Finite-size scaling investigation of the liquid-liquid critical point in ST2 water and its stability with respect to crystallization.

The liquid-liquid critical point scenario of water hypothesizes the existence of two metastable liq- uid phases low-density liquid (LDL) and high-density liquid (HDL) deep within the supercooled region. The hypothesis originates from computer simulations of the ST2 water model, but the stabil- ity of the LDL phase with respect to the crystal is still being debated. We simulate supercooled ST2 water at constant pressure, constant temperature, and constant number of molecules N for N ≤ 729 and times up to 1 μs. We observe clear differences between the two liquids, both structural and dynamical. Using several methods, including finite-size scaling, we confirm the presence of a liquid-liquid phase transition ending in a critical point. We find that the LDL is stable with respect to the crystal in 98% of our runs (we perform 372 runs for LDL or LDL-like states), and in 100% of our runs for the two largest system sizes (N = 512 and 729, for which we perform 136 runs for LDL or LDL-like states). In all these runs, tiny crystallites grow and then melt within 1 μs. Only for N ≤ 343 we observe six events (over 236 runs for LDL or LDL-like states) of spontaneous crystal- lization after crystallites reach an estimated critical size of about 70 ± 10 molecules.

Crystallization and properties of poly(ethylene terephtalate) copolymers containing 5-tert-butyl isophtalic units

The influence of incorporating 5-tert-butyl isophthalic units (tBI) in the polymer chain of poly(ethylene terephthalate) (PET) on the crystallization behavior, crystal structure, and tensile and gas transport properties of this polyester was evaluated. Random poly(ethyleneterephthalate-co-5-tert-butyl isophthalate) copolyesters (PETtBI) containing between 5 and 40 mol% of tBI units were examined. Isothermal crystallization studies were performed on amorphous glassy films at 120 8C and on molten samples at 200 8C by means of differential scanning calorimetry. Furthermore, the non-isothermal crystallization behavior of the copolyesters was investigated. It was observed that both crystallinity and crystallization rate of the PETtBI copolyesters tend to decrease largely with the comonomeric content, except for the copolymer containing 5 mol% of tBI units, which crystallized faster than PET. Fiber X-ray diffraction patterns of the semicrystalline PETtBI copolyesters proved that they adopt the same triclinic crystal structure as PET with the comonomeric units being excluded from the crystalline phase. Although PETtBI copolyesters became brittle for higher contents in tBI, the tensile modulus and strength of PET were barely affected by copolymerization. The ncorporation of tBI units slightly increased the permeability of PET, but copolymers containing up to 20 mol% of the comonomeric units were still able to present barrier properties.

Cell size distribution in a random tessellation of space governed by the Kolmogorov-Johnson-Mehl-Avrami model: Grain size distribution in crystallization

The space subdivision in cells resulting from a process of random nucleation and growth is a subject of interest in many scientific fields. In this paper, we deduce the expected value and variance of these distributions while assuming that the space subdivision process is in accordance with the premises of the Kolmogorov-Johnson-Mehl-Avrami model. We have not imposed restrictions on the time dependency of nucleation and growth rates. We have also developed an approximate analytical cell size probability density function. Finally, we have applied our approach to the distributions resulting from solid phase crystallization under isochronal heating conditions

Crystallization behaviour of some melt spun Nd-Fe-B alloys

The kinetics of crystallization of four amorphous (or partially amorphous) melt spun Nd-Fe-B alloys induced by thermal treatment is studied by means of differential scanning calorimetry and scanning electron microscopy, In the range of temperatures explored experimentally, the crystallization process is thermally activated and generally proceeds in various stages. The Curie temperature and the crystallization behavior have been measured. The apparent activation energy of crystallization of most of the crystallization stages has been determined for each melt spun alloy. The explicit form of the kinetic equation that best describes the first stage of crystallization has been found. It follows in general the Johnson-Mehl-Avrami-Erofe'ev model, but clear deviations to that model occur for one alloy. Scanning electron microscopy demonstrates that preferentially hetereogeneous nucleation occurs at the ribbon surface which was in contact with the wheel. From crystallization kinetics results the lower part of the experimental time-temperature-transformation curves for all studied alloys are deduced and extrapolated to the high temperature limit of their range of validity, also deduced.

