Volume Fraction Of Homopolymer Research Articles

Formation of a C15 Laves Phase with a Giant Unit Cell in Salt-Doped A/B/AB Ternary Polymer Blends.

Salt-doped A/B/AB ternary polymer blends, wherein an AB copolymer acts as a surfactant to stabilize otherwise incompatible A and B homopolymers, display a wide range of nanostructured morphologies with significant tunability. Among these structures, a bicontinuous microemulsion (BμE) has been a notable target. Here, we report the surprising appearance of a robust C15 Laves phase, at compositions near where the BμE has recently been reported, in lithium bis(trifluoromethane) sulfonimide (LiTFSI)-doped low-molar-mass poly(ethylene oxide) (PEO)/polystyrene (PS)/symmetric PS-b-PEO block copolymer blends. The materials were analyzed by a combination of small-angle X-ray scattering (SAXS), 1H NMR spectroscopy, and impedance spectroscopy. The C15 phase emerges at a high total homopolymer volume fraction ϕH = 0.8 with a salt composition r = 0.06 (Li+/[EO]) and persists as a coexisting phase across a large area of the isothermal phase diagram with high PS homopolymer compositions. Notably, the structure exhibits a huge unit cell size, a = 121 nm, with an unusually high micelle core volume fraction (fcore = 0.41) and an unusually low fraction of amphiphile (20%). This unit cell dimension is at least 50% larger than any previously reported C15 phase in soft matter, despite the low molar masses used, unlocking the possibility of copolymer-based photonic crystals without compromising processability. The nanostructured phase evolution from lamellar to hexagonal to C15 along the EO60 isopleth (ϕPEO,homo-LiTFSI/ϕH = 0.6) is rationalized as a consequence of asymmetry in the homopolymer solubility limit for each block, which leads to exclusion of PS homopolymer from the PS-b-PEO brush prior to exclusion of the PEO homopolymer, driving increased interfacial curvature and favoring the emergence of the C15 Laves phase.

Nanostructure stability and swelling of ternary block copolymer/homopolymer blends: A direct comparison between dissipative particle dynamics and experiment

ABSTRACTTernary block copolymer (BCP)‐homopolymer (HP) blends offer a simple method for tuning nanostructure sizes to meet application‐specific demands. Comprehensive dissipative particle dynamic (DPD) simulations were performed to study the impact of polymer interactions, molecular weight, and HP volume fraction (φHP) on symmetric ternary blend morphological stability and domain spacing. DPD reproduces key features of the experimental phase diagram, including lamellar domain swelling with increasing φHP, the formation of an asymmetric bicontinuous microemulsion at a critical HP concentration , and macrophase separation with further HP addition. Simulation results matched experimental values for and lamellar swelling as a function of HP to BCP chain length ratio, α = NHP/NBCP. Structural analysis of blends with fixed φHP but varying α confirmed that ternary blends follow the wet/dry brush model of domain swelling with the miscibility of HPs and BCPs depending on α. Longer HPs concentrate in the center of domains, boosting their swelling efficiencies compared to shorter chains. These results advance our understanding of BCP‐HP blend phase behavior and demonstrate the value of DPD for studying polymeric blends. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 794–803

Liquid-crystal Assembly of Semiflexible-coil/Homopolymer Blends: a Dissipative Particle Dynamics Study

The liquid-crystal assembly of semiflexible-coil diblock copolymers with coil or semiflexible homopolymers is studied by dissipative particle dynamics simulation. Phase diagrams of the blends and orientation ordering parameters among semiflexible blocks are constructed as a function of chain stiffness and homopolymer volume fraction. For semiflexible-coil/coil blends with varying stiffness of semiflexible blocks, we display the rich phase behaviors of the system transited from coil-coil/coil to rod-coil/coil blends. The disorder-lamellae or lamellae-liquid crystalline transition and “dry brush” phenomenon induced by coil homopolymers are observed. For semiflexible-coil/semiflexible blends, adding semiflexible homopolymers also leads to a disorder-order transition and even a transition between monolayer and bilayer smectic-A phase. The results demonstrate that blending homopolymers into semiflexible copolymers can induce liquid-crystal assembly and even improve the orientation ordering of semiflexible blocks effectively.

