Self-assembly Of Block Polymers Research Articles

Cylinders-in-Undulating-Lamellae Morphology from ABC Bottlebrush Block Terpolymers.

Block polymer self-assembly affords a versatile bottom-up strategy to develop materials with the desired properties dictated by specific symmetries and dimensions. Owing to distinct properties compared with linear counterparts, bottlebrush block polymers with side chains densely grafted on a backbone have attracted extensive attention. However, the morphologies found in bottlebrush block polymers so far are limited, and only lamellar and cylindrical ordered phases have been reported in diblock bottlebrushes. The absence of complex morphologies, such as networks, might originate from the intrinsically stiff backbone architecture. We experimentally investigated the morphologies of nonfrustrated ABC bottlebrush block terpolymers, based on two chemistries, poly(ethylene-alt-propylene)-b-polystyrene-b-poly(dl-lactic acid) (PEP-PS-PLA) and PEP-b-PS-b-poly(ethylene oxide) (PEP-PS-PEO), synthesized by ring-opening metathesis polymerization of norbornene-terminated macromonomers. Structural characterization based on small-angle X-ray scattering and transmission electron microscopy measurements revealed an unprecedented cylinders-in-undulating-lamellae (CUL) morphology with p2 symmetry for both systems. Additionally, automated liquid chromatography was employed to fractionate the PEP-PS-PLA bottlebrush polymer, leading to fractions with a spectrum of morphologies, including the CUL. These findings underscore the significance of macromolecular dispersity in nominally narrow dispersity bottlebrush polymers while demonstrating the power of this fractionation technique.

Enhanced electrocatalytic activity of 2D ordered mesoporous nitrogen-rich carbon nanosheets functional NiFe2O4 nanospheres for ultrasensitive detection of chlorogenic acid in natural samples

Two-dimensional (2D) porous carbon nanosheets loaded with bimetallic oxide nanospheres are expected to be very attractive electrocatalysts. In this work, we constructed ordered mesoporous nitrogen-rich carbon on the surface of ultrathin-reduced graphene oxide (rGO) using the self-assembly of block polymers and compared the effect of pore structure on the sensing performance. The rGO wrapped by N-doped ordered porous carbon possesses a large specific surface area of 784.9 m2/g. The composite with NiFe2O4 nanospheres with rough surfaces effectively prevented the interlayer accumulation of mNPC@rGO. Meanwhile, the multivalent form of metal elements in NiFe2O4 facilitates the redox reaction. These distinct advantages combine to create an active surface that strongly binds to chlorogenic acid molecules (CGA). Importantly, we have computationally analyzed the reaction mechanism of mNPC@rGO/NiFe2O4 electrocatalytic CGA molecules by density functional theory. In the best case, the mNPC@rGO/NiFe2O4/GCE sensor has a limit of detection (LOD) as low as 2 × 10−11 M and a wide linear range (1 × 10−10−2 × 10−5 M). The sensor displays a remarkable level of selective response to CGA in the presence of other co-interfering species. Furthermore, it has superb repeatability and reproducibility for CGA. The sensor has shown outstanding recovery (95.9%−104.9%) in the practical viability of detecting CGA in food, natural products, and biological samples. This work not only provides a new candidate for the accurate detection of CGA, but also provides insight into the exploration of advanced sensing materials.

Core-Shell Gyroid in ABC Bottlebrush Block Terpolymers.

Block polymer self-assembly provides a versatile platform for creating useful materials endowed with three-dimensional periodic network morphologies that support orthogonal physical properties such as high ionic conductivity and a high elastic modulus. However, coil configurations limit conventional linear block polymers to finite ordered network dimensions, which are further restricted by slow self-assembly kinetics at high molecular weights. A bottlebrush architecture can circumvent both shortcomings owing to extended backbone configurations due to side chain crowding and molecular dynamics substantially free of chain entanglements. However, until now, network morphologies have not been reported in AB bottlebrush block copolymers, notwithstanding favorable mean-field predictions. We explored the phase behavior by small-angle X-ray scattering of 133 poly(ethylene-alt-propylene)-b-polystyrene (PEP-PS) diblock and PEP-PS-PEO triblock bottlebrush copolymers prepared by ring-opening metathesis polymerization (ROMP) of norbornene-functionalized poly(ethylene-alt-propylene) (PEP), poly(styrene) (PS), and poly(ethylene oxide) (PEO) macromonomers with total backbone degrees of polymerization Nbb between 20 and 40. The PEP-PS diblocks exhibited only cylindrical and lamellar morphologies over the composition range of ca. 30-70%. However, addition of variable-length bottlebrush PEO blocks to diblocks containing 30-50% PS led to the formation of a substantial core-shell double gyroid (GYR) phase window containing 20 bottlebrush triblock specimens, which is the focus of this report. Encouragingly, the GYR unit cell dimensions increased as d ∼ Nbb0.92, portending the ability to access larger network dimensions than previously obtained with linear AB or ABC block polymers. This work highlights extraordinary opportunities associated with applying facile ROMP chemistry to multiblock bottlebrush polymers.

