Microstructure blend

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. 

The evaluation of the components of the tinplate container showed that the preferred enamel for irradiation processing was the epoxy phenolic the preferred end-sealing compound was the blend of cured and uncured isobutylene—isoprene copolymer. Component testing of tinplate and solder for possible changes in mechanical properties, microstructure, and corrosion resistance indicated that the radiation caused... 

When dealing with polymer blends or blockcopolymers, surface enrichment or microstructures may be observed as already discussed in Sect. 3.1. Quite similar effects may be expected for buried interfaces e.g. between polymer and substrate where one component may be preferentially enriched. In a system of PS, PVP and diblock copolymer PS-6-PVP it has been shown by FRS that the copolymer enrichment is strongly concentration dependent [158]. In a mixed film of PS(D) and end-functionalized PS on a silicon wafer the end-functionalized chains will be attached to the silicon interface and can be detected by NR [159],... 

The yield of cross-linking depends on the microstructure of polybutadiene and purity of the polymer as well as on whether it is irradiated in air or in vacuum. The cross-link yield, G(X), has been calculated to be lowest for trans and highest for vinyl isomer [339]. The introduction of styrene into the butadiene chain leads to a greater reduction in the yield of cross-linking, than the physical blends of polybutadiene and polystyrene [340]. This is due to the intra- and probably also intermolecular energy transfer from the butadiene to the styrene constituent and to the radiation stability of the latter unit. 

Many commercially important polymers are actually mixtures of two or more polymer components that differ from one another in composition (for copolymers) or in microstructure (for homopolymers). Such mixtures may be the deliberate result of polymer blending, polymer synthesis, or the presence of different types of initiators or catalytic sites that produce different polymer chains. The ung spectral data of the whole polymer in such systems would include contributions from all its components, and as such should be treated with care. 

The physical properties (7-10) of our E-V copolymers are sensitive to their microstructures. Both solution (Kerr effect or electrical birefringence) and solid-state (crystallinity, glass-transitions, blend compatibility, etc.) properties depend on the detailed microstructures of E-V copolymers, such as comonomer and stereosequence distribution. I3C NMR analysis (2) of E-V copolymers yields microstructural information up to and including the comonomer triad level. However, properties such as crystallinity depend on E-V microstructure on a scale larger than comonomer triads. 

Copolymers (graft or block) made of immiscible sequences give rise to biphasic morphologies depending on the ratio of immiscible sequences (or of their lengths). Such possible microstructures are reported in Figure 33. A minor phase can be dispersed as nodules (spheres) or filaments (cylinders) while, when concentrations of both phases get similar, lamellar (interpenetrated) structures can appear. It should be noted that rather similar morphologies could also be found in (compatibilised) polymer blends. 

Figure 14.7 Schematic highlighting the microstructure of rubber-toughened PET and performance improvements when non-reactive elastomers are blended with reactive elastomers (adapted from Atofina literature entitled Lotader and Lotryl )...

The effect of blending LDPE with EVA or a styrene-isoprene block copolymer was investigated (178). The properties (thermal expansion coefficient. Young s modulus, thermal conductivity) of the foamed blends usually lie between the limits of the foamed constituents, although the relationship between property and blend content is not always linear. The reasons must he in the microstructure most polymer pairs are immiscible, but some such as PS/polyphenylene oxide (PPO) are miscible. Eor the immiscible blends, the majority phase tends to be continuous, but the form of the minor phase can vary. Blends of EVA and metallocene catalysed ethylene-octene copolymer have different morphologies depending on the EVA content (5). With 25% EVA, the EVA phase appears as fine spherical inclusions in the LDPE matrix. The results of these experiments on polymer films will apply to foams made from the same polymers. 

