Homogeneous Nucleation Mechanism Research Articles

How CO2 gas accelerates water nucleation at low temperature.

We conducted homogeneous nucleation experiments for dilute binary H2O-CO2 mixtures in Ar-N2 carrier gas with different CO2/H2O ratios at temperatures of 57 and 75K and total pressures of ∼40 and 70Pa, respectively. Direct experimental information on the number and type of molecules in the clusters and on the cluster number concentration is obtained by mass spectrometric detection of nucleating clusters that form in the uniform region of Laval expansions. Only homo-molecular water clusters are observed in the mass spectra. However, as the CO2/H2O ratio increases, a significant increase in the nucleation rate is observed. A simple kinetic model suggests that this acceleration of nucleation is due to the formation of short-lived, transient hetero-molecular H2O-CO2 dimers. Comparison with homogeneous binary nucleation of toluene-CO2 and unary nucleation of H2O shows that nucleation becomes more efficient in systems with stronger intermolecular interactions and a larger number of degrees of freedom. Such studies at the molecular level will improve our understanding of homogeneous nucleation mechanisms in atmospheric and industrial processes.

Modeling of the perovskite nickelate SmNiO3 nucleation from amorphous thin films: A Volmer's thermodynamical approach

We present a thermodynamical model based on Volmer's nucleation theory adapted to the case of the perovskite nickelate SmNiO3 crystallization (SNO) from an amorphous (aSNO) thin film. This amorphous phase is synthesized via reactive magnetron sputtering and then subsequently annealed in air at temperatures between 725 and 925 K to crystallize it. This model allows to predict the theoretical nucleation rate of the crystallized perovskite phase according to the annealing temperature, the type of the nucleation (homogeneous and heterogeneous mechanisms) and to estimate some physical and thermodynamical data related to this transformation. A theoretical evaluation of the nucleation rate shows that the optimum temperature for crystallization is close to 800 K for which the nucleation rate can reach 1021 m-3.s-1 if considering both homogeneous and heterogeneous nucleation mechanisms. As the annealing temperature moves away from 800 K, the theoretical nucleation rate drops drastically, as observed experimentally by X-ray Diffraction (XRD) when we annealed 200 nm thick aSNO films. The good agreement between the presented model and the experimental crystallization results allows us to numerically evaluate some physical parameters not yet reported to date in the literature for SNO perovskites such as the surface energy between the amorphous and the crystallized SNO phases, the strain energy when the crystallization occurs and the enthalpy associated with crystallization.

The effect of chemical short-range order on incipient plastic behavior in FCC structured high entropy alloys

Chemical short-range order (CSRO) was assumed as one of the most important structure feature of high entropy alloys and the influence of CSRO on mechanical properties is a fundamental issue yet to be fully understood. In this work, we performed extensively nanoindentation experiments on CoCrFeNiAlx alloys to study the effect of CSRO on the incipient nanomechanical properties. The statistical nature of strengths at the first pop-in event was analyzed to gain insight of deformation mechanisms. All samples examined here exhibit bimodal distribution which indicate non-unique dislocation nucleation mechanisms. The bimodal distributions can be decomposed into two Gaussian distributions and the activation volumes can be obtained in the range of 0.73–1.38b3. The peaks shift to higher stress level after the development of CSRO. The heterogeneous dislocation nucleation plays a dominant role at low indentation stress with the aid of pre-existing crystalline defects. The homogeneous dislocation nucleation mechanism prevails when indentation stress close to theoretical values. The transmission electron microscopy characterization indicates the presence of chemical ordering in the aged samples. Both the degree of chemical ordering and lattice distortion are much higher in the Al containing HEAs due to the distinctive difference of properties in Al and other transition element atoms.

