Ternary polymer blend

There have been various studies of ternary homopolymers and random copolymer blend systems over a wide range of compositions [85 to 90). Regions of miscibility and phase separation have been determined. The additional third component can increase [86,87] or decrease [88,89] miscibility between two polymer components. 

Other interesting ternary systems exist. Polystyrene is not miscible with polycarbonate, poly(methyl methacrylate), or poly(vinyl acetate). However, addition of copolymer p-(hexa-fluoro-2-hydroxypropyl)styrene forms a ternary blend with miscible regions for polystyrene with polycarbonate or polystyrene with poly(methyl methacrylate) or polystyrene with poly(vinyl acetate) [86,90]. 

In this chapter, we have described the behavior of ternary systems. This includes ternary low molecular weight systems (Section 6.2). Polymers with two low molecular weight liquids (Section 6.3) binary polymer blends with a low molecular weight liquid (Section 6.4), binary polymer blends with amphiphilic molecules or block/graft copolymers (Sections 6.5 through 6.7), high impact polystyrene (Section 6.8) and ternary polymer blends (Section 6.9). 

We have made the important observation that these systems tend not to be truly random or completely miscible. For a polymer dissolved in a mixed solvent, one solvent will often preferentially associate with the polymer. A low molecular weight liquid mixed into a polymer blend will preferentially dissolve in one of the polymer components. An amphiphilic molecule or block/graft copolymer can situate itself at the interface between two polymeric phases and modify the interface properties such as interfacial tension. Indeed if high in molecular weight, it can act as a compatibilizing agent , which in addition enhances the mechanical behavior (e.g., the toughness) of the blend. 

Planck, Treatise on Thermodynamics, 17th German Editor (1892) English edition (1926), Dover, NY 

There are a number of examples where polymers A, B and C form three miscible binary blends. Many of these will exhibit miscibility over the entire ternary diagram however, there are cases where windows of immiscibility can occur. Styrene-acrylic acid (SAA) copolymers are miscible with PMMA above 6 mol% AA and miscible with PEO above 15 mol% AA [ 1129]. In a ternary blend of SAA(21 mol% AA)/PEO/PMMA, where all the binary blends are miscible, a window of immiscibility was observed. The ternary blend of PCL/SAN (24wt% AN)/SMA(25 wt% MA) showed a significant region of immiscibility, even though all the binary pairs were miscible [1130]. This is illustrated in Fig. 4.31. 

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Figure B3.6.5. Phase diagram of a ternary polymer blend consisting of two homopolymers, A and B, and a synnnetric AB diblock copolymer as calculated by self-consistent field theory. All species have the same chain length A and the figure displays a cut tlirough the phase prism at%N= 11 (which corresponds to weak segregation). The phase diagram contains two homopolymer-rich phases A and B, a synnnetric lamellar phase L and asynnnetric lamellar phases, which are rich in the A component or rich in the B component ig, respectively. From Janert and Schick [68].

Terg-O-Tometer Terg-o-tometer Terlinguaite [12394-37-5] Termamyl Terminal lakes Terminal sterilization Ternary polymer blends Terne metal... 

Ternary blends One way to overcome these limitations is the use of ternary polymer blends. This approach makes use of the principle described in section 1.1.2, in which one of the polymer components wets the interface of the other two. By providing a pre-pattemed substrate with surface regions, to which these two polymer segregate, it is possible to form structures in the intercalated polymer with dimensions that are not directly connected to the substrate pattern. 

Kawai and collaborators have extensively studied copolymers of styrene and isoprene. They have synthetized and studied SI copolymers63,169, SIS copolymers64, and ternary polymer blends of SI block copolymers with polystyrene and polyisoprene170-171 and proposed a thermodynamic interpretation of the domain structure in solvent-cast films of SI, SIS, and blends of these copolymers with their homopoly-mers63 64,172. ... 

Le Menestrel, C. Bhagwagar, D.E. Graf, J.F. Painter, P.C. Coleman, M.M. Hydrogen bonding in ternary polymer blend systems determination of association parameters. Macromolecules 1992, 25, 7101. 

Lee T. W., Park O. O., Cho H. N., and Kim Y. C. Cascade enerev transfer in dye-dot>ed ternary polymer blend lieht-emittine diodes Synthetic Metals, Volume 131, Issues 1-3, 20 November 2002, Pages 129-133... 

Park J H, Lee T W, Kim Y C, Park O O and Kim J K, "White polymer light-emitting devices from ternary-polymer blend with concentration gradient" Chem. Phys. Lett. 403 2005 293... 

Morkved, T.L., Stepanek, P., Krishnan, K., Bates, F.S. and Lodge, T.P. (2001) Static and dynamic scattering from ternary polymer blends Bicontinuous microemulsions, Lifshitz lines, and amphiphilicity. /. Chem. Phys., 114, 7247-7259. 

