Modeling of the alloy solidification modified by refractory nano-size particles

Ice formation induced by atmospheric particles through heterogeneous nucleation is not well understood. Onset conditions for heterogeneous ice nucleation and water uptake by particles collected in Los Angeles and Mexico City were determined as a function of temperature (200–273 K) and relative humidity with respect to ice (RHice). Four dominant particle types were identified including soot associated with organics, soot with organic and inorganics, inorganic particles of marine origin coated with organic material, and Pb/Zn‐containing particles apportioned to emissions relevant to waste incineration. Single particle characterization was provided by micro‐spectroscopic analyses using computer controlled scanning electron microscopy with energy dispersive analysis of X‐rays (CCSEM/EDX) and scanning transmission X‐ray microscopy with near edge X‐ray absorption fine structure spectroscopy (STXM/NEXAFS). Above 230 K, significant differences in onsets of water uptake and immersion freezing of different particle types were observed. Below 230 K, particles exhibited high deposition ice nucleation efficiencies and formed ice atRHicewell below homogeneous ice nucleation limits. The data suggest that water uptake and immersion freezing are more sensitive to changes in particle chemical composition compared to deposition ice nucleation. The data demonstrate that anthropogenic and marine influenced particles, exhibiting various chemical and physical properties, possess distinctly different ice nucleation efficiencies and can serve as efficient IN at atmospheric conditions typical for cirrus and mixed‐phase clouds.

Objective: To understand the structural and characteristic properties of phase change materials which are predominant for development of existing as well as future technologies. Crystallization kinetics and unlikeness between the amorphous and crystalline phases are the two main characterizations of phase change materials. Methods: This review demonstrates the different crystallization techniques in details. For re-writable DVD, the crystallization rate should be large enough to enable a high data rate at inflated temperature. Findings: Se-Te based chalcogenide alloys are frequently used in optical memory devices. But due to some drawbacks of these alloys, we have made an attempt to enhance their properties by addition of third element. Activation energy of crystallization (using Kissinger model) and rate of crystallization for ternary glassy alloys have been listed. It has been found that Ge is the favorable dopant for data storage applications because it has low activation energy of crystallization and high rate of crystallization. Applications: The chalcogenide fibers are used in fiber optic chemical sensor systems for remote detection and identification as well as detecting chemicals in mixtures. Keywords: Chalcogenide Glasses, Crystallization Techniques, Kissinger Model, Phase Change Materials, Rate of Crystallization

Semisolid metal (SSM) processing is a forming process which occurs within solidus and liquidus temperatures, and it requires feedstock billets with spheroidal microstructures. In this paper, a novel gas-assisted direct thermal method (DTM) is proposed as a method to create feedstock billets with fine spheroidal microstructures. Effect of different combination parameters between pouring temperature and holding time during the gas-assisted DTM technique on the microstructure of aluminium alloy 7075 feedstock billets was investigated. Pouring of molten aluminium alloy 7075 was conducted at temperatures between 645 and 685 °C, while holding time was set between 20 and 60 s. The melt was cooled down within the semisolid temperature range in a cylindrical copper mould with the help of carbon dioxide (CO2) gas before quenching in room temperature water. Results revealed that the smallest primary phase grain size formed at the combination parameters of 645 °C pouring temperature and 20-s holding time. Furthermore, the same combination parameters also produced the highest circularity value. The addition of external CO2 gas surrounded the copper mould as a rapid cooling agent was found to have a significant improvement of 36.4% to the formation of smaller primary grain and spheroidal structure. It is concluded that the lowest pouring temperature and shortest holding time coupled with rapid cooling condition from the addition of external CO2 during DTM produced the finest and most globular structure of primary phase size.