Nanofluidic Platform for Studying the First-Order Phase Transitions in Superfluid Helium-3

The symmetry-breaking first-order phase transition between superfluid phases 3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^3$$\\end{document}He-A and 3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^3$$\\end{document}He-B can be triggered extrinsically by ionising radiation or heterogeneous nucleation arising from the details of the sample cell construction. However, the role of potential homogeneous intrinsic nucleation mechanisms remains elusive. Discovering and resolving the intrinsic processes may have cosmological consequences, since an analogous first-order phase transition, and the production of gravitational waves, has been predicted for the very early stages of the expanding Universe in many extensions of the Standard Model of particle physics. Here we introduce a new approach for probing the phase transition in superfluid 3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^3$$\\end{document}He. The setup consists of a novel stepped-height nanofluidic sample container with close to atomically smooth walls. The 3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^3$$\\end{document}He is confined in five tiny nanofabricated volumes and assayed non-invasively by NMR. Tuning of the state of 3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^3$$\\end{document}He by confinement is used to isolate each of these five volumes so that the phase transitions in them can occur independently and free from any obvious sources of heterogeneous nucleation. The small volumes also ensure that the transitions triggered by ionising radiation are strongly suppressed. Here we present the preliminary measurements using this setup, showing both strong supercooling of 3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^3$$\\end{document}He-A and superheating of 3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^3$$\\end{document}He-B, with stochastic processes dominating the phase transitions between the two. The objective is to study the nucleation as a function of temperature and pressure over the full phase diagram, to both better test the proposed extrinsic mechanisms and seek potential parallel intrinsic mechanisms.

Size-Independent Nucleation and Growth Model of Potassium Sulfate from Supersaturated Solution Produced by Stirred Crystallization.

This paper explores the kinetics of the crystallization of potassium sulfate in a stirred bed crystallizer through experimental investigation. Employing classical nucleation theory, the homogeneous and heterogeneous nucleation mechanisms of potassium sulfate were investigated. The induction time and critical nucleation parameters, including the surface tension (γ), critical nucleation radius (r*), critical nucleation free energy (ΔG*), and critical nucleation molecule number (i*), were meticulously determined under varying temperatures and supersaturation ratios. The experimental findings revealed that as the temperature and supersaturation ratio increased, the induction time, critical nucleation free energy, critical nucleation radius, and critical molecule number decreased whereas the nucleation rate increased. The crystalline shape remains relatively unaltered with respect to temperature and supersaturation ratio, yet the particle size (D10, D50, D90) increases as the supersaturation and temperature increase. The variations in the measured nucleation parameters align well with the predictions of classical nucleation theory. Furthermore, the kinetic equations of crystal nucleation and the growth rate in a stirred crystallization system were fitted using population balance equations. The results demonstrate that the growth rate increases with increasing supersaturation and stirring rates. Additionally, the effects of the parameters in the nucleation rate equation suggested that the suspension density exerted the greatest influence, followed by the supersaturation ratio and stirring rate. This extensive research provides invaluable theoretical guidance for optimizing the crystallization process and designing industrial crystallizers.

Methods to modify supersaturation rate in membrane distillation crystallisation: Control of nucleation and crystal growth kinetics (including scaling)

While water vapour flux is often regarded as the critical parameter in membrane distillation crystallisation (MDC), there are multiple factors that will determine the kinetics of nucleation and crystal growth. A Nývlt-like equation is therefore introduced that can relate how multiple conditional parameters (membrane area, flux, temperature difference, crystalliser volume, magma density) independently modify nucleation rate and supersaturation, enabling a normalising approach for the characterisation of nucleation and crystal growth kinetics within MDC. Each parameter can be modified to increase supersaturation rate, which reduced induction time and broadened the metastable zone width (MSZW) at induction. An increase in supersaturation mitigated scaling and favoured bulk nucleation. This is due to the increase in volume free energy provided by the elevated supersaturation that reduces the critical energy requirement for nucleation to favour a homogeneous primary nucleation mechanism. An increase in temperature difference or magma density narrowed the MSZW. For each parameter, either supersaturation rate, supersaturation or induction time were fixed, while the other two factors were amended. While higher supersaturation rates generally favoured larger crystal sizes with broader size distributions, a high level of supersaturation at a low supersaturation rate increased particle size and narrowed the size distribution. In practice, these factors may be applied collectively and synergistically to deliver strict control over crystal growth, which remains a challenge for current evaporative technology. This was illustrated when facilitating an increase in supersaturation rate with membrane area, where an identical nucleation order was identified between membrane systems, from which it can be implied that MDC affords an inherently scalable solution for crystallisation.