Accuracy in the experimental calorimetric study of the crystallization kinetics and predicitve transformation diagrams: Application to a Ga-Te amorphous alloy

The uncertainties inherent to experimental differential scanning calorimetric data are evaluated. A new procedure is developed to perform the kinetic analysis of continuous heating calorimetric data when the heat capacity of the sample changes during the crystallization. The accuracy of isothermal calorimetric data is analyzed in terms of the peak-to-peak noise of the calorimetric signal and base line drift typical of differential scanning calorimetry equipment. Their influence in the evaluation of the kinetic parameters is discussed. An empirical construction of the time-temperature and temperature heating rate transformation diagrams, grounded on the kinetic parameters, is presented. The method is applied to the kinetic study of the primary crystallization of Te in an amorphous alloy of nominal composition Ga20Te80, obtained by rapid solidification.

Effect of the nanoparticles on the structure and crystallization of amorphous silicon thin films produced by rf glow discharge

Thin films of nanostructured silicon (ns-Si:H) were deposited by plasma-enhanced chemical vapor deposition in the presence of silicon nanoparticles at 100 C substrate temperature using silane and hydrogen gas mixture under continuous wave (cw) plasma conditions. The nanostructure of the films has been demonstrated by diverse ways: transmission electron microscopy, Raman spectroscopy and x-ray diffraction, which have shown the presence of ordered silicon clusters (1!=2 nm) embedded in an amorphous silicon matrix. Due to the presence of these ordered domains, the films crystallize faster than standard hydrogenated amorphous silicon samples, as evidenced by electrical measurements during the thermal annealing.

Anomalous crystallization of hydrogenated amorphous silicon during fast heating ramps

Thermal crystallization experiments carried out using calorimetry on several a-Si:H materials with different microstructures are reported. The samples were crystallized during heating ramps at constant heating rates up to 100 K/min. Under these conditions, crystallization takes place above 700 C and progressively deviates from the standard kinetics. In particular, two crystallization processes were detected in conventional a-Si:H, which reveal an enhancement of the crystallization rate. At100 K/min, such enhancement is consistent with a diminution of the crystallization time by a factor of 7. In contrast, no systematic variation of the resulting grain size was observed. Similar behavior was also detected in polymorphous silicon and silicon nanoparticles, thus showing that it is characteristic of a variety of hydrogenated amorphous silicon materials.

Molecular dynamics study of orientational cooperativity in water

Recent experiments on liquid water show collective dipole orientation fluctuations dramatically slower than expected (with relaxation time >tation, the self-dipole randomization time tr, which is an upper limit on ta; we find that tr5ta. Third, to check if there are correlated domains of dipoles in water which have large relaxation times compared to the individual dipoles, we calculate the randomization time tbox of the site-dipole field, the net dipole moment formed by a set of molecules belonging to a box of edge Lbox. We find that the site-dipole randomization time tbox2.5ta for Lbox3 , i.e., it is shorter than the same quantity calculated for the self-dipole. Finally, we find that the orientational correlation length is short even at low T.

Velocity fluctuations of fracturelike disruptions of associating polymer solutions

Velocity has been measured as a function of time for propagating crack tips as water is injected into solutions of end-capped associating polymers in a rectanguar Hele-Shaw cell. Measurements were performed for flows with different values of cell gap, channel width, polymer molecular weight, and polymer concentration. The condition for the onset of fracturelike behavior is well described by a Deborah number which uses the shear-thinning shear rate of the polymer solution as a characteristic frequency for network relaxation. At low molecular weight, the onset of fracturelike pattern evolution is accompanied by an abrupt jump in tip velocity, followed by a lower and approximately constant acceleration. At high molecular weight, the transition to fracturelike behavior involves passing through a regime that may be understood in terms of stick-slip dynamics. The crack-tip wanders from side to side and fluctuates (in both speed and velocity along the channel) with a characteristic frequency which depends linearly on the invading fluid injection rate.

Velocity-jump instabilities in Hele-Shaw flow of associating polymer solutions

We study fracturelike flow instabilities that arise when water is injected into a Hele-Shaw cell filled with aqueous solutions of associating polymers. We explore various polymer architectures, molecular weights, and solution concentrations. Simultaneous measurements of the finger tip velocity and of the pressure at the injection point allow us to describe the dynamics of the finger in terms of the finger mobility, which relates the velocity to the pressure gradient. The flow discontinuities, characterized by jumps in the finger tip velocity, which are observed in experiments with some of the polymer solutions, can be modeled by using a nonmonotonic dependence between a characteristic shear stress and the shear rate at the tip of the finger. A simple model, which is based on a viscosity function containing both a Newtonian and a non-Newtonian component, and which predicts nonmonotonic regions when the non-Newtonian component of the viscosity dominates, is shown to agree with the experimental data.