Blends of LDPE with ethylene styrene interpolymers (ESI, see Section 3.2) also have a complex microstructure. The semi-crystalline LDPE is immiscible with the amorphous ESI, which has a glass transition temperature (Tg) just above room temperature. Consequently there are rigid crystalline regions and rubbery amorphous LDPE, mixed on a 0.1 pm scale, together with regions of leathery ESI on a 5 to 10 pm scale (71). 

The essential step is the efficient grinding and blending of raw materials. The final properties of cement strongly depend on its mineral composition so that raw composition and firing conditions are adjusted, depending on the type of cement to be produced. The microstructure of the steel fiber-cement paste interface was studied by scanning electron microscopy (SEM). The interfacial zone surrounding the fiber was found to be substantially different from the bulk paste further away from the fiber surface. The interfacial zone consisted of... 

The Metravib Micromecanalyser is an inverted torsional pendulum, but unlike the torsional pendulums described earlier, it can be operated as a forced-vibration instrument. It is fully computerized and automatically determines G y G"y and tan 8 as a function of temperature at low frequencies (10-5 1 Hz). Stress relaxation and creep measurements are also possible. The temperature range is —170 to 400°C. The Micromecanalyser probably has been used more for the characterization of glasses and metals than for polymers, but has proved useful for determining glassy-state relaxations and microstructures of polymer blends (285) and latex films (286). 

The electrical conductivity of two-phase, incompatible polymer blends containing carbon black has been shown to depend on the relative affinity of the conductive particles to each of the polymer components in the blend, the concentration of carbon black in the filler-rich phase, and the structural continuity of this phase [82]. Hence, by judicious manipulation of the phase microstructure, these three-phase filled composites can exhibit double percolation behaviour. 

VIGNETTE 1.6 POLYMER COMPOSITES Polymer-Blend Composites as Thermodynamically Stable, Microstructured Materials... 

One can have the same type of situation in a blend of two mutually immiscible polymers (e.g., polymethylbutene [PMB], polyethylbutene [PEB]). When mixed, such homopolymers form coarse blends that are nonequilibrium structures (i.e., only kinetically stable, although the time scale for phase separation is extremely large). If we add the corresponding (PEB-PMB) diblock copolymer (i.e., a polymer that has a chain of PEB attached to a chain of PMB) to the mixture, we can produce a rich variety of microstructures of colloidal dimensions. Theoretical predictions show that cylindrical, lamellar, and bicontinuous microstructures can be achieved by manipulating the molecular architecture of block copolymer additives. 

In fact, even in pure block copolymer (say, diblock copolymer) solutions the self-association behavior of blocks of each type leads to very useful microstructures (see Fig. 1.7), analogous to association colloids formed by short-chain surfactants. The optical, electrical, and mechanical properties of such composites can be significantly different from those of conventional polymer blends (usually simple spherical dispersions). Conventional blends are formed by quenching processes and result in coarse composites in contrast, the above materials result from equilibrium structures and reversible phase transitions and therefore could lead to smart materials capable of responding to suitable external stimuli. 

Fig. 6.7 Domain spacing of blends of a PS-PI diblock with PS homopolymer relative to that for the pure diblock (du = 26.7 nm) (Hashimoto et al. 1990). The diblock has M = 31.6kgmol, and 48wt% PS, the homopolymers have (o) M = 2.3kgmor , (A) Mn = 4.4 kg mol 1, ( ) M = 10.2 kg mol 1, ( ) Mn = 16.7 kg mol 1. Experiments were performed at room temperature. The symbols L, C and S denote lamellar, cylindrical and spherical microstructures.

Fig. 6.10 Phase diagrams for blends of PS homopolymers with PS-PI diblocks of approximately constant molecular weight (average M = 54.3 kgmol"L), annealed at 125 C (Winey et al. 1992ft). (a) Mn (PS) = 5.9kgmor (b) M (PS) = 14kgmol-1, (c) M (PS) = SVkgmor1. Here L, C and S denote lamellar, cylindrical and spherical microstructures respectively, DM indicates disordered micelles, BC a bicontinuous cubic structure and 2

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