Stress crystallization

Considering the crystal imperfections that are typically found in all crystals, the crystal quality of organic pigments is a major concern. The external surface of any crystal exhibits a number of defects, which expose portions of the crystal surface to the surrounding molecules. Impurities and voids permeate the entire interior structure of the crystal. Stress, brought about by factors such as applied shear, may change the cell constants (distances between atoms, crystalline angles). It is also possible for the three dimensional order to be incomplete or limited to one or two dimensions only (dislocations, inclusions). 

We now consider various examples of two-component crystals, stressing the ways in which the chemical environment of a molecule may be varied from that in its own crystalline phase and, of course, from that in any fluid phase, and the chemical consequences of this variation. 

The crystallographic c/a ratio of ice doped with HF and NH4F is slightly shortened. This confirms the concept of substitutional emplacement of these impurity molecules. A hexagonal microstructure, which develops as a consequence either of crystallization stress or of aging, is relieved in highly doped crystals. 

Sun, B., Suo, Z. and Evans, A. G. (1994), Emergence of cracks by mass transport in elastic crystals stressed at high temperatures. Journal of the Mechanics and Physics of Solids 42, 1653-1677. 

The following is the summary of the results of the studies (31) on the effect of stereoregularity on stress-induced crystallization and mechanical properties of the vulcanlzates of propylene oxide copolymers. In the studies on stress-induced crystallization, stress (O ) and birefringence ( ) were measured as a function of temperature using an Instron tester fitted with a thermostatted Insulated chamber and an optical system. In an amorphous rubber, the quantity (T Vo) (where T is absolute temperature) is almost constant. Stress-induced crystallization leads to the formation of crystals oriented in the stretching direction which substantially Increase the birefringence. 

Angle between the tensile axis and the slip direction for a single crystal stressed in tension (Figure 7.7)... 

In Chapter III, surface free energy and surface stress were treated as equivalent, and both were discussed in terms of the energy to form unit additional surface. It is now desirable to consider an independent, more mechanical definition of surface stress. If a surface is cut by a plane normal to it, then, in order that the atoms on either side of the cut remain in equilibrium, it will be necessary to apply some external force to them. The total such force per unit length is the surface stress, and half the sum of the two surface stresses along mutually perpendicular cuts is equal to the surface tension. (Similarly, one-third of the sum of the three principal stresses in the body of a liquid is equal to its hydrostatic pressure.) In the case of a liquid or isotropic solid the two surface stresses are equal, but for a nonisotropic solid or crystal, this will not be true. In such a case the partial surface stresses or stretching tensions may be denoted as Ti and T2-... 

Actual crystal planes tend to be incomplete and imperfect in many ways. Nonequilibrium surface stresses may be relieved by surface imperfections such as overgrowths, incomplete planes, steps, and dislocations (see below) as illustrated in Fig. VII-5 [98, 99]. The distribution of such features depends on the past history of the material, including the presence of adsorbing impurities [100]. Finally, for sufficiently small crystals (1-10 nm in dimension), quantum-mechanical effects may alter various physical (e.g., optical) properties [101]. 

An indirect estimate of surface tension may be obtained from the change in lattice parameters of small crystals such as magnesium oxide and sodium chloride owing to surface tensional compression [121] however, these may represent nonequilibrium surface stress rather than surface tension [68]. Surface stresses may produce wrinkling in harder materials [122]. 

Most solid surfaces are marred by small cracks, and it appears clear that it is often because of the presence of such surface imperfections that observed tensile strengths fall below the theoretical ones. For sodium chloride, the theoretical tensile strength is about 200 kg/mm [136], while that calculated from the work of cohesion would be 40 kg/mm [137], and actual breaking stresses are a hundreth or a thousandth of this, depending on the surface condition and crystal size. Coating the salt crystals with a saturated solution, causing surface deposition of small crystals to occur, resulted in a much lower tensile strength but not if the solution contained some urea. 

Parodi O 1970 Stress tensor for a nematic liquid crystal J.PhysiqueZ 581-4... 