Analcime crystallization and compositional profiles - Comparing approaches to detect post-depositional alterations in archaeological pottery

The approaches of comparative studies and profile measurements, often used in order to detect post-depositional alterations of ceramics, have been applied simultaneously to two sets of Roman pottery, both of which include altered individuals. As analytical techniques, Neutron Activation Analysis and X-Ray Diffraction have been used. Both approaches lead to substantially different results. This shows that they detect different levels of alteration and should complement each other rather than being used exclusively. For the special process of a glassy phase decomposition followed by a crystallization of the Na-zeolite analcime, the results suggest that it changes high-fired calcareous pottery rapidly, and so fundamentally that the results of various archaeometric techniques can be severely disturbed.

Crystallization and resolution of the lipoxygenase of Pseudomonas aeruginosa 42A2 and phylogenetic study of the subfamilies of the lipoxygenases

Lipoxygenases are non-heme iron enzymes essential in eukaryotes, where they catalyze the formation of the fatty acid hydroperoxides that are required by a large diversity of biological and pathological processes. In prokaryotes, most of them totally lacking in polyunsaturated fatty acids, the possible biological roles oflipoxygenases have remained obscure. In this study, it is reported the crystallization of a lipoxygenase of Pseudomonas aeruginosa (Pa_LOX), the first from a prokaryote. High resolution data has been acquired which is expected to yield structural clues to the questions adressed. Besides, a preliminar phylogenetic analysis using 14 sequences has confirmed the existence of this subfamily of bacterial lipoxygenases, on one side, and a greater diversity than in the corresponding eukaryotic ones, on the other. Finally, an evolutionary study of bacteriallipoxygenases on the same set of lipoxygenases, show a selection pressure of a basically purifying or neutral character except for a single aminoacid, which would have been selected after a positive selection event.

Crystallization and resolution of the lipoxygenase of Pseudomonas aeruginosa 42A2 and phylogenetic study of the subfamilies of the lipoxygenases

Lipoxygenases are non-heme iron enzymes essential in eukaryotes, where they catalyze the formation of the fatty acid hydroperoxides that are required by a large diversity of biological and pathological processes. In prokaryotes, most of them totally lacking in polyunsaturated fatty acids, the possible biological roles oflipoxygenases have remained obscure. In this study, it is reported the crystallization of a lipoxygenase of Pseudomonas aeruginosa (Pa_LOX), the first from a prokaryote. High resolution data has been acquired which is expected to yield structural clues to the questions adressed. Besides, a preliminar phylogenetic analysis using 14 sequences has confirmed the existence of this subfamily of bacterial lipoxygenases, on one side, and a greater diversity than in the corresponding eukaryotic ones, on the other. Finally, an evolutionary study of bacteriallipoxygenases on the same set of lipoxygenases, show a selection pressure of a basically purifying or neutral character except for a single aminoacid, which would have been selected after a positive selection event.

Anomalous crystallization of hydrogenated amorphous silicon during fast heating ramps

Thermal crystallization experiments carried out using calorimetry on several a-Si:H materials with different microstructures are reported. The samples were crystallized during heating ramps at constant heating rates up to 100 K/min. Under these conditions, crystallization takes place above 700 C and progressively deviates from the standard kinetics. In particular, two crystallization processes were detected in conventional a-Si:H, which reveal an enhancement of the crystallization rate. At100 K/min, such enhancement is consistent with a diminution of the crystallization time by a factor of 7. In contrast, no systematic variation of the resulting grain size was observed. Similar behavior was also detected in polymorphous silicon and silicon nanoparticles, thus showing that it is characteristic of a variety of hydrogenated amorphous silicon materials

Solid phase crystallization under continuous heating: kinetic and microstructure scaling laws

The kinetics and microstructure of solid-phase crystallization under continuous heating conditions and random distribution of nuclei are analyzed. An Arrhenius temperature dependence is assumed for both nucleation and growth rates. Under these circumstances, the system has a scaling law such that the behavior of the scaled system is independent of the heating rate. Hence, the kinetics and microstructure obtained at different heating rates differ only in time and length scaling factors. Concerning the kinetics, it is shown that the extended volume evolves with time according to αex = [exp(κCt′)]m+1, where t′ is the dimensionless time. This scaled solution not only represents a significant simplification of the system description, it also provides new tools for its analysis. For instance, it has been possible to find an analytical dependence of the final average grain size on kinetic parameters. Concerning the microstructure, the existence of a length scaling factor has allowed the grain-size distribution to be numerically calculated as a function of the kinetic parameters