Isothermal nanocrystallization kinetics during polymorphic transformation

In supercooled water, ice nucleation is a stochastic process that requires ∼250-300 molecules to transiently achieve structural ordering before an embryonic seed crystal can nucleate. This happens most easily on crystalline surfaces, in a process termed heterogeneous nucleation; without such surfaces, water droplets will supercool to below -30 °C before eventually freezing homogeneously. A variety of fundamental processes depends on heterogeneous ice nucleation, ranging from desert-blown dust inducing precipitation in clouds to frost resistance in plants. Recent experiments have shown that crystals of nanophase magnetite (Fe3O4) are powerful nucleation sites for this heterogeneous crystallization of ice, comparable to other materials like silver iodide and some cryobacterial peptides. In natural materials containing magnetite, its ferromagnetism offers the possibility that magneto-mechanical motion induced by external oscillating magnetic fields could act to disrupt the water-crystal interface, inhibiting the heterogeneous nucleation process in subfreezing water and promoting supercooling. For this to act, the magneto-mechanical rotation of the particles should be higher than the magnitude of Brownian motions. We report here that 10-Hz precessing magnetic fields, at strengths of 1 mT and above, on ∼50-nm magnetite crystals dispersed in ultrapure water, meet these criteria and do indeed produce highly significant supercooling. Using these rotating magnetic fields, we were able to elicit supercooling in two representative plant and animal tissues (celery and bovine muscle), both of which have detectable, natural levels of ferromagnetic material. Tailoring magnetic oscillations for the magnetite particle size distribution in different tissues could maximize this supercooling effect.

Thermal analyses were performed for determining the equilibrium melting temperatures T of the respective α‐ and β‐crystal in melt‐crystallized polymorphic poly(heptamethylene terephthalate) (PHepT) using both linear and nonlinear Hoffman‐Weeks (H‐W) methods for comparison of validity. These two crystals in PHepT do not differ much in their melting temperatures. The equilibrium melting temperatures of the α‐ and β‐crystal as determined by the linear H‐W method are 98 °C and 100.1 °C, respectively; but the nonlinear H‐W method yielded higher values for both crystals. The equilibrium melting temperatures of the α‐ and β‐crystal according to the nonlinear H‐W method are 121 °C and 122.5 °C, respectively. Both methods consistently indicate that T of the β‐crystal is only slightly higher than that of the α‐crystal. Such small difference in T between the α‐ and the β‐crystal causes difficulties in judging the relative thermodynamic stability of these two crystals. Thus, kinetics of these two crystals was compared using the Avrami and Ozawa theory. The crystallization produced by quenching from Tmax = 110 °C and 150 °C shows a heterogeneous and homogeneous nucleation mechanism, respectively. The lower Tmax = 110 °C leads to heterogeneous nucleation and only α‐crystal in PHepT, whose crystallization rates at same Tc are much higher than crystallization rates by quenching from Tmax = 150 °C leading to either α‐ or β‐crystal with homogeneous nucleation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1839–1851, 2009

Silver (Ag) nanoparticles were synthesized by a facile route in the presence of oleic acid and n-propylamine. It was shown that the average primary size of the as-synthesized Ag nanoparticles was approximately 10 nm and the surface of as-synthesized Ag nanoparticles was capped with monolayer surfactants with the content of 19.6%. Based on as-synthesized Ag nanoparticles, polyoxymethylene (POM)/Ag nanocomposites were prepared. The influence of Ag nanoparticles on non-isothermal crystallization behavior of POM was investigated by differential scanning calorimetry (DSC). The Jeziorny, Jeziorny-modified Avrami, Ozawa, Liu and Mo, Ziabicki and Kissinger models were applied to analyze the non-isothermal melt crystallization data of POM/Ag nanocomposites. Results of half time (t1/2), crystallization rate parameter (CRP), crystallization rate function (K(T)), kinetic parameter (F(T)), the kinetic crystallizability at unit cooling rate (GZ) and the crystallization activation energy (∆E) were determined. Small amounts of Ag nanoparticles dispersed into POM matrix were shown to act as heterogeneous nuclei, which could enhance the crystallization rate of POM, increase the number of POM spherulites and reduce POM spherulites size. However, the higher loading of Ag nanoparticles were easily aggregated, which restrained POM crystallization to some degree. Furthermore, the POM/Ag nanocomposites showed robust antibacterial activity against Escherichia coli and Staphylococcus aureus.

This paper suggests a mathematical model of processes occurring during nucleation and crystal growth in gels. Calculations showed that there is a locality in a gel that provides the best conditions for nucleation and growing of crystals. Possible reasons restricting crystal growth are discussed. The qualitative agreement of calculations and experimental data allows to assume that the model suggested adequately describes processes occurring during crystal growth. Experimental data interpretation in terms of the model allowed to obtain the diffusion constants of reagents in a gel and the crystal growth rate.

