Amorphous domain

Polymers can exhibit a hierarchical organization of structure at four successive levels, the molecular, nano-, micro-, and macrolevel [33, 34], On the scale of tens of microns, semicrystalline polymers contain spherulites, the spherulites have a lamellar texture, and the molecules within the lamellae are organized in crystals and amorphous domains. Amorphous polymers are structured on the molecular and macroscopic scale only [34]. Thermoplastic SMPs are usually phase-segregated materials, i.e., they consist of at least two different domains, which are related to different thermal transition temperatures (Tinms)- Therein hard domains have a TJrans (glass transition temperature Tg or melting temperature 7]n) usually much higher than room temperature and determine the permanent shape, while switching domains show a lower thermal transition (Tg or 7]n). SMP networks contain chemical crosslinks instead of hard domains to fix the permanent shape. 

Fig. 1.14 Crystalline polymers regular domains, amorphous polymers, coiled irregular domains...

Amorphous Domain n (and crystalline domains) Amorphous or noncrystalline portions of a solid polymer conversely, crystalline a domains are nonamorphous. A single crystalline polymer chain can possess amorphous regions (domains), e.g., polyethylene. 

Polymers are difficult to model due to the large size of microcrystalline domains and the difficulties of simulating nonequilibrium systems. One approach to handling such systems is the use of mesoscale techniques as described in Chapter 35. This has been a successful approach to predicting the formation and structure of microscopic crystalline and amorphous regions. 

No polymer is ever 100% crystalline at best, patches of crystallinity are present in an otherwise amorphous matrix. In some ways, the presence of these domains of crystallinity is equivalent to cross-links, since different chains loop in and out of the same crystal. Although there are similarities in the mechanical behavior of chemically cross-linked and partially crystalline polymers, a significant difference is that the former are irreversibly bonded while the latter are reversible through changes of temperature. Materials in which chemical cross-linking is responsible for the mechanical properties are called thermosetting those in which this kind of physical cross-linking operates, thermoplastic. 

Between T j, and Tg, depending on the regularity of the polymer and on the experimental conditions, this domain may be anything from almost 100% crystalline to 100% amorphous. The amorphous fraction, whatever its abundance, behaves like a supercooled liquid in this region. The presence of a certain degree of crystallinity mimics the effect of crosslinking with respect to the mechanical behavior of a sample. 

Solvent Resistance. At temperatures below the melting of the crystallites, the parylenes resist all attempts to dissolve them. Although the solvents permeate the continuous amorphous phase, they are virtually excluded from the crystalline domains. Consequently, when a parylene film is exposed to a solvent a slight swelling is observed as the solvent invades the amorphous phase. In the thin films commonly encountered, equilibrium is reached fairly quickly, within minutes to hours. The change in thickness is conveniently and precisely measured by an interference technique. As indicated in Table 6, the best solvents, specifically those chemically most like the polymer (eg, aromatics such as xylene), cause a swelling of no more than 3%. 

Attention must also be focused on the noncrystalline domains. Many important properties of fibers can be directly related to these noncrystalline or amorphous regions. For example, absorption of dyes, moisture, and other penetrants occurs in these regions. These penetrants are not expected to diffuse into the crystalline domains, although there may be adsorption on crystaUite surfaces. The extensibUity and resUience of fibers is also directly associated with the noncrystalline regions. 

Noncrystalline domains in fibers are not stmctureless, but the stmctural organization of the polymer chains or chain segments is difficult to evaluate, just as it is difficult to evaluate the stmcture of Hquids. No direct methods are available, but various combinations of physicochemical methods such as x-ray diffraction, birefringence, density, mechanical response, and thermal behavior, have been used to deduce physical quantities that can be used to describe the stmcture of the noncrystalline domains. Among these quantities are the amorphous orientation function and the amorphous density, which can be related to some of the important physical properties of fibers. 

The properties of elastomeric materials are also greatly iafluenced by the presence of strong interchain, ie, iatermolecular, forces which can result ia the formation of crystalline domains. Thus the elastomeric properties are those of an amorphous material having weak interchain iateractions and hence no crystallisation. At the other extreme of polymer properties are fiber-forming polymers, such as nylon, which when properly oriented lead to the formation of permanent, crystalline fibers. In between these two extremes is a whole range of polymers, from purely amorphous elastomers to partially crystalline plastics, such as polyethylene, polypropylene, polycarbonates, etc. 

The outstanding morphological feature of these rubbers arises from the natural tendency of two polymer species to separate one from another, even when they have similar solubility parameters. In this case, however, this is restrained because the blocks are covalently linked to each other. In a typical commercial triblock the styrene content is about 30% of the total, giving relative block sizes of 14 72 14. At this level the styrene end blocks tend to congregate into spherical or rod-like glassy domains embedded in an amorphous rubbery matrix. These domains have diameters of about 30 nm. 

Whilst, chemically, SBS triblocks are similar to SBR, for example they do not show measurable breakdown on mastication, they are seriously deficient in one respect, they show a high level of creep. This would indicate that the concept of all the styrene blocks being embedded in the domains with all of the polybutadiene blocks being in the amorphous matrix is rather too simplistic. It has also resulted in these materials not being used extensively in traditional rubber applications. One exception from this is in footwear, where blends of SBS and polystyrene have been used with noted success for crepe soles. 

In the case of the polycrystalline polyester thermoplastic rubbers the simple domain theory does not seem to apply. With these rubbers it would appear that they contain spherulitic structures consisting of 4GT radial lamellae with inter-radial amorphous regions that are mixtures of PTMEG soft segments and noncrystalline hard segments. 

Mangipudi et al. [63,88] reported some initial measurements of adhesion strength between semicrystalline PE surfaces. These measurements were done using the SFA as a function of contact time. Interestingly, these data (see Fig. 22) show that the normalized pull-off energy, a measure of intrinsic adhesion strength is increased with time of contact. They suggested the amorphous domains in PE could interdiffuse across the interface and thereby increase the adhesion of the interface. Falsafi et al. [37] also used the JKR technique to study the effect of composition on the adhesion of elastomeric acrylic pressure-sensitive adhesives. The model PSA they used was a crosslinked network of random copolymers of acrylates and acrylic acid, with an acrylic acid content between 2 and 10%. 

Fig. 22. Nomialized pull-off energy measured for polyethylene-polyethylene contact measured using the SFA. (a) P versus rate of crack propagation for PE-PE contact. Change in the rate of separation does not seem to affect the measured pull-off force, (b) Normalized pull-off energy, Pn as a function of contact time for PE-PE contact. At shorter contact times, P does not significantly depend on contact time. However, as the surfaces remain in contact for long times, the pull-off energy increases with time. In seinicrystalline PE, the crystalline domains act as physical crosslinks for the relatively mobile amorphous domains. These amorphous domains can interdiffuse across the interface and thereby increase the adhesion of the interface. This time dependence of the adhesion strength is different from viscoelastic behavior in the sense that it is independent of rate of crack propagation.

Fig. 5. Log-iog plot illustrating the hardness dependence of density for PE samples crystallized from the melt. The plot yields two straight sections which can be ascribed to two preferential deformation modes a crystal destruction and b compression of amorphous domains...

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