Phase transition of block copolymer/homopolymer binary blends under 2D confinement

Constraints imposed by nanometer scale confinement lead to the changes in bulk equilibrium behavior of block copolymers (BCPs). Cylindrical pores with diameter corresponding to the equivalent length of several copolymer chains have been employed to investigate the influence of two-dimensional (2D) confinement on the behavior of BCPs. Herein, we reported the microdomain transition behavior of block copolymer/homopolymer (AB/A) binary blends in cylindrical confinement. Lamellae forming poly(styrene-b-butadiene) (PS-b-PBD) and PS homopolymers (hPS) were drawn into the pores of anodized aluminum oxide (AAO) and isolated by selective etching of the AAO templates. Concentric ring morphologies of neat PS-b-PBD in the cylindrical confinement varied with on the addition of hPS. Given the volume fraction of homopolymers, the phase behavior of polymer blends was dependent on the molecular weight of homopolymers. When the ratio between the molecular weight of hPS and PS block was much lower than unity (α«1) (i.e., wet brush regime), the concentric ring structure was transformed into helical or spherical structure depending on the volume fraction of hPS. For α≈1 (i.e., dry brush regime), additional hPS chains were localized at the center of concentric ring where the entropic penalty of copolymer chains induced by confinement is maximized. Over the capability of hPS in the BCP domains in radial axis, the phase transition into microemulsions occurred in the dry brush regime. In both wet and dry brush regimes, the effect of hPS on the phase transition of BCP was significantly enhanced in the nanoscale 2D confinement compared to the bulk state due to the loss of conformational entropy of polymer chains.

Directed self-assembly of ternary blends of block copolymer and homopolymers on chemical patterns

In this work ternary blends of symmetric lamellae-forming poly(styrene-block-methyl methacrylate) block copolymer and polystyrene and PMMA homopolymers were prepared for the directed self-assembly (DSA) on chemically nanopatterned substrates using 2× density multiplication. Homopolymers with comparable molecular weights to that of the corresponding blocks in the block copolymer were used to adjust the periods of the blends. The periods of the blends increased from 38.5 to 50 nm as the volume fraction of homopolymers increased from 0 to 30%. The periods were analyzed by grazing-incidence small-angle X-ray scattering, direct measurement from and fast Fourier transform of scanning electron microscopy images. DSA results indicate that the perfection and registration of the assembled films were mainly determined by the commensurability between the periods of the blends and the chemical patterns. Patterns with relatively small w/LS (guiding stripe width/period of chemical pattern) led to mixed structures of dots and parallel structures. The process window of LS where the block copolymer alignment shows a high degree of perfection was estimated at ±3.6% to ±4.6% Lo.

Phase Behavior of Binary Blends of Diblock Copolymer/Homopolymer Confined in Spherical Nanopores

Binary blends of a diblock copolymer (AB) and an incompatible homopolymer (C) confined in spherical cavities are studied using a simulated annealing technique. The phase behavior of the blends is examined for four typical cases, representing the different selectivity of the pore surface to the A, B, and C species. The internal morphology of the spherical polymeric particles is controlled by the homopolymer volume fraction, the degree of confinement, and the composition of the copolymer. Inside a particle, the homopolymers segregate to form one or, under some conditions, two domains; thus, the homopolymers may act as an additional controlling parameter of the shape and symmetry of the copolymer domain. A rich array of confinement-induced novel diblock copolymer morphologies is predicted. In particular, core-shell particles with the copolymers as the shell wrapping around a homopolymer core or a copolymer-homopolymer combined core and Janus-like particles with the copolymers and the homopolymers on different sides are obtained.

