Melting of polymer single crystals studied by dynamic Monte Carlo simulations

We report dynamic Monte Carlo simulations of lattice polymers melting from a metastable chain-folded lamellar single crystal. The single crystal was raised and then melted in an ultrathin film of polymers wetting on a solid substrate, mimicking the melting observations made by using Atomic Force Microscopy. We observed that the thickness distribution of the single crystal appears quite inhomogeneous and the thickness increases gradually from facetted edges to the center. Therefore, at low melting temperatures, melting stops at a certain crystal thickness, and melting-recrystallization occurs when allowing crystal thickening; at intermediate temperatures, melting maintains the crystal shape and exhibits different speeds in two stages; at high temperatures, fast melting makes a melting hole in the thinnest region, as well as a saw-tooth-like pattern at the crystal edges. In addition, the linear melting rates at low temperatures align on the curve extrapolated from the linear crystal growth rates. The temperature dependence of the melting rates exhibits a regime transition similar to crystal growth. Such kinetic symmetry persists in the melting rates with variable frictional barriers for c -slip diffusion in the crystal as well as with variable chain lengths. Visual inspections revealed highly frequent reversals upon melting of single chains at the wedge-shaped lateral front of the lamellar crystal. We concluded that the melting kinetics is dominated by the reverse process of intramolecular secondary crystal nucleation of polymers.     

Effect of intense laser irradiation on the lattice stability of semiconductors and metals

The effect of intense ultrashort irradiation on interatomic forces, crystal stability, and possible melting transition of the underlying lattice is not completely elucidated. By using ab initio linear response to compute the phonon spectrum of gold, silicon, and aluminum, we found that silicon and gold behave in opposite ways when increasing radiation intensity: whereas a weakening of the silicon bond induces a lattice instability, gold undergoes a sharp increase of its melting temperature, while a significantly smaller effect is observed for aluminum for electronic temperatures up to 6 eV.     

Monte Carlo Simulation for the Photoinduced Phase Transition on a Two-Dimensional Stripe-Structure

By means of Monte Carlo simulations for a kinetic Ising model on a two-dimensional square lattice, we demonstrate that a photoinduced phase transition is accomplished more rapidly even for weaker light in a stripe-structure consisting of two kinds of constituent units than in a homogeneous structure. This is due to accelerated nucleation of a final phase in the constituent unit that is relatively close to instability locally.     

Vortex liquid crystals in anisotropic type II superconductors

In an isotropic type II superconductor in a moderate magnetic field, the transition to the normal state occurs by vortex lattice melting. In certain anisotropic cases, the vortices acquire elongated cross sections and interactions. Systems of anisotropic, interacting constituents generally exhibit liquid crystalline phases. We examine the possibility of a two step melting in homogeneous type II superconductors with anisotropic superfluid stiffness from a vortex lattice into first a vortex smectic and then a vortex nematic at high temperature and magnetic field. We find that fluctuations of the ordered phase favor an instability to an intermediate smectic-A in the absence of intrinsic pinning.     

Atomic mechanism of homogeneous melting of bcc Fe at the limit of superheating

Atomic mechanism of homogeneous melting of bcc Fe is studied via monitoring spatiotemporal arrangements of the liquid-like atoms, which are detected by the Lindemann criterion of melting, during the heating process. Calculations are performed by molecular dynamics (MD) simulations. Calculations show that liquid-like atoms occur randomly in the crystalline matrix at temperature far below the melting point due to local instability of the crystalline lattice. Number of liquid-like atoms increases with increasing temperature and they have a tendency to form clusters. Subsequently, a single percolated liquid-like cluster is formed in the crystalline model and at the melting point 99% atoms in the model become liquid-like to form a liquid phase. Melting is also accompanied by the sudden changes in various static and thermodynamic quantities. However, total melting is reached just at the point above the melting one. Three characteristic temperatures of the homogeneous melting of bcc Fe are determined.     

Stability-instability transitions in silicon crystal growth

In order for a crystal to grow, source atoms must be incorporated into the underlying lattice. Typically, this process occurs on the surface in one of two modes: either through island nucleation or through step flow. However, a third, morphologically unstable growth mode has been predicted. Monitoring the surface of ultraflat substrates with an in situ scanning electron microscope, we prove that for the (111) face of silicon there is a transition from stable step flow to morphological instability and then to island nucleation.     