As outlined in the previous section, the good charge storage of the binary PPE/PS blends was in part attributed to the proposed presence of heterogeneities in the polymer bulk. In this section, heterogeneities are further introduced by adding a third component, namely the triblockcopolymer poly(styrene-Msobutylene-fe-styrene) (SIBS) to form ternary polymer blends with PPE and PS [65], The chemical struc-... 

Figure 8.25 shows TEM micrographs of two different ternary polymer blends. Eigure 8.25a... 

Nauman and He [1994] simulated two dimensional spinodal decomposition for ternary polymer mixtures. Variations in volume fraction and interaction parameters of the constituents yielded a multiplicity of different morphologies, some of which were verified in the film experiments. A phase classification was presented for the morphologies obtainable with ternary polymer blends. 

The ternary polymer blends based on PP, PA6 (or PA66), and elastomers have been studied worldwide during last several decades. Many researchers tried to well understand the compatibility, morphology, and mechanical behavior of such ternary polymer blends. The blend systems studied include PP/PA66/SEBS-g-MA (1-5), PP/PA6/EPR-g-MA (3-5), PP/PA6/PP-g-MA (6), PP/PA6/EPDM-g-MA (7), and so on. Since several years, a research group has begun research work on PP/PA6/ POE-g-MA blends (8-12). 

Morphology of the uncompatibilized (a, a a") and compatibilized (b, b b") ternary poly-propylene/polystyrene/polyamide (PP/PS/PA6) (70/15/15) blends (a,b) cryofractured surface, (a, b ) cryofractured and PS phase extracted using tetrahydrofuran (THF), (a", b") cryofractured and PA6 phase extracted using HCOOH. (Reproduced from Wang, D., Li, Y., Xie, X.-M., and Guo, B.-H. 2011. Compatibilization and morphology development of immiscible ternary polymer blends. Polymer 52 191-200 with permission from Elsevier.)... 

Virgilio, N., Desjardins, R, L Esperance, G., and Favis, B. D. 2010. Modified interfacial tensions measured in situ in ternary polymer blends demonstrating partial wetting. Polymer 51 1472-1484. 

Walheim, S., Ramstein, M., Steiner, U. Morphologies in ternary polymer blends after spincoating. Langmuir 15(14), 4828 836 (1999)... 

Cyganik, P., Budkowski, A., Raczkowska, J., Postawa, Z. AFM/LFM surface studies of a ternary polymer blend cast on substrates covered by a self-assembled monolayer. Surf. Sci. 507-510, 700-706 (2002)... 

N. R. Washburn, T. P. Lodge, F. S. Bates, Ternary Polymer Blends as Model Surfactant Systems. J. Phys. Chem. B 2000,104,6987-6997. 

White light emission was obtained from a device made of a ternary polymer blend, comprised of PVK, poly(9,9 -dihexylfluorene-2,7-divinylene-m-phenyl-ene vinylene-stat-p-phenylenevinylene) (CPDHFPV). 

Lovera D, Ruckdaschel H, Altstadt V, Schmidt HW. Charge storage of ternary polymer blends based on poly(phenylene ether). Polym Int 2009 58( 11) 1260-6. 

FIGURE 2 Huggins constant versus blend composition for two ternary polymer blend solutions in chloroform, PHB blended with poly(ethylene oxide) (PEO)—( ), and poly(e-caprolactone) (PCL)—(o), soM curves represent regression curves after Equation (22) dashed curves were calculated with AK = 0. 

In general, two main problems are associated with binary blends containing LCP a poor interfacial adhesion between the LCP and thermoplastic matrix and a difficulty in controlling the LCP fibrillation. Ternary polymer blends are gaining an important share in the field of polymer property diversification... 

There have been also some recent theoretical approaches addressing mainly the thermodynamic properties of binary and ternary polymer blends. Campos et al. (1996) extended the Flory-Huggins theory to predict the thermodynamic properties of binary polymer blends and blends in solution. Their approach was applied for PVDF/PS dry blend and in solutirm in dimethylformamide (DMF) with inclusion of an interaction functirai. It could be inferred that this blend behave as slightly incompatible under envirorunental cruiditions, in agreement with previously reported data. That incompatibility was suppressed when a low molar mass component, such as DMF, was added, reaching the semidilute regime (total... 

The second study (Meghala and Ranganathaiah 2012) was dedicated to the evaluation of interfaces in poly(styrene-co-acrylonitrile) (SAN)-based ternary polymer blends using also positron lifetime spectroscopy. The method successfully applied for binary blends (single interface), mentioned above, was theoretically modified for ternary blends and experimentally verified by measuring free volume content in blends and their constituents. They tested the efficacy of this method in two ternary blends S AN/PVC/PMMA and SAN/EVA/PVC at different compositions. The effective hydrodynamic parameter evaluated using individual values turned out to be handy in predicting the overall miscibility level of a ternary blend. 