Heterogeneous nucleation models to predict grain size in solidification

The mechanisms of ‘neck-like’ deformation in high-speed melt spinning. 2. Effects of polymer crystallization

Polylactic acid (PLA) is a biopolymer that can replace thermoplastic polymers such as polypropylene (PP) in various applications due to strength, young modulus, biocompatibility, biodegradability, good clarity, oil resistance, and oxygen barrier ability. However, PLA has some drawbacks, including brittle, high glass transition temperature (Tg), and low degradation and crystallization rates. Therefore, modification is needed with the addition of nucleating agents and plasticizers to overcome these limitations of PLA. This research aims to study the effect of plasticizers and microfibril cellulose of oil palm frond (OPF) on thermal stability and to review the crystallization kinetics of PLA biocomposites. Polyethylene glycol and triacetin were used as plasticizers. Thermal analysis was performed using Thermal Gravimetry analysis (TGA) and Differential Scanning Calorimetry (DSC). The crystallization kinetics study was analyzed using a modified Avrami model under non-isothermal conditions. PLAP4000 has better thermal stability than PLAP200 and PLAG with Tonset and Tmax values reaching 349.17°C and 374.68°C, respectively, which are close to pure PLA. All types of plasticizers influenced decreasing the Tg value in the range of 27–42%, whereas OPF microfiber addition contributes to a Tg reduction of 37-55 %. Crystallization kinetic study was informed for heterogeneous and simultaneous nucleation mechanisms with an n value range of about 2-3 for PLAP4000 and PLAOP4000. The crystallization rate was multiplied 4-9-fold for PLAOP200 and 2-3-fold for PLAOP4000.

Experiments have been conducted to examine the effect of the following agents: TiO2, CaO, MgO, BaSO4, SiO2, and Al2O3 as modifiers on the poly(ethylene terephthalate) crystallization kinetics. Modifier concentration in the polymer varied from 0.5% to 3%. Crystallization rate measurements at a temperature of 237°C were performed by dilatometric method and measurements of spherulitic growth rate, by microscopic method. It has been stated that the addition of a modifier affects the crystallization rate, dimension, and homogeneity of spherulitic sizes. The spherulitic growth rate, with the exception of that modified by CaO, does not depend on the kind and the concentration of a modifier. Heterogeneous nucleating agents exert an effect, then, mainly on the heterogeneous nucleation process. In the presence of the agents, the nucleation in the poly(ethylene terephthalate) is of athermal character. The kind of a modifier applied exerts also an effect on the final crystallization degree.

Silica were introduced to segmented copolyester system (poly(butylene terephthalate)‐poly(ethylene terephthalate‐co‐isophthalate‐co‐sebacate) (PBT‐PETIS)) by in situ polymerization. Investigations on melting behavior and crystalline structure were undertaken, and the dispersion situation of silica in segmented copolyester composites was detected. A diverse crystallization characteristic has been found when the modified Avrami analytical method was applied to investigate nonisothermal crystallization behavior of the composites. Crystallization rate was restricted rather than be promoted by increasing loading of silica. The values of Avrami exponent ranged from 2.25 to 2.45, presenting a mechanism of three‐dimensional spherulitic growth with heterogeneous nucleation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1052–1058, 2006

Layered montmorillonite is frequently employed in the fabrication of polymer nanocomposites, with the aim of enhancing the mechanical properties, flame retardancy, and thermal stability of these materials. Beyond its role in augmenting the physical and mechanical attributes of polymeric materials by serving as physical cross‐linking points through non‐covalent interactions between inorganic and organic components, montmorillonite can also be endowed with novel properties through functional modification. We synthesized a heterogeneous nucleating agent endowed with antibacterial capabilities by depositing graphitic carbon nitride (g‐C 3 N 4 ) onto the surface of layered montmorillonite at elevated temperatures, thereby conferring superior antibacterial properties to the composite. During the polyester molding process, the crystallization rate and degree of crystallinity of the polyester are enhanced through the heterogeneous nucleation effect, which in turn significantly ameliorates the material's oxygen and water vapor barrier properties. Concurrently, the photocatalytic activity of the g‐C 3 N 4 on the montmorillonite surface generates reactive oxygen species, which exhibit bactericidal effects. This modified montmorillonite nucleating agent, with its integrated antibacterial functionality, is poised to be utilized in the fabrication and processing of biomedical and food packaging materials. Furthermore, it offers novel insights into the development of functional packaging materials with advanced properties.

This article presents typical values for the most used types of thermophysical property data that are needed for processing and modeling of solidification and casting processes. It describes methods to determine thermophysical properties, such as specific heat capacity and enthalpy of transformation; enthalpy of melting; solidus and liquidus temperatures; coefficient of thermal expansion; density; surface tension; viscosity; electrical and thermal conductivity; and emissivity.