Pattern Dimensions and Feature Shapes of Ternary Blends of Block Copolymer and Low Molecular Weight Homopolymers Directed To Assemble on Chemically Nanopatterned Surfaces

Ternary blends of cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) and low molecular weight PS and PMMA were directed to assemble on chemically patterned surfaces with hexagonal symmetry. The chemical patterns consisted of strongly PMMA preferential spots, patterned by electron-beam lithography, in a matrix of PS. The spot-to-spot spacing of the chemical patterns (L(s)) was varied between 0.9L(0) and 1.1L(0), where L(0) is the cylinder-to-cylinder spacing of the pure block copolymer in bulk. The homopolymer volume fraction of the blends (ϕ(H)) was varied between 0 and 0.3. In addition, chemical patterns were formed with selected spots missing from the perfect hexagonal array, such that the interpolation of domains between patterned spots could be examined on patterns where the polymer/pattern feature density ranged from 1:1 to 4:1. The assemblies were analyzed with top-down SEM, from which orientational order parameter (OP(o)) values were determined. The SEM analysis was complemented by Monte Carlo simulations, which offered insights into the shapes of the assembled cylindrical domains. It was found that, in comparison to pure block copolymer, adding homopolymer increased the range of L(s) values over which assemblies with high OP(o) values could be achieved for 1:1 assemblies. However, the corresponding simulations showed that in the 1:1 assemblies the shape of the cylinders was more uniform for pure block copolymer than for blends. In the case of the 4:1 assemblies, the range of L(s) values over which assemblies with high OP(o) values could be achieved was the same for all values of ϕ(H) tested, but the domains of the pure block copolymer had a more uniform shape. Overall, the results provided insights into the blend composition to be used to meet technological requirements for directed assembly with density multiplication.

Phase Behavior of Rod–Coil Diblock Copolymer and Homopolymer Blends from Self-Consistent Field Theory

The phase behavior of binary blends of rod-coil diblock copolymers and coil or rod homopolymers is studied by the self-consistent field theory (SCFT). The rod blocks are modeled as wormlike chains and the corresponding SCFT equations are solved using a hybrid method, in which the orientation-dependent functions are discretized on a unit sphere, while the positional space-dependent functions are treated using a spectral method. Phase diagrams of the blends are constructed as a function of the homopolymer volume fraction and phase segregation strength. It is discovered that the phase behavior of the system depends on the flexibility of the homopolymers. The addition of coil-homopolymers stabilizes the smectic phases. Low-molecular weight coil-homopolymers tend to mix with the coil-blocks, whereas high-molecular weight coil-homopolymers are mostly localized at the center of the coil-domains. On the other hand, the addition of rod-homopolymers strongly affects the orientation ordering of the system, leading to transitions between monolayer smectic-C, monolayer smectic-A and bilayer smectic-A phases.

The vesicle formation in a binary amphiphilic diblock copolymer/homopolymer solution

The formation of vesicles in a binary blend of an amphiphilic diblock copolymer AB/homopolymer C was studied in a dilute solution using the real space two-dimensional self-consistent field theory (SCFT). Special attention was played to the role played by the homopolymer C in controlling the vesicle formation. In the simulations, it was found that as the averaged volume fraction of homopolymer C was decreased while keeping the total averaged volume fraction of block copolymer AB and homopolymer C unchanged, there was a morphological transition from the bilayer vesicles to rod-like/circle-like micelles. The compound vesicle structure was observed in the simulations. When the averaged volume fraction of block copolymer AB was further increased while the total averaged volume fraction of AB and C remained unchanged, the compound vesicle structure became less favored entropically than the unilamellar vesicle structure. The effect of the degree of polymerization of the homopolymer C on the vesicle formation of the amphiphilic system was examined. By reducing the degree of polymerization of the homopolymer C to unity, the component C became a small solvent molecule immiscible with the bulk solvent. It was found that the small solvent C exerted no influence on the morphological stability of the vesicles.

