Microstructure examples

In this chapter, we will first review the basics of refraction, diffraction and reflection which are used in understanding optical effects caused by patterns or microstructures. Examples from nature will then be given that illustrate these principles. The major part of this chapter will deal with technical structures developed for optical purposes, with a discussion of their fabrication methods and of typical applications. 

A first example of application of microtomography is taken from life sciences. Here X-ray microscopy and microtomography allows to reconstruct the internal three-dimensional microstructure without any preparation and sometimes even of living objects. Fig. la shows an X-ray transmission microscopical image of bone (femoral head). Several reconstructed cross-sections are shown in Fig.lb. Fig.lc shows the three-dimensional reconstruction of this bone. 

Barnes and co-workers have studied mixed-monolayer systems [278,281,283,284] and found some striking nonidealities. Mixed films of octadecanol and cholesterol, for example, show little evaporation resistance if only 10% cholesterol is present [278] apparently due to an uneven granular microstructure in films with cholesterol [284]. Another study of cellulose decanoate films showed no correlation between holes in the monolayer and permeation rate [285]. Polymerized surfactants make relatively poor water evaporation retarders when compared to octadecanol [286]. There are problems in obtaining reproducible values for r [287] due to impurities in the monolayer material or in the spreading solvent. 

All polymer molecules have unique features of one sort or another at the level of individual repeat units. Occasional head-to-head or tail-to-tail orientations, random branching, and the distinctiveness of chain ends are all examples of such details. In this chapter we shall focus attention on two other situations which introduce variation in structure into polymers at the level of the repeat unit the presence of two different monomers or the regulation of configuration of successive repeat units. In the former case copolymers are produced, and in the latter polymers with differences in tacticity. Although the products are quite different materials, their microstructure can be discussed in very similar terms. Hence it is convenient to discuss the two topics in the same chapter. 

In Sec. 7.3 we noted that variations in the 1 12 product led to differences in the microstructure of the polymer, even when the overall composition of two compared systems is the same. Structures [I]-[III] are examples of this situation. In this section we shall take a closer look at this variation, using the approach which is best suited for this kind of detail statistics. 

The following example demonstrates the use of some of these relationships pertaining to microstructure. 

Examples of the unique insights obtained by solid state NMR applications to materials science include the Si/Al distribution in zeolites, the hydrogen microstructure in amorphous films of hydrogenated silicon, and the mechanism for the zeolite-catalyzed oligomerization of olefins. ... 

Most materials scientists at an early stage in their university courses learn some elementary aspects of what is still miscalled strength of materials . This field incorporates elementary treatments of problems such as the elastic response of beams to continuous or localised loading, the distribution of torque across a shaft under torsion, or the elastic stresses in the components of a simple girder. Materials come into it only insofar as the specific elastic properties of a particular metal or timber determine the numerical values for some of the symbols in the algebraic treatment. This kind of simple theory is an example of continuum mechanics, and its derivation does not require any knowledge of the crystal structure or crystal properties of simple materials or of the microstructure of more complex materials. The specific aim is to design simple structures that will not exceed their elastic limit under load. 

The first detailed book to describe the practice and theory of stereology was assembled by two Americans, DeHoff and Rhines (1968) both these men were famous practitioners in their day. There has been a steady stream of books since then a fine, concise and very clear overview is that by Exner (1996). In the last few years, a specialised form of microstructural analysis, entirely dependent on computerised image analysis, has emerged - fractal analysis, a form of measurement of roughness in two or three dimensions. Most of the voluminous literature of fractals, initiated by a mathematician, Benoit Mandelbrot at IBM, is irrelevant to materials science, but there is a sub-parepisteme of fractal analysis which relates the fractal dimension to fracture toughness one example of this has been analysed, together with an explanation of the meaning of fractal dimension , by Cahn (1989). 

As materials chemistry has developed, it has come to pay more and more attention to that archetypal concern of materials scientists, microstructure. That concern came in early when the defects inherent in non-stoichiometric oxides were studied by the Australian. I.S. Anderson and others (an early treatment was in a book edited by Rabenau 1970), but has become more pronounced recently in the rapidly growing emphasis on self-assembly of molecules or colloidal particles. This has not yet featured much in books on materials chemistry, but an excellent recent popular account of the broad field has a great deal to say on self-assembly (Ball 1997). The phenomenon of graphoepitaxy outlined in Section 10.5.1.1 is a minor example of what is meant by self-assembly. 

Most materials, be they natural or synthetic, have limited utility. However, technical ingenuity has increased the utility of these materials beyond anyone s wildest imagination. The enormous range of steel that can be produced by adding carbon or other elements to give it the required balance of properties, such as strength and hardness, related to changes in their microstructure [1-3] is just one example. 

Some of the above discussed precursor phenomena are also observed prior to diffusion driven phase transformations. A typical example are the conventional EM tweed images obtained in the tetragonal parent phase in high Tc superconductors and other ceramics. In a recent survey by Putnis St e of such observations it was concluded that in these cases the tweed contrast resulted from underlying microstructures fomied by symmetry changes driven by cation ordering. These symmetry changes yield a fine patchwork of twin related domains which coarsen when the transfomiation proceeds. However, in view of the diffusion driven character of the latter examples, these cases should be clearly separated from those in the field of the martensites. 

Since multiple electrical and optical functionality must be combined in the fabrication of an OLED, many workers have turned to the techniques of molecular self-assembly in order to optimize the microstructure of the materials used. In turn, such approaches necessitate the incorporation of additional chemical functionality into the molecules. For example, the successive dipping of a substrate into solutions of polyanion and polycation leads to the deposition of poly-ionic bilayers [59, 60]. Since the precursor form of PPV is cationic, this is a very appealing way to tailor its properties. Anionic polymers that have been studied include sulfonatcd polystyrene [59] and sulfonatcd polyanilinc 159, 60]. Thermal conversion of the precursor PPV then results in an electroluminescent blended polymer film. 

If we look at the mechanistic and crystallographic aspects of the operation of polycomponent electrodes, we see that the incorporation of electroactive species such as lithium into a crystalline electrode can occur in two basic ways. In the examples discussed above, and in which complete equilibrium is assumed, the introduction of the guest species can either involve a simple change in the composition of an existing phase by solid solution, or it can result in the formation of new phases with different crystal structures from that of the initial host material. When the identity and/or amounts of phases present in the electrode change, the process is described as a reconstitution reaction. That is, the microstructure is reconstituted. 

Fig. 1A-L. Examples of polymer microstructures comprising tethered chains...

Comprehension of the interactions among microstructures composed of tethered chains is central to the understanding of many of their important properties. Their ability to impart stability against flocculation to suspensions of colloidal particles [52, 124, 125] or to induce repulsions that lead to colloidal crystallization [126] are examples of practical properties arising from interactions among tethered chains many more are conceivable but not yet realized, such as effects on adhesion, entanglement or on the assembly of new block copolymer microstructures. We will be rather brief in our treatment of interactions between tethered chains since a comprehensive review has been published recently of direct force measurements on interacting layers of tethered chains [127]. 

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