Homogeneous nucleation of glide dislocation loops in nanoceramics

A theoretical model is proposed for the homogeneous nucleation of glide dislocation loops in nanocrystalline ceramics under deformation at low and high temperatures. The nucleation of a dislocation loop in a crystalline grain is considered an ideal nanoscopic shear whose magnitude (the Burgers vector of the dislocation) increases gradually as the loop is nucleating. The characteristics of the homogeneous nucleation of glide dislocation loops in nanocrystalline ceramics based on cubic silicon carbide are calculated. It is shown that, in general, the homogeneous nucleation of a dislocation loop in nanocrystalline ceramics at high temperatures proceeds in two stages, namely, the athermal nucleation of a loop of a “noncrystallographic” partial dislocation and its thermally activated transformation into an ordinary partial lattice dislocation loop.     

Crystal nucleation of colloidal suspensions under shear

We use Brownian dynamics simulations in combination with the umbrella sampling technique to study the effect of shear flow on homogeneous crystal nucleation. We find that a homogeneous shear rate leads to a significant suppression of the crystal nucleation rate and to an increase of the size of the critical nucleus. A simple, phenomenological extension of classical nucleation theory accounts for these observations. The orientation of the crystal nucleus is tilted with respect to the shear direction.     

Surface nucleation in the crystallisation of polyethylene droplets

The division of semi-crystalline polymeric material into small domains is an effective tool for studying crystal nucleation. The scaling behavior of the nucleation rate as a function of domain size can reveal important information about the mechanism responsible for the birth of a crystal nucleus. We have investigated the process of crystal nucleation in a system of dewetted polyethylene droplets. Through the use of a correlation sample analysis, we are able to differentiate between heterogeneous and homogeneous nucleation mechanisms in a droplet sample. An analysis of the dependence of the nucleation rate on droplet size reveals that the nucleation probability scales with the surface area of the droplet.     

Direct visualisation of homogeneous and heterogeneous crystallisation in an ensemble of confined domains of poly(ethylene oxide)

We present a study of homogeneous and heterogeneous nucleation in polymer crystallisation. In bulk samples the crystallization is typically dominated by nucleation from defects (heterogeneous nucleation), and consequently studies must rely on sample preparation to minimize this effect. We present a study of nucleation within discrete droplets of poly(ethylene oxide) that are formed by the dewetting of a thin film on an unfavourable substrate. The samples provide an ensemble of impurity-free droplets, with length scales that can easily be measured. We show that the data for heterogeneous and homogeneous nucleation is qualitatively different, and that the data mirrors the fundamental differences in the underlying mechanisms for the two nucleation processes. The experiments presented here provide a simple method that can be used to study heterogeneous and homogeneous nucleation in great detail.Received: 1 January 2003, Published online: 30 October 2003PACS: 61.41. + e Polymers, elastomers, and plastics - 68.55.-a Thin film structure and morphology - 81.10.-h Methods of crystal growth; physics of crystal growth     

Dynamics of the crystallized one-component plasma

The dynamics and energy of the crystallized one-component plasma (OCP) is evaluated using the self-consistent-phonon (SCP) theory of lattice dynamics. Melting of the crystal is also examined. The OCP crystal is harmonic for particle rms vibrational amplitudes as large as 25% of the interparticle spacing. This is due to the soft (r^?1) core of the Coulomb potential. Anharmonic effects are, however, entirely responsible for the eventual mechanical instability, identified here with melting, of the crystal at large enough rms amplitudes. This takes place at r_s = 180 at T = 0 K for the most sophisticated SCP theory. In the classical limit, this SCP theory predicts the crystal to be more stable than does the “exact” Monte Carlo study of melting by Pollock and Hansen. This suggests that including further anharmonic terms in the SCP theory leads to melting at even larger r_s at T = 0 K. However, comparison of crystal and fluid energies by Ceperley, Hansen, and Mazighi suggest melting in the range r_s = 65 to 135. Near melting the anharmonic contributions shift the phonon frequencies by a factor of 2 and the phonon lifetimes become very short.     

The thermo-elastic instability model of melting of alkali halides in the Debye approximation

The Debye model of lattice vibrations of alkali halides is used to show that there is a temperature below the melting temperature where the vibrational pressure exceeds the electrostatic pressure. The onset temperature of this thermo-elastic instability scales as the melting temperature of NaCl, KCl, and KBr, suggesting its role in the melting of the alkali halides in agreement with a previous more rigorous model.     

Modulational Instability of Spinor Condensates in an Optical Lattice

We obtain analytically the static states and corresponding collective-excitation spectra of a quasi-onedimensional spin-1 condensate modulated by a long-wavelength optical lattice in the weak lattice limit. It is demonstrated that both ferromagnetic and antiferromagnetic condensates may exhibit dynamical instability, which agree with the results with numerical simulation. In the homogeneous limit, our results reduce to the previous results for homogeneous spinor condensates, i.e., dynamical instability can occur only for ferromagnetic interaction and an antiferromagnetic condensate is always dynamically stable.     