Interplay between microscopic and macroscopic phase separations in ternary polymer melts: Insight from mesoscale modelling

We present a mesoscale computational study of a ternary polymer melt comprising of two immiscible homopolymers A and B, and a symmetric diblock copolymer AB. The system exhibits rich phase behavior such as microphase separations in the copolymer-rich region and macrophase separations in the homopolymer-rich region. We use Dissipative Particle Dynamics (DPD) and Dynamic mean-field Density Functional Theory (DDFT) to predict the phase behavior along a temperature–homopolymer volume fraction isopleth for an A/B/AB mesoscale system that mimics a real system of low molecular weight poly(dimethyl siloxane) (PDMS) and poly(ethyl ethylene) (PEE) homopolymers, and a nearly symmetric PDMS–PEE diblock copolymer. The mesoscale polymer parameters are derived using a top-down coarse-graining approach that utilizes order–disorder and critical temperatures. Boundaries between disordered, lamellar and two-phase regions of the phase diagram are determined by visual inspection of configurational snapshots in combination with the abrupt changes that are exhibited by the diblock-copolymer orientational order parameter and bead order parameter when the phase boundaries are crossed. Phase diagrams predicted by DPD and DDFT agree reasonably well with the experimental phase diagram of the PDMS/PEE/PDMS–PEE system except for a narrow channel of bicontinuous microemulsion that is not predicted by either the DPD or the DDFT models. We discuss possible refinements of the models to capture this bicontinuous phase.

Phase Behavior and Dimensional Scaling of Symmetric Block Copolymer−Homopolymer Ternary Blends in Thin Films

The phase behavior and dimensional scaling of symmetric ternary blends composed of poly(styrene-block-methyl methacrylate) block copolymers and the corresponding polystyrene and poly(methyl methacrylate) homopolymers in thin films were investigated as a function of χN (the product of the Flory−Huggins interaction parameter and the overall degree of polymerization of the block copolymer), α (the ratio of the degree of polymerization of the homopolymers to that of the block copolymer), and ϕH (the volume fraction of homopolymers in the blends). The phase transitions were characterized by three methods: disappearance of high-order peaks in the fast Fourier transform (FFT) spectra from scanning electron microscopy (SEM) images, application of the amphiphilicity factor determined from the FFTs, and, in the case of thicker films, the appearance of either microphase- or macrophase-separated domains in SEM images. Above the order−disorder transition (ODT) in the χN−ϕH phase diagram, the symmetric ternary blends t...

Directed assembly of asymmetric ternary block copolymer-homopolymer blends using symmetric block copolymer into checkerboard trimming chemical pattern

Here, the authors studied the directed assembly of the asymmetric ternary blends, composed of polystyrene-block-poly(methyl methacrylate) copolymer (PS-b-PMMA) and the corresponding PS and PMMA homopolymers, on a checkerboard chemical pattern which was fabricated by e-beam lithography, controlling the periodicity (LS), length (D), and spacing of the exposed lines or dashed lines in the chemical pattern. The checkerboard chemical pattern, which cannot be generated with typical self-assembled block copolymer morphologies, consists of either offset, parallel, dashed lines, or alternating lines and dashed lines, and is used in the fabrication of dynamic random access memory. The degree of perfection and domain uniformity of the assembled block copolymer thin films on the complex pattern were a function of the commensurability of the volume fraction of PS in the blend (ϕS) with the fraction of area on the pattern wet by PS (FS), as well as the volume fraction of homopolymer in the blend (ϕH). The best assembly occurred ϕS and FS were commensurate, and ϕH was optimized for the given blend and pattern.

Phase Behavior of Symmetric Ternary Block Copolymer-Homopolymer Blends in Thin Films and on Chemically Patterned Surfaces

The phase diagram of symmetric ternary blends of diblock copolymers and homopolymers in thin films was determined as a function of increasing volume fraction of homopolymer (phi(H)) and was similar to that for these materials in the bulk. Blends with compositions in the lamellar region of the diagram (phi(H)< or =0.4) could be directed to assemble into ordered lamellar arrays on chemically striped surfaces if the characteristic blend dimension (L(B)) and the period of the stripes (L(S)) were commensurate such that L(S)=L(B)+/-0.10L(B). Blends with compositions in the microemulsion region of the diagram (phi(H) approximately 0.6) assembled into defect-free lamellar phases on patterned surfaces with L(S)> or =L(B), but formed coexisting lamellar (with period L(S)) and homopolymer-rich phases when L(S)<L(B).

Which is More Efficient as Compatibilizer: Di-block or Multiblock Copolymer?

