Elastomer blends, miscible thermodynamics

Polymer blends are a mixture of at least two polymers, their combination being supposed to lead to new materials with different properties. The classification of polymer blends into (1) immiscible polymer blends, (2) compatible polymer blends, and (3) miscible polymer blends is given by the thermodynamic properties of the resulting compound by means of the number of glass transition temperatures observed for the final product. To improve the compatibility between the blended polymers, some additives or fillers are used. To the same extent, rubber blends are mixtures of elastomers, which are usually combined to obtain an improved product, with properties derived from each individual component. 

The majority of elastomer blends are phase separated, but of interest, as crosslinking can achieve mechanical compatibilization due to crosslinking between the phases as noted in Chapter 3. This compatibilization method can lead to unique and useful blends with a compromise in properties, offering useful commercial products as well illustrated by the applications in tire construction. The unsaturated hydrocarbon elastomers without polar functional groups are rarely miscible with each other, because no specific interactions are present to achieve the necessary thermodynamic driving force for miscibility. The few miscible examples noted generally exhibit matched solubility parameters. 

Miscible blends of elastomers differ from corresponding blends of thermoplastics in two important areas. First, the need for elastic properties requires elastomers to be high molecular weight. This reduces both the kinetic rate and the thermodynamic driving force for the interdiffusion and thus formation of a miscible single phase of dissimilar elastomers. Second, elastomers are plasticized in conventional compounding with process oils. The presence of plasticizers leads to both a higher free volume for the blend components and a decrease of the endothermal interactions. 

The extension of thermodynamics to a blend of elastomers has been discussed by Roland [4], Miscible blends are most commonly formed from elastomers with similar three-dimensional [7] solubility parameters. An example of this is blends from copolymer elastomers (e.g., ethylene-propylene or styrene-butadiene copolymers) from component polymers of different composition, microstructure, and molecular weights. When the forces between the components of the polymer blend are mostly entirely dispersive, miscibiUty is only achieved in neat polymers with a very close match in Hansen s three-dimensional solubility parameter [7]. 

The recent proliferation of metallocene-based polyolefins and polyolefin elastomers have gained their popularity owing to their density, cost, and ease of processabUity. PVC/POE blends have therefore been investigated as flexible PVC compounds. However, these blends are thermodynamically immiscible and needed suitable compatibiUzers such as the chlorinated polyethylenes (Eastman and Dadmun 2002). Since they are not miscible, POEs do not lower the PVC modulus sufficiently unless some plasticizer or a compatible elastomer such as EPE is also added. Commercially, some PVC/POE alloys are offered by TeknorApex under Flexalloy trade name with a shore A hardness 40-60 and brittle points down to —50 °C. They are claimed to have excellent low-temperature toughness, flexibility, compression set-resistance, and oil resistance. Suitable applications include automotive hoses, seals, gaskets, wire jacketing, etc. 

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