Effect of high strain rate hot compression on the microstructure evolution and subsequent α precipitation of TC17 alloy during single-step and duplex aging

The modified α precipitation based on severely deformed β phase and optimized aging treatments is essential to the strengthening of titanium alloys. This study investigated the β phase features of high strain rate (20 s−1) hot compressed (810–900 °C) TC17 alloy coupled with the precipitation behavior and mechanism of α phase during single-step and duplex aging. The dynamic recovery (DRV) dominated the microstructure evolution of alloy and the low compression temperature resulted to high flow stress, strong β texture and dense low angle boundaries (LAGBs). The α precipitation of un-compressed alloy was dominated by homogeneous nucleation mechanism and the intragranular α laths in duplex aged alloy changed from lamellar to skeletal with pre-aging temperature increased from 320 °C to 380 °C. The α precipitates in compressed alloy however were coarsened a lot and the duplex aging at 350 °C/2.5 h + 600 °C/3.5 h caused finer and more uniform α distribution compared with the single-step aging. Generally, the high strain rate hot compression dramatically promoted the nucleation and growth of α phase during both two aging treatments due to its introduction of dense dislocations/sub-structures, whereas the duplex aging is more beneficial to the refinement of α precipitates as the pre-aging can inhibit the rapid growth of local intragranular α lamellas.

Nonisothermal crystallization kinetics of potassium chloride produced by stirred crystallization

The elucidation of the crystal nucleation and growth process can help control crystal size and quality. Here,the classical theory of primary nucleation was first used to study the homogeneous and heterogeneous nucleation mechanism of potassium chloride (KCl) crystallization. The growth kinetics in the presence of seed in KCl was then investigated. To understand the nucleation mechanism of KCl, the induction period of KCl was analyzed using classical nucleation theory to calculate the interfacial tension (γ) and various nucleation parameters, including the radius of the critical nucleus (r*), the critical free energy of the nucleus (ΔG*), and the molecular number of the critical nucleus (i*). The results showed a homogeneous nucleation mechanism at high supersaturation ratios (≥1.10) and a heterogeneous nucleation mechanism at low supersaturation ratios (<1.08). Meanwhile, the KCl crystal exhibited a continuous growth mechanism as inferred by the surface entropy factor (f) value. The SEM data demonstrated that the increase in crystallization temperature and supersaturation ratio could increase the average crystal size. The particle size-independent growth model is suitable for the growth process according to the relationship between crystal particle number density and particle size. In addition, the crystal nucleation and growth rates in stirred crystallization were calculated using the population balance equation, and then various kinetic parameters were estimated. The estimated parameters suggested an increase in growth with an increase in supersaturation ratio and stirring rate. Meanwhile, the impact of each parameter in the nucleation rate equation showed that the degree of influence is suspension density, supersaturation ratio, and finally, stirring rate.

Machine learning interatomic potentials for aluminium: application to solidification phenomena

In studying solidification process by simulations on the atomic scale, the modeling of crystal nucleation or amorphization requires the construction of interatomic interactions that are able to reproduce the properties of both the solid and the liquid states. Taking into account rare nucleation events or structural relaxation under deep undercooling conditions requires much larger length scales and longer time scales than those achievable by ab initio molecular dynamics (AIMD). This problem is addressed by means of classical molecular dynamics simulations using a well established high dimensional neural network potential trained on a set of configurations generated by AIMD relevant for solidification phenomena. Our dataset contains various crystalline structures and liquid states at different pressures, including their time fluctuations in a wide range of temperatures. Applied to elemental aluminium, the resulting potential is shown to be efficient to reproduce the basic structural, dynamics and thermodynamic quantities in the liquid and undercooled states. Early stages of crystallization are further investigated on a much larger scale with one million atoms, allowing us to unravel features of the homogeneous nucleation mechanisms in the fcc phase at ambient pressure as well as in the bcc phase at high pressure with unprecedented accuracy close to the ab initio one. In both cases, a single step nucleation process is observed.