Monte Carlo simulations were used to investigate the compatibilizing behaviors of multi-block copolymers with different architectures in A/B/(block copolymer) ternary blends. The volume fraction of homopolymer A, employed as the dispersed phase, was 19%. The simulations illustrate how a di- or multi-block copolymer aggregates at the interfaces and influences the phase behaviour of such incompatible polymer blends. The di-block copolymer chains tend to "stand" on the interface whereas the multi-block chains lie on the interface. In comparison with the di-block copolymer, the block copolymers with 4, or 10 blocks can occupy more areas on the interface, and thus the multi-block copolymers have higher efficiency for the retardation of the phase separation.

Morphologies of Diblock Copolymer/Homopolymer Blend Films

AbstractSummary: Using bond length fluctuation and cavity diffusion algorithm, the morphologies of diblock copolymer/homopolymer blend films, AB/C and AB/A, confined between two hard walls are studied via Monte Carlo (MC) simulation on a cubic lattice. For the AB/C film, the C homopolymer is supposed to be more compatible with the A block than with the B block, while A and B are mutually incompatible. Effects of the composition of the diblock copolymer/homopolymer mixture, the symmetry of the diblock copolymer chain, the film thickness and the selective wall field on morphologies are studied in detail. Furthermore, the simulated results are compared with that of corresponding ABA and ABC triblock copolymer thin films. Comparisons with experiments and SCF theory also show good agreement. The results indicate that both the AB/C and AB/A can be used to prepare porous AB diblock copolymer membranes, the size of the pore channel can be controlled by the volume fraction of homopolymer C or homopolymer A.Morphology of A6B14/C10 polymer blend film.magnified imageMorphology of A6B14/C10 polymer blend film.

Influence of block lengths and symmetries of block copolymers on phase behavior of polymer A/polymer B/block copolymer ternary blends

Monte Carlo simulations were used to investigate the compatibilizing effects of diblock copolymers in A/B/A–B diblock copolymer ternary blends and triblock copolymers in A/B/triblock copolymer ternary blends, respectively. The volume fraction of homopolymer A was 19% and was the dispersed phase. The simulation results show that diblock copolymers with longer A-blocks are more efficient as compatibilizers, and symmetric triblock copolymers with a shorter middle block length are easily able to bridge each other through the association of the end blocks. This kind of triblock copolymers have relatively high ability to retard phase separation as compatibilizers.

Tricontinuous Cubic Structures inABC/A/CCopolymer and Homopolymer Blends

Using the Monte Carlo lattice-simulation technique, we present numerical evidence of the formation of gyroid and nongyroid tricontinuous cubic phases in high polymeric systems of ABC/A/C triblock copolymer and homopolymer blends. By increasing the volume fraction of homopolymer, a remarkable phase sequence G (gyroid) --> D (diamond) --> P (primitive) is observed, which is common to certain surfactant systems. Our results indicate that the ABC triblock copolymer system with blending homopolymers may be a zoo of cubic phases, suitable for comparative studies of these phases.

Phase Behavior of an ABC Triblock Copolymer Blended with A and C Homopolymers

The structures of ternary blends composed of a nearly symmetric poly(styrene-b-isoprene-b-dimethylsiloxane) (SID) triblock copolymer (volume fractions of S/I/D = 0.20/0.59/0.21, Mn = 40 000 g/mol) and equal volume fractions of low-molecular-weight polystyrene (Mn = 2360 g/mol) and poly(dimethylsiloxane) (Mn = 2200 g/mol) are investigated by small-angle X-ray and neutron scattering and transmission electron microscopy. When the total homopolymer volume fraction exceeds 65%, the blend macroscopically separates into ordered homopolymer-poor and -rich regions. Between 45 and 65% homopolymer volume fraction, hexagonally packed core−shell cylinders form with PDMS cores and PI shells. Between 15 and 45% homopolymer volume fraction, a core−shell gyroid morphology is observed with PDMS cores and PI shells. These core−shell variations of the classical structures of diblock copolymers are attributed to a small asymmetry in segment−segment interaction parameters. The neat SID block copolymer has a new complex ordered...