystallisation behave as particles interacting via a very short-range attractive potential. The microscopic origin of this attractive term, and its strong dependence on the nature of the crystallisation agent, is, however, still obscure. The interplay of crystal nucleation with formation of weakly bonded amorphous aggregates also deserves further analysis.