Cooling under stress

Secondary bonds are considerably weaker than the primary covalent bonds. When a linear or branched polymer is heated, the dissociation energies of the secondary bonds are exceeded long before the primary covalent bonds are broken, freeing up the individual chains to flow under stress. When the material is cooled, the secondary bonds reform. Thus, linear and branched polymers are generally thermoplastic. On the other hand, cross-links contain primary covalent bonds like those that bond the atoms in the main chains. When a cross-linked polymer is heated sufficiently, these primary covalent bonds fail randomly, and the material degrades. Therefore, cross-linked polymers are thermosets. There are a few exceptions such as cellulose and polyacrylonitrile. Though linear, these polymers are not thermoplastic because the extensive secondary bonds make up for in quantity what they lack in quahty. 

Fig. 2. The shape-memory process, where Tis temperature, (a) The cycle where the parent phase undergoes a self-accommodating martensite transformation on cooling to the 24 variants of martensite. No macroscopic shape change occurs. The variants coalesce under stress to a single martensite variant, resulting in deformation. Then, upon heating, they revert back to the original austenite crystallographic orientation, and reverse transformation, undergoing complete recovery to complete the cycle, (b) Shape deformation. Strain recovery is typically ca 7%.

As with thermoplastics melt processes, the setting is achieved by cooling. It will be appreciated that such cooling is carried out while the polymer is under stress so that there is considerable frozen-in orientation. This can be maintained throughout the life of the article. It is possible with the higher molecular weight materials to heat shapes made from blanks many years previously and see them return to the original shape of the blank. 

A further source of stress may arise from incorrect mould design. For example, if the ejector pins are designed in such a way to cause distortion of the mouldings, internal stresses may develop. This will happen if the mould is distorted while the centre is still molten, but cooling, since some molecules will freeze in the distorted position. On recovery by the moulding of its natural shape these molecules will be under stress. 

Operator error probability under stressful conditions depends upon the time to complete a sequence of events. The total time available for limiting sequences was 7.9 hours which is the time to completely drain the cooling water basin. Sequence (6) required the most operator actions (11) was... 

Nitrogen isotope ratios ( N/ " N) inerease from plants to herbivores to eami-vores and ean be used to estimate the degree of camivory in human diets. Some field studies observe a greater differenee in 5 N between trophie levels in dry, hot habitats than in wet, cool ones. Two hypotheses have been proposed to explain this variation in difference in 8 N between trophic levels. (1) Elevated excretion of -depleted urea in heat/water-stressed animals (2) recycling of nitrogen on protein-deficient diets. Both predict increased diet-tissue 8 N difference under stress. 

Dan Shen is bitter and slightly cold, and enters the Heart and liver meridians. Besides promoting blood circulation, it can effectively cool the blood and remove congealed blood, and treat chest pain, hypochondriac pain, a stifling sensation in the chest and irritability, especially under stress. 

If a sample of an amorphous polymer is heated to a temperature above its glass transition point and then subjected to a tensile stress, the molecules will tend to align themselves in the general direction of the stress. If the mass is then cooled below its transition temperature while the molecule is still under stress, the molecules will become frozen in an oriented state. Such an orientation can have significant effects on the properties of the polymer mass. The polymer is thus anisotropic. 

Copolymer test specimens were prepared by pressing slabs for 0.5-3 min at temperatures approximately 20°C above the copolymer melting point, followed by cooling under pressure to room temperature in 5-10 min. Test samples were conditioned at 24°C and 50% relative humidity for at least 48 hr before testing. Stress-strain and tear-strength measurements were made on 0.6 to 0.8-mm-thick specimens. Thicker specimens yield lower values for tensile strength and elongation at break. The test methods used were ... 

By rapid cooling-down of the filament - under stress - the obtained orientation is frozen in, combined with a very fast fibrillar crystallisation or recrystallisation. 

Thermal stresses are a major concern in reactor systems due to the magnitude of the stresses involved. With rapid heating (or cooling) of a thick-walled vessel such as the reactor pressure vessel, one part of the wall may try to expand (or contract) while the adjacent section, which has not yet been exposed to the temperature change, tries to restrain it. Thus, both sections are under stress. Figure 1 illustrates what takes place. 

The SMP with permanently set shape and dimensions is heated above the transition temperature the polymer is then deformed to the desired shape and dimensions. The new conhguration is allowed to cool under moderate stress to allow consolidation of the temporary shape and dimensions. To revert back to the permanent shape and dimensions, the SMP is heated again above the transition temperature and allowed to cool. 

In order to deal with the four non-crystalline forms in a unified way, we define a network chain in a crosslinked system, as the section of network between neighbouring crosslinks (Fig. 3.6). The shape of both a network chain in a rubber, and a molecule in a polymer melt, can be changed dramatically by stress, and both can respond elastically. However, when the polymer is cooled below Tg, the elastic strains are limited to a few per cent (unless a glassy polymer yields), so the molecular shape is effectively fixed. If the melt or rubber was under stress when cooled, the molecular shape in the glass is non-equilibrium. This molecular orientation may be deliberate, as in biaxially stretched polymethylmethacrylate used in aircraft windows, or a by-product of processing, as the oriented skin on a polystyrene injection moulding. Details are discussed in Chapter 5. 

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