There is a very important point to stress about the above procedure. Strike listed ether, DCM and ethanol as crystallization solvents. But the one chemists should use is DCM. That s right...DCM Strike is telling all of you right now that DCM is an absolutely superior solvent for crystallization. In fact it is so good that one need not purify the freebases acquired from the ends of half of the recipes in this book. 

The measurement of mass using a quartz crystal microbalance is based on the piezoelectric effect.When a piezoelectric material, such as a quartz crystal, experiences a mechanical stress, it generates an electrical potential whose magnitude is proportional to the applied stress. Gonversely, when an alternating electrical field is... 

The isothermal curves of mechanical properties in Chap. 3 are actually master curves constructed on the basis of the principles described here. Note that the manipulations are formally similar to the superpositioning of isotherms for crystallization in Fig. 4.8b, except that the objective here is to connect rather than superimpose the segments. Figure 4.17 shows a set of stress relaxation moduli measured on polystyrene of molecular weight 1.83 X 10 . These moduli were measured over a relatively narrow range of readily accessible times and over the range of temperatures shown in Fig. 4.17. We shall leave as an assignment the construction of a master curve from these data (Problem 10). 

The nucleation, growth, and morphology of crystals are influenced by both temperature and stress. 

This class of smart materials is the mechanical equivalent of electrostrictive and magnetostrictive materials. Elastorestrictive materials exhibit high hysteresis between strain and stress (14,15). This hysteresis can be caused by motion of ferroelastic domain walls. This behavior is more compHcated and complex near a martensitic phase transformation. At this transformation, both crystal stmctural changes iaduced by mechanical stress and by domain wall motion occur. Martensitic shape memory alloys have broad, diffuse phase transformations and coexisting high and low temperature phases. The domain wall movements disappear with fully transformation to the high temperature austentic (paraelastic) phase. 

A common measurement usehil in predicting threadline behavior is fiber tension, frequentiy misnamed spinline stress. It is normally measured after the crystallization point in the threadline when the steady state is reached and the threadline is no longer deformed. Fiber tension increases as take-up velocity increases (38) and molecular weight increases. Tension decreases as temperature increases (41). Crystallinity increases slightiy as fiber tension is increased (38). At low tension, the birefringence increases as tension is increased, leveling off at a spinline tension of 10 MPa (1450 psi) (38). 

Terephthahc acid (TA) or dimethyl terephthalate [120-61 -6] (DMT) reacts with ethyleae glycol (2G) to form bis(2-hydroxyethyl) terephthalate [959-26-2] (BHET) which is coadeasatioa polymerized to PET with the elimination of 2G. Moltea polymer is extmded through a die (spinneret) forming filaments that are solidified by air cooling. Combinations of stress, strain, and thermal treatments are appHed to the filaments to orient and crystallize the molecular chains. These steps develop the fiber properties required for specific uses. The two general physical forms of PET fibers are continuous filament and cut staple. 

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). 

Weathering. Articles fabricated from FEP are unaffected by weather, and thek resistance to extreme heat, cold, and uv kradiation suits them for apphcations in radar and other electronic components. For example, after 15 years of solar exposure in Florida, the tensile strength (73) and light transmission (96%) of a 25-p.m thick film was unchanged and the film remained crystal clear. Elongation increased slightly for the first 5 to 7 years of outdoor exposure, probably as a result of stress relaxation. Beyond 10 years, a small decrease was observed. 

AH intrinsic germanium metal sold is specified to be N-type with a resistivity of at least 40 H-cm at 25°C or 50 H-cm at 20°C. Germanium metal prepared for use in infrared optics is usuaHy specified to be N-type with a resistivity of 4-40 Hem, to be stress-free and fine annealed, and to have certain minimum transmission (or maximum absorption) characteristics in the 3—5 or 8—12 pm wavelength ranges. Either polycrystaHine or single-crystal material is specified. 

Fig. 2. Yield stress as a function of temperature for NiAl, Ni Al, and several commercial superaUoys where <001> is the paraHel-to-tensile axis for single crystals and (° ) are data points for NiAl + (2). See text. To convert MPa to psi, multiply by 145.

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