Crystal-lattice coupling to the vortex-melting transition in YBa(2)Cu(3)O(7-delta)

Distinct discontinuities in the thermal expansion of the crystal lattice are observed at the melting transition of the vortex lattice in a naturally untwinned reversible YBa(2)Cu3O(7-delta) single crystal using high-resolution dilatometry. This coupling between the vortex transition and the crystal lattice demonstrates that the crystal lattice is more than a mere host for the vortices, and it is attributed to a strong pressure dependence of the superconducting transition temperature and thus to the condensation energy at the vortex-melting temperature.     

Melting and resolidification of gold film irradiated by nano- to femtosecond lasers

Rapid melting and resolidification of a free-standing gold film subject to nano- to femtosecond laser pulses are investigated using the two-temperature model in conjunction with an interfacial tracking method. The interfacial velocity, as well as elevated melting temperature and depressed solidification temperature, in the ultra-fast phase-change process are obtained by considering the interfacial energy balance and nucleation dynamics. A nonlinear electron heat capacity and a temperature-dependent electron–lattice coupling factor for the rapid phase change are taken into account. Effects of laser pulse width and fluence on melting and resolidification are also studied. PACS 42.62.Eh; 63.20.Kr; 64.70.Dv     

A New View of Incipient Plastic Instability during Nanoindentation

Whether the dislocation nucleation or the sudden dislocation multiplication dominates the incipient plastic instability during the nanoindentation of initial defect-free single crystal still remains unclear. In this work, the dislocation mechanism corresponding to the incipient plastic instability is numerically investigated by coupling discrete dislocation dynamics with the finite element method. The coupling model naturally introduces the dislocation nucleation and accurately captures the heterogeneous stress field during nanoindentation. The simulation results show that the first dislocation nucleation induces the initial pop-in event when the indenter is small, while for larger indenters, the incipient plastic instability is ascribed to the cooperation between dislocation nucleation and multiplication. Interestingly, the local dislocation densities for both cases are almost the same when the sudden load drop occurs. Thus it is inferred that the adequate dislocations generated by either nucleation or multiplication, or both, are the requirement for the trigger of incipient plastic instability. A unified dislocation-based mechanism is proposed to interpret the precipitate incipient plastic instability.     

Theoretical strength of 2D hexagonal crystals: application to bubble raft indentation

By means of lattice and molecular dynamics we study the theoretical strength of homogeneously strained, defect-free 2D crystals whose atoms interact via pair potentials with short- and longer-ranged interactions, respectively. We calculate the instability surface, i.e. the boundary in the 3D homogeneous strain space (ε _xx ,?ε _yy ,?ε _xy ), at which the first vanishing of the frequency of a vibrational mode occurs, taking into account all 2(N???1)?+?3 modes of a 2D periodic system of N atoms. We also compute the strain energies of the crystal on the instability surface, thus defining the most dangerous direction(s) of strain where the critical energy density is small. A theory is developed to incorporate the effect of loading device–sample interactions in the lattice instability criterion. The results are applied to the model problem of bubble raft indentation. We analyse the distribution of the unstable phonon modes in the first Brillouin zone as a function of the loading parameter, and discuss the post-critical behaviour of the lattice in the presence of strain gradients as in nano-indentation experiments.     

Isothermal Crystallization Kinetics and Melting Behavior of a Luminescent Conjugated Polymer,Poly(9,9-Dihexylfluorene-Alt-2,5-Didodecyloxybenzene)

A study of the isothermal crystallization behaviors of poly(9,9-dihexylfluorene-alt-2,5-didodecyloxybenzene) (PF6OC12) was carried out using differential scanning calorimetry (DSC). The crystallization kinetics under isothermal conditions could be described by the Avrami equation. The Avrami exponent n ranges from 3.43 to 3.71 for PF6OC12 at crystallization temperatures between 100.0°C and 90.0°C, indicating a three-dimensional spherical crystal growth with homogeneous nucleation in the primary crystallization stage for the isothermal melt crystallization process. In the DSC scan, after the isothermal crystallization, multiple melting behavior was found. The multiple endotherms could be attributed to melting of recrystallized materials produced originally during different crystallization processes. According to the Arrhenius equation, the activation energy was determined to be 211.29 kJmol^?1 for the isothermal melt crystallization of PF6OC12.