Immiscible polymers, phase morphology

The effect of viscosity ratio on the morphology of immiscible polymer blends has been studied by several researchers. Studies with blends of LCPs and thermoplastics have shown indications that for good fibrillation to be achieved the viscosity of the dispersed LCP phase should be lower than that of the matrix [22,38-44]. 

The properties of immiscible polymers blends are strongly dependent on the morphology of the blend, with optimal mechanical properties only being obtained at a critical particle size for the dispersed phase. As the size of the dispersed phase is directly proportional to the interfacial tension between the components of the blend, there is much interest in interfacial tension modification. Copolymers, either preformed or formed in situ, can localize at the interface and effectively modify the interfacial tension of polymer blends. The incorporation of PDMS phases is desirable as a method to improve properties such as impact resistance, toughness, tensile strength, elongation at break, thermal stability and lubrication. 

Several factors can be identified as being crucial for the foaming of immiscible polymer blends the blend morphology, the phase size of the blend constituents, the interfacial properties between the blend partners, and, last but not least, the properties of the respective blend phases such as the melt-rheological behavior, the glass transition temperature, the gas solubility, as well as the gas diffusion coefficient. Most of these factors also individually influence the melt-rheological behavior of two-phase blends. 

Goldel A, Ruckdaschel H, Muller AHE, Potschke P, Altstadt V (2008) Controlling the phase morphology of immiscible poly(2,6-dimethyl-l,4-phenylene ether)/poly(styrene-coacrylonitrile) blends via addition of polystyrene. e-Polymers 151... 

Because the components must initially form miscible solutions or swollen networks a degree of affinity between the reacting components is needed. Therefore, most of the investigations into epoxy IPNs have involved the use of partially miscible components such as thermoplastic urethanes (TPU) with polystyrenes [57], acrylates [58-61] or esters which form loose hydrogen-bound mixtures during fabrication [62-71 ]. Epoxy has also been modified with polyetherketones [72],polyether sulfones [5] and even polyetherimides [66] to help improve fracture behavior. These systems, due to immiscibility, tend to be polymer blends with distinct macromolecular phase morphologies and not molecularly mixed compounds. 

The following discussion will be restricted to evolution of phase morphologies preferably in late stages in solutions and blends of immiscible polymers wherein phase separation is initiated by solvent evaporation during casting and thermal agitation, respectively. 

Blend solutions. Solutions of blends comprising immiscible polymers Pj and P2 in a nonselective solvent have miscibility gaps as shown schematically in Fig. 14. When the polymer concentration increases by solvent evaporation the polymer coils start to interpenetrate above a certain concentration. As a consequence, interactions between the polymers become operative and phase separation must start above a critical polymer concentration p. The composition of the new phases will be situated on the branches of the coexistence curve. Finally, the unmixing process is arrested owing to enhanced viscosity. This simple scheme reveals the factors directing morphology evolution in blend solutions ... 

The question might be addressed now to know whether phase morphology and properties of Immiscible polymer blends can be modified by a way different from the previously described emulsification. 

A polyurethane (PU)/poly(n-butyl methacrylate) (PBMA) system has been selected for an investigation of the process of phase separation in immiscible polymer mixtures. Within this system, studies are made of the XX, lx, xl, and the 11 forms. In recognition of the incompatibility of PBMA with even the oligomeric soft segment precursor of the PU, no attempt was made to equalize the rates of formation of the component linear and network polymers. Rather, a slow PU formation process is conducted at room temperature in the presence of the PBMA precursors. At suitable times, a relatively rapid photopolymerization of the PBMA precursors is carried out in the medium of the slowly polymerizing PU. The expected result is a series of polymer mixtures essentially identical in component composition and differing experimentally only in the time between the onset of PU formation and the photoinitiation of the acrylic. This report focuses on the dynamic mechanical properties cf these materials and the morphologies seen by electron microscopy. 

Blends of immiscible polymers exhibit a coarse and unstable phase morphology with poor interfacial adhesion. The ultimate properties of these blends are often poorer than those of either component. The poor mechanical properties can be improved with a small amount of an interfacial agent that lowers interfacial tension in the melt and enhances interfacial adhesion in the solid. High-strain properties, such as strength, tensile elongation, and impact strength, especially benefit from compatibilization (I, 2). 

The morphology can be stabilized by (i) thick interphase, (ii) partial crosslinking, or (iii) addition of an immiscible polymer with a suitable spreading coefficient [Yeung et al., 1994]. The adhesion between the phases in the solid state is improved by (i) addition of a copolymer that covalently bonds the phases, (ii) reduction of size of the crystalline domains, (iii) adequate adhesion, e.g., by the use of polyetherimine, PEIm [Bjoerkengren and Joensson, 1980], and... 

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