Polymers morphological features

Mention may also be made of an application in which careful control of polymer morphology has led to the production of novel materials. By treatment of solutions of high-density polyethylene, products are obtained with a celluloselike morphology and which are known as, fibrides or synthetic wood pulp. They are used for finishing paper and special boards to impart such features as sealability and improved wet strength. They are also reported to be used for such diverse applications as tile adhesives, thixotropic agents, battery separators and teabags ... 

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. 

When a polymer film is exposed to a gas or vapour at one side and to vacuum or low pressure at the other, the mechanism generally accepted for the penetrant transport is an activated solution-diffusion model. The gas dissolved in the film surface diffuses through the film by a series of activated steps and evaporates at the lower pressure side. It is clear that both solubility and diffusivity are involved and that the polymer molecular and morphological features will affect the penetrant transport behaviour. Some of the chemical and morphological modification that have been observed for some epoxy-water systems to induce changes of the solubility and diffusivity will be briefly reviewed. 

Having said this, it was felt therefore that there is a need for a book addressing analysis and characterisation of polymers from the point of view of what we wish to call the primary analytical question. Many excellent textbooks and reference works exist which address one or more individual analytical techniques, see, for example, references [1-10]. These books form the basis of the knowledge of the technique expert. They also contain many excellent and varied examples on successful applications of analytical techniques to polymer analysis and characterisation. There are also books which address the multitude of analytical techniques applied in polymer analysis, see, for example, references [11-24], However, a synthetic chemist may wish to know the constitution of his/her polymer chain, a material scientist may want to find out the reasons why a fabricated sample had failed. What technique is best or optimal to study chain constitution will depend on the situation. Polymer failure may result from morphological features, which needs to be avoided, a contaminant, a surface property degradation, etc. When a sample has been processed, e.g., a film blown, molecular orientation may be the key parameter to be studied. A formulation scientist may wish to know why an additive from a different supplier performs differently. It is from such points of view that polymer analysis and characterisation is addressed in this book. 

If crystallization is carried out from concentrated solutions, multilamellar aggregates are formed. In particular, melt crystallization of polyethylene gives bunched-up lamellae with an overall spherical symmetry. The space between the lamellae contains uncrystallized amorphous polymer. These objects are called spherulites, and their radii grow linearly with time, in spite of their intricate morphological features [9]. Another remarkable feature of spheruhtes formed by linear polyethylene is that they are gigantically chiral, although the molecules are achiral. 

The polarizing microscope can be used to observe morphological features of all crystalline polymers that can be prepared as thin films. Birefringence measurement is applicable to all polymers in which orientation or anisotropy can be induced. 

At the recent European Symposium on Polymer Blends [59] about half of the contributions dealt with thermodynamic effects on molecular architecture, on polymer morphology, and on processing and performance of polymer blend materials. Although some attention has been focused mainly on the interface (material) in heterogeneous blends, in general most thermodynamic studies of such heterogeneous blends deal with two- or more bulk phases. Essential morphological features such as droplet size, cocontinuous phases, micellar or... 

Appearance of Fused Product. From the fabrication point of view, if two polymers give a smooth band on a two-roll mill, the polyblend is said to be compatible. If the fused product is cheezy, it is said to be incompatible. Frequently, the fused product is pressed into a flat sheet. Transparency of the sheet signifies compatibility, whereas an opaque appearance means incompatibility. Obviously, these criteria are arbitrary and crude. They are subject to great variation owing to difference in individual judgement. In addition, they give no information on the morphological feature of the system. 

Samples for the viscoelastic experiments were prepared by a conventional slow-solvent-evaporation technique (1) followed by vacuum drying. For ease in handling in certain experiments, some samples were lightly cured using a 30-MRad dose of electrons other experiments were carried out on uncured materials. Transmission electron microscopy (Phillips Model 200) was used to investigate possible morphological features in the block polymers and blends. Details of the various staining techniques used are presented elsewhere (1,11,12,13). 

The morphology of a crystallizable polymer is a description of the forms that result from crystallization and the aggregation of crystallites. The various morphological features which occur in bulk crystallized polymers are reviewed in this section. 

In addition to the various morphological features listed, intermediate super-molecular structures and mixtures of these entities will be observed. The mechanical properties of finished articles will depend on the structural state of a semicrystalline polymer, and this in turn is a function of the molecular structure of the polymer and to a significant extent also of the process whereby the object was fabricated. 

The formation of shear bands under compression is found in crystalline polymers when loaded at temperatures lower than 0.75 T. Under such a condition the shear bands interact with certain morphological features such as spherulite boundaries or lamellar arrangements inside the spherulites. The band initiation stress, ct, increases and the strain at break, Cp, decreases with decreasing temperature and increasing stiffness of the tested polymer, i.e. increasing degree of crystallinity. 

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