Molecular crystals speed

Application of Eq. 19 to the /7-HMX isotherm from simulations leads to the Us-Up curve shown in Fig. 11, where negative curvature in the simulation results is clearly evident (filled circles). While such behavior would be anomalous for metals, it is actually expected for pressures below about one GPa in the case of polyatomic molecular crystals, due to complicated molecular packings and intramolecular flexibility, and has in fact been reported for the high explosives pentaerythritol tetranitrate (PETN) where careful studies were performed for low levels of compression [77], By contrast, the experimental results for /3-HMX in the Us-Up plane do not exhibit significant curvature due to lack of data at pressures below about one Gpa [78], Thus, estimates of isothermal sound speeds, and hence isothermal bulk moduli, based on... 

Flow processes iaside the spinneret are governed by shear viscosity and shear rate. PET is a non-Newtonian elastic fluid. Spinning filament tension and molecular orientation depend on polymer temperature and viscosity, spinneret capillary diameter and length, spin speed, rate of filament cooling, inertia, and air drag (69,70). These variables combine to attenuate the fiber and orient and sometimes crystallize the molecular chains (71). 

At HOY speeds, the rate of increase in orientation levels off but the rate of crystallization increases dramatically. Air drag and inertial contributions to the threadline stress become large. Under these conditions, crystallization occurs very rapidly over a small filament length and a phenomenon called neck-draw occurs (68,75,76). The molecular stmcture is stable, fiber tensde strength is adequate for many uses, thermal shrinkage is low, and dye rates are higher than traditional slow speed spun, drawn, and heat-set products (77). 

Tensile Properties. Tensile properties of nylon-6 and nylon-6,6 yams shown in Table 1 are a function of polymer molecular weight, fiber spinning speed, quenching rate, and draw ratio. The degree of crystallinity and crystal and amorphous orientation obtained by modifying elements of the melt-spinning process have been related to the tenacity of nylon fiber (23,27). 

We have so far assumed that the atoms deposited from the vapor phase or from dilute solution strike randomly and balHstically on the crystal surface. However, the material to be crystallized would normally be transported through another medium. Even if this is achieved by hydrodynamic convection, it must nevertheless overcome the last displacement for incorporation by a random diffusion process. Therefore, diffusion of material (as well as of heat) is the most important transport mechanism during crystal growth. An exception, to some extent, is molecular beam epitaxy (MBE) (see [3,12-14] and [15-19]) where the atoms may arrive non-thermalized at supersonic speeds on the crystal surface. But again, after their deposition, surface diffusion then comes into play. 

The rapid rise in computer speed over recent years has led to atom-based simulations of liquid crystals becoming an important new area of research. Molecular mechanics and Monte Carlo studies of isolated liquid crystal molecules are now routine. However, care must be taken to model properly the influence of a nematic mean field if information about molecular structure in a mesophase is required. The current state-of-the-art consists of studies of (in the order of) 100 molecules in the bulk, in contact with a surface, or in a bilayer in contact with a solvent. Current simulation times can extend to around 10 ns and are sufficient to observe the growth of mesophases from an isotropic liquid. The results from a number of studies look very promising, and a wealth of structural and dynamic data now exists for bulk phases, monolayers and bilayers. Continued development of force fields for liquid crystals will be particularly important in the next few years, and particular emphasis must be placed on the development of all-atom force fields that are able to reproduce liquid phase densities for small molecules. Without these it will be difficult to obtain accurate phase transition temperatures. It will also be necessary to extend atomistic models to several thousand molecules to remove major system size effects which are present in all current work. This will be greatly facilitated by modern parallel simulation methods that allow molecular dynamics simulations to be carried out in parallel on multi-processor systems [115]. 

The dramatic slowing down of molecular motions is seen explicitly in a vast area of different probes of liquid local structures. Slow motion is evident in viscosity, dielectric relaxation, frequency-dependent ionic conductance, and in the speed of crystallization itself. In all cases, the temperature dependence of the generic relaxation time obeys to a reasonable, but not perfect, approximation the empirical Vogel-Fulcher law ... 

Ziabicki and Jericki reported the crystallization characteristics of PET as well as a theory of molecular orientation and oriented crystallization [5a], Besides these theoretical considerations, the rate of recrystallization understandably seems to play an important role, particularly in high-speed spinning. Little is known about the crystallinity gradient caused during melt spinning at high take-up speeds. 

The critical state of stress-induced crystallization at high spinning speeds is governed by the viscoelasticity of the polymer in combination with its crystallization behavior. Any kind of coarse particle obviously disturbs the structure and affects the resistance against deformation. The development of stress is controlled by the rheological properties of the polymer. Shimizu et al. [4] found that increasing the molecular weight drastically promotes the crystallinity under stress conditions. 

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