Nano-mechanical properties and onset of plasticity in Fe–Mn–Al–Ni–C duplex lightweight steel processed by high temperature compression

In the present study, nano-indentation tests have been performed on the Fe–Mn–Al–Ni–C duplex lightweight steel following hot compression at 1223 K and 1423 K at a strain rate of 0.1 s−1. The nano-hardness values of various composite regions are determined and correlated with the complex deformed microstructural features, strain gradient, elemental partitioning, intergranular/intragranular precipitates and lattice distortion effect. The estimated elastic modulus value of FCC and BCC matrix regions in the studied steel is relatively higher than those reported for other conventional duplex steels, highlighting the contribution of intragranular B2 and к-carbide precipitates on the overall elastic modulus. Additionally, the deformation behavior of the matrix regions reveals that the onset of plasticity is governed by both homogeneous dislocation nucleation mechanism and multiplication of pre-existing dislocations under the indenter tip. The BCC + B2 region exhibits higher maximum shear stress (τmax) value as compared to the FCC + к-carbide region, indicating that the plastic deformation would first initiate in the latter region. This is related to the pre-existing high strain gradient in the soft FCC + к-carbide region that would facilitate the onset of plasticity more easily as compared to the BCC + B2 region during indentation. Moreover, it is observed that the elasto-plastic regime of the indentation loading curve exhibits random pop-in events associated with the resistance generated by the various intragranular precipitates in the FCC and BCC matrix regions, against the dislocation motion during nano-indentation test.

An investigation of the kinetics and thermodynamics of NaCl nucleation through composite clusters.

Having a good understanding of nucleation is critical for the control of many important processes, such as polymorph selection during crystallization. However, a complete picture of the molecular-level mechanisms of nucleation remains elusive. In this work, we take an in-depth look at the NaCl homogeneous nucleation mechanism through thermodynamics. Distinguished from the classical nucleation theory, we calculate the free energy of nucleation as a function of two nucleus size coordinates: crystalline and amorphous cluster sizes. The free energy surface reveals a thermodynamic preference for a nonclassical mechanism of nucleation through a composite cluster, where the crystalline nucleus is surrounded by an amorphous layer. The thickness of the amorphous layer increases with an increase in supersaturation. The computed free energy landscape agrees well with the composite cluster-free energy model, through which phase specific thermodynamic properties are evaluated. As the supersaturation increases, there is a change in stability of the amorphous phase relative to the solution phase, resulting in a change from one-step to two-step mechanism, seen clearly from the free energy profile along the minimum free energy path crossing the transition curve. By obtaining phase-specific diffusion coefficients, we construct the full mesoscopic model and present a clear roadmap for NaCl nucleation.

Homogeneous nucleation and condensation mechanism of methane gas: A molecular simulation perspective

Liquefied natural gas (LNG) occupies an increasing proportion in global natural gas industry. However, there is a lack of microscopic understanding of methane condensation mechanism. Furthermore, the accuracy of existing nucleation theories for alkane gases remains unclear. Herein, methane nucleation and growth pathways are elucidated and the influence mechanisms of initial conditions on nucleation thermodynamics and kinetics are analyzed using molecular dynamics (MD) simulations. It is discovered that a system with a controlled carrier gas temperature is more consistent with the actual condensation process. For such a system, the heat transfer processes between monomers and clusters make the condensed molecules easier to vaporize and its nucleation and growth stages last longer. Besides, the condensation processes end earlier with higher nucleation rates and liquefaction degrees at high initial pressures and low cooling temperatures. Higher pressures lead to higher temperatures of monomers and clusters during nucleation, while avoiding secondary evaporation. Furthermore, as initial pressures and cooling temperatures increase, the effects of system quenching on pressure relieve, and the fall in pressure mainly depends on the liquefaction degree. Compared with Classical Nucleation Theory (CNT), Internally Consistent Classical Theory (ICCT) has higher accuracy for the nucleation calculation of methane under high-pressure and low-temperature conditions.