G.C. Reichart, W.W. Graessley, R.A. Register, R. Krishnamoorti, D.J. Lohse, Measurement of thermodynamic interactions in ternary polymer blends by small-angle neutron scattering. Macromolecules 30(11), 3363-3368 (1997)... 

Narayanan, B., Pryamitsyn, V., and Ganesan, V. (2006) Shear-induced phase transition in ternary polymer blends. Phys. Rev. Lett., 96 (2), 028302-1-028302-4. 

Auliawan et al7 studied ternary polymer blends of PLLA, poly(methyl methacrylate) (PMMA) and poly(ethylene oxide) (PEO) as matrix for nanocomposites. Their conclusions were that nanoclays enhanced the non-isothermal crystallization of the blend, since this ternary polymer blend hardly crystallized when cooled from the melt. The addition of vermiculite at loadings larger than 1% by weight retarded the crystallization process, while montmorillonite enhanced the crystallization process to some extent before retarding it. 

M. Sprenger, S. Walheim, A. Budkowski, U. Steiner, Hierarchic structure formation in binary and ternary polymer blends. Interface Science 11 (2(X)3) 225-235. 

Quipeng [169] demonstrated that glass-transition temperatures for PCL/PVME mixtures were single and composition dependent these authors made no reference to crystal melting temperatures. They observed LCST behaviour for this system with a critical point at about 200 ° C for a 50 50 w/w mixture. This study was part of an investigation of ternary polymer blends (Sect. 20). 

K. R. Sharma, Ternary Polymer Blend for Hydrogen Production vs. Inorganic High Surface Area Materials, Interpack 99, Mauii, HI, July 1999. 

K. R. Shartna, Ternary Polymer Blends for Hydrogen Prodnction vs Inorganic High Surface Area Zeolite Materials, 218th ACS National Meeting, New Orleans, LA, August 1999. 

Can the discussions on binary polymer blends be extended to ternary polymer blends ... 

Particularly synergistic properties can be obtained using ternary polymer blends that cannot be achieved with binary blends. Ternary blends based on NR, BR and EPDM have been used for tyre sidewalls and show excellent ultimate properties, better ozone resistance and fatigue resistance under dynamic load. Spedlic morphology development, crosslinking behaviour and their correlation to mechanical properties of different ternary rubber blends like butyl rubber (IIR)/NR/SBR and NR/BR/SBR blends have been well... 

Figure 3. These images represent the types of structural and chemical information that can be obtained using the OCM-CFM dual-mode technique (a,), CARS (b.f and immersive visualization (cf The OCM-CFM images (a) are of fetal chick osteoblasts cultured on porous polycaprolactone scaffolds. Differences in pore size and crystalline regions of the polymer could be determinied at 145 pm from the surface. Figure b is a broadband CARS micrograph of a phase-separated ternary polymer blend. The colors green, blue, and red represent polystyrene, poly(ethylene terphthalate) and poly(methyl methacrylate), respectively. Figure c is a 3D respresentation of cells on polycaprolactone scaffold taken from the immersive visualization laboratory. This visual image provides additional information on cell shape, orientation, and position within the scaffold.

Dadmun M (1996) Effect of copolymer architecture on the interfacial structure and miscibility of a ternary polymer blend containing a copolymer and two homopolymers. Macromolecules 29 3868-3874... 

Su, CC. and Lin, JH. (2004) Ringed sphemlites in ternary polymer blends of poly(e-caprolactone), poly(styrene-co-acrylonitrile), and polymethacrylate. Colloid Polym. Sci., 283 (2), 182-193. 

Hsu, W.P. (2003) Phase behavior of hydrogen-bonded ternary polymer blends. J. Appl. Polym. Sci., 89, 2088-2094. 

The molecular dynamics of ternary polymer blends of PP/PA6/acrylonitrile butadiene styrene copolymer (ABS) in the presence of compatibilizers and multiwall carbon nanotubes (MWNTs) was investigated using DRS [69]. The relaxation time of the PA6 chains was found to have increased significantly when small amounts of compatibilizers (PP-g-MA) or styrene maleic anhydride (SMA) were added. The variation in relaxation time was found to depend heavily on the com-patibilizer efficiency. The variation in relaxation time for PA6 in the presence of 1 wt% MWNTs in the respective ternary blends also followed a similar trend however, the extent of mobility of the PA6 phase was influenced by the state of dispersion of MWNTs in the corresponding blends. 

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