Structure of crystalline and amorphous materials in the NASICON system Na1+xAlxGe2-x(PO4)3.

The structure of crystalline and amorphous materials in the sodium (Na) super-ionic conductor system Na1+xAlxGe2-x(PO4)3 with x = 0, 0.4, and 0.8 was investigated by combining (i) neutron and x-ray powder diffraction and pair-distribution function analysis with (ii) 27Al and 31P magic angle spinning (MAS) and 31P/23Na double-resonance nuclear magnetic resonance (NMR) spectroscopy. A Rietveld analysis of the powder diffraction patterns shows that the x = 0 and x = 0.4 compositions crystallize into space group-type R3̄, whereas the x = 0.8 composition crystallizes into space group-type R3̄c. For the as-prepared glass, the pair-distribution functions and 27Al MAS NMR spectra show the formation of sub-octahedral Ge and Al centered units, which leads to the creation of non-bridging oxygen (NBO) atoms. The influence of these atoms on the ion mobility is discussed. When the as-prepared glass is relaxed by thermal annealing, there is an increase in the Ge and Al coordination numbers that leads to a decrease in the fraction of NBO atoms. A model is proposed for the x = 0 glass in which super-structural units containing octahedral Ge(6) and tetrahedral P(3) motifs are embedded in a matrix of tetrahedral Ge(4) units, where superscripts denote the number of bridging oxygen atoms. The super-structural units can grow in size by a reaction in which NBO atoms on the P(3) motifs are used to convert Ge(4) to Ge(6) units. The resultant P(4) motifs thereby provide the nucleation sites for crystal growth via a homogeneous nucleation mechanism.

Molecular modeling of Ag4 cluster formation

Nucleation is the main process which affects on the characteristics of the formed metal nanoparticles. At the same time the mechanism of homogeneous nucleation of metal particles in solutions are still debatable. There are two contrary points of view which briefly may be presented as “Instantaneous” and “Continuous”. Instantaneous nucleation postulated by classical nucleation theory (CNT) means formation of nuclei as a result of supersaturation of solution via set of equilibrium reactions (on the whole nA⇔An) but Continuous nucleation implies step-by-step irreversible addition of monomer to formation of nuclei and/or nanoparticle (A→A2→…→An). Using DFT calculations the thermodynamic parameters of all possible reactions leading to formation of Ag4 cluster which may be considered as intermediate in the nucleation process have been estimated. It was found that formation of Ag4 is thermodynamically possible via both of mechanisms. At the same time it was noted that addition of Ag+ to silver cluster is more preferred than association of uncharged particles. Taking into account the much higher concentration of silver ions compared to silver atoms this fact may indicate on the preference of stepwise mechanism of nucleation of metal nanoparticles in real solutions.

Progress in rod bundle CHF in the past 40 years

Critical Heat Flux (CHF) prediction remains one of the most important tasks in thermal hydraulics of Light Water Reactors (LWR’s). During recent years, tremendous progress has been made in understanding and predicting rod bundle CHF. However, due to the unique features associated with rod bundle subchannel systems, including complex and compact anisotropic geometry, non-uniform axial/radial heating, open channel interactions, periodic (positional) mixing vane grids (MVG’s) mixing (Yang et al., 2014), and a broad range of operation conditions (Yang and Han et al., 2019), a precise prediction of CHF in rod bundles, entirely based on analytical methods without the support of any extensive experimental database, is still beyond the present modelling and computational capabilities. For Pressurized Water Reactors (PWR’s), CHF occurs at a relatively low coolant quality and is primarily driven by the Departure from Nucleate Boiling (DNB) type event, which can be triggered by liquid sublayer dryout, bubble crowding, homogeneous nucleation, or other mechanisms causing local starvation of liquid under subcooled flow boiling or low quality saturated boiling conditions, and the dryout event, which describes CHF under a high void situation when liquid film on the fuel surface dries out, usually happens in a high quality saturated annular flow. Boiling Water Reactors (BWR’s) operate at a relatively lower pressure and can reach much higher coolant qualities that correspond to annular two-phase flow conditions. This dominant CHF mechanism, dryout, is based on the gradual thinning and drying out of the liquid film.This paper provides an overview of the progress made in the experimental and analytical investigations of CHF in both PWR and BWR rod bundles during the past 40 years. A complete comprehensive concept map is developed to outline most of the key mechanistic CHF models covering the entire range of flow regimes. The limitation and the potential approaches for the application of mechanistic models to rod bundle CHF prediction are reviewed. This includes the recently proposed, rod bundle specific NHNM (Non-uniform heater Homogeneous Nucleation Model [Yang, 2017]). Various industrial empirical correlations are reviewed together with their corresponding subchannel codes and required rod bundle CHF experiments. The need for clear guidelines and standards for benchmarking new rod bundle CHF test facilities is discussed.Various approaches on investigating, understanding, modeling, and predicting the occurrence of rod bundle CHF are reviewed from mechanistic models, semi-empirical and empirical approaches to advanced CFD simulation. The achievements and limitations in those methods are discussed with suggestions for future advancement.

Determination of nucleation kinetics from the induction time of 1,1-diamino-2,2-dinitroethylene (FOX-7) in DMSO/Water

Elucidation of the crystal nucleation process can provide guidance for controlling crystal size and quality. To understand the nucleation process of 1,1-diamino-2,2-dinitroethylene (FOX-7), the induction time and nucleation kinetics of FOX-7 were studied using a turbidity method in a binary solvent system (DMSO ​+ ​water, xDMSO ​= ​0.3364) under cooling crystallization conditions. Using the CrystalSCAN system, the induction time was determined at a range of temperatures (325.05, 335.25, 343.15, 348.15, and 354.65 ​K) and supersaturations (S) (1.20, 1.22, 1.24, 1.27, 1.30, 1.32, 1.35, 1.37), and it was found that induction time decreases as supersaturation increases. The system displayed a homogeneous nucleation mechanism at high supersaturation ratios (≥1.27) and heterogeneous nucleation at low supersaturation ratios, below 1.25. The FOX-7 crystal exhibited a continuous growth mechanism, as inferred from the value of the surface entropy factor (f). The induction time data were analyzed using the classical nucleation theory to calculate the interfacial energy (γ) and various nucleation parameters, including the radius of the critical nucleus (r∗), critical free energy of the nucleus (ΔG∗), molecular number of the critical nucleus (i∗), and the nucleation rate (J). The morphology of FOX-7 crystals changed negligibly with varying temperature and supersaturation, while the average particle size decreased with an increase in supersaturation and a decrease in temperature.

Enhanced Nonisothermal Crystallization and Heat Resistance of Poly(l-lactic acid) by d-Sorbitol as a Homogeneous Nucleating Agent

We report on enhancing crystallization and heat resistance of poly(l-lactic acid) (PLLA) by d-sorbitol as a small molecule nucleating agent via melt blending. During the reheating process, the cold crystallization disappeared and the crystallinity of nucleated PLLA exceeded 50%. The heat deflection temperature of PLLA was elevated from 56 to 132 °C by simply increasing the mold temperature (90 °C) without an additional annealing treatment. We also observed the polymorphic crystals of PLLA during melt crystallization, i.e., the coexistence of hexagonal and lenticular crystals, along with their various geometrical aggregates in addition to plenty of conventional spherulites. On the basis of the fact that the nonisothermal crystallization temperature of PLLA (110 °C at a cooling rate of 10 °C/min) was higher than the melting point of d-sorbitol (about 93 °C), we speculated that d-sorbitol promoted the crystallization of PLLA through a homogeneous nucleation mechanism.

Molecular Understanding of Homogeneous Nucleation of CO2 Hydrates Using Transition Path Sampling.

Carbon dioxide hydrate is a solid built from hydrogen-bond stabilized water cages that encapsulate individual CO2 molecules. As potential candidates for reducing greenhouse gases, hydrates have attracted attention from both the industry and scientific community. Under high pressure and low temperature, hydrates are formed spontaneously from a mixture of CO2 and water via nucleation and growth. Yet, for moderate undercooling, i.e., moderate supersaturation, studying hydrate formation with molecular simulations is very challenging due to the high nucleation barriers involved. We investigate the homogeneous nucleation mechanism of CO2 hydrate as a function of temperature using transition path sampling (TPS), which generates ensembles of unbiased dynamical trajectories across the high barrier between the liquid and solid states. The resulting path ensembles reveal that at high driving force (low temperature), amorphous structures are predominantly formed, with 4151062 cages being the most abundant. With increasing temperature, the nucleation mechanism changes, and 51262 becomes the most abundant cage type, giving rise to the crystalline sI structure. Reaction coordinate analysis can reveal the most important collective variable involved in the mechanism. With increasing temperature, we observe a shift from a single feature (size of the nucleus) to a 2-dimensional (size and cage type) variable as the salient ingredient of the reaction coordinate, and then back to only the nucleus size. This finding is in line with the underlying shift from an amorphous to a crystalline nucleation channel. Modeling such complex phase transformations using transition path sampling gives unbiased insight into the molecular mechanisms toward different polymorphs, and how these are determined by thermodynamics and kinetics. This study will be beneficial for researchers aiming to produce such hydrates with different polymorphic forms.

Experimental Evaluation of the Miniemulsion Polymerization of Vinyl Pivalate: The role of the Main Process Variables

AbstractPoly(vinyl pivalate) (PVPi) nanoparticles obtained via miniemulsion have particular properties useful for several applications. Thus, the present study aims to synthesize and characterize PVPi nanoparticles through the miniemulsion polymerization process, studying the effects of water‐soluble and oil‐soluble initiators, polymerization temperature, and the co‐stabilizer concentration on the final properties of the polymer, nanoparticle size, and conversion. The polymeric nanoparticles are characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance (1H and 13C NMR), thermogravimetric analysis, differential scanning calorimetry, gel permeation chromatography, dynamic light scattering, and transmission electron microscopy. The miniemulsion polymerization process ensures the formation of a polymeric fluid with high colloidal and thermal stability, with maximum conversions of ≈85% and average particle diameter of 97.2 ± 21.8 nm. The polymeric properties, such as molar mass and glass transition temperature (Tg), are influenced by process variables such as synthesis temperature and the type of initiator. The use of potassium persulfate and 2,2‐azobisisobutyronitrile (AIBN) initiators favors the homogeneous nucleation mechanism, resulting in a decrease in the average particle diameter and in the growth of the chains, result in greater average molar masses and, consequently, greater Tg.

Preparation, mechanism and applications of oriented MFI zeolite membranes: A review

Oriented MFI zeolite membranes are membrane materials formed by closely stacking and crosslinking MFI grains or nanosheets in a specific direction. Compared with a-, c-, and (h0h)-oriented zeolite membranes, b-oriented membranes can effectively improve the molecular transmission rate and are widely used in the fields of mixture separation and catalysis. However, twinning can easily occur during the zeolite membrane preparation, and controlling the membrane orientation is difficult owing to the limitations in the crystal growth kinetics. In this review, recent important progress in the preparation strategies and methods of oriented zeolite membranes are introduced, and the microscopic mechanism of the membrane orientation regulation is analyzed, including heterogeneous nucleation and homogeneous nucleation mechanisms. Moreover, the application status of oriented zeolite membranes in the fields of mixture separation and catalysis is summarized. Finally, current challenges and future development perspectives of oriented MFI zeolite membranes are addressed.