Next-Generation Ultrafiltration Membranes Enabled by Block Polymers

Reliable and equitable access to safe drinking water is a major and growing challenge worldwide. Membrane separations represent one of the most promising strategies for the energy-efficient purification of potential water sources. In particular, porous membranes are used for the ultrafiltration (UF) of water to remove contaminants with nanometric sizes. However, despite exhibiting excellent water permeability and solution processability, existing UF membranes contain a broad distribution of pore sizes that limit their size selectivity. To maximize the potential utility of UF membranes and allow for precise separations, improvements in the size selectivity of these systems must be achieved. Block polymers represent a potentially transformative solution, as these materials self-assemble into well-defined domains of uniform size. Several different strategies have been reported for integrating block polymers into UF membranes, and each strategy has its own set of materials and processing considerations to ensure that uniform and continuous pores are generated. This Review aims to summarize and critically analyze the chemistries, processing techniques, and properties required for the most common methods for producing porous membranes from block polymers, with a particular focus on the fundamental mechanisms underlying block polymer self-assembly and pore formation. Critical structure-property-performance metrics will be analyzed for block polymer UF membranes to understand how these membranes compare to commercial UF membranes and to identify key research areas for continued improvements. This Review is intended to inform readers of the capabilities and current challenges of block polymer UF membranes, while stimulating critical thought on strategies to advance these technologies.

Impact of Architectural Asymmetry on Frank-Kasper Phase Formation in Block Polymer Melts.

In recent decades, the discoveries of complex low-symmetry phases in soft matter have inspired advances in molecular and materials design. However, understanding the mechanisms underlying symmetry selection across soft matter remains an important challenge in materials science. Block polymers represent attractive model materials because they permit wide synthetic tunability and provide access to multiple length scales (1-100 nm). However, to date the block polymer design space has been largely limited to variations in molecular weight, block volume fraction, and conformational asymmetry. The molecular architecture-the way in which chains are connected-offers rich potential but remains relatively unexplored in experimental block polymers. Our work bridges this gap, connecting molecular architecture, space-filling demands, and symmetry selection in block polymer self-assembly. Three series of block polymers were synthesized by living polymerization, tuning the architectural asymmetry across the linear-b-linear and linear-b-bottlebrush limits. The bottlebrush architecture amplifies two key ingredients for the formation of Frank-Kasper phases: high conformational asymmetry and high self-concentration. Analysis by small-angle X-ray scattering provides insight into the impact of architectural asymmetry on block polymer self-assembly. Increasing the asymmetry between blocks opens the complex phase window, expanding opportunities to tune symmetry selection in block polymer melts.

Enhanced Conductivity via Homopolymer-Rich Pathways in Block Polymer-Blended Electrolytes

The optimization of ionic conductivity and lithium-ion battery stability can be achieved by independently tuning the ion transport and mechanical robustness of block polymer (BP) electrolytes. However, the ionic conductivity of BP electrolytes is inherently limited by the covalent attachment of the ionically conductive block to the mechanically robust block, among other factors. Herein, the BP electrolyte polystyrene-block-poly(oligo-oxyethylene methacrylate) [PS-b-POEM] was blended with POEM homopolymers of varying molecular weights. The incorporation of a higher molecular weight homopolymer additive (α > 1 state) promoted a "dry brush-like" homopolymer distribution within the BP self-assembly and led to higher lithium salt concentrations in the more mobile homopolymer-rich region, increasing overall ionic conductivity relative to the "wet brush-like" (α < 1 state) and unblended composites, where α is the molecular weight ratio between the POEM homopolymer and the POEM block in the copolymer. Neutron and X-ray reflectometry (NR and XRR, respectively) provided additional details on the lithium salt and polymer distributions. From XRR, the α > 1 blends showed increased interfacial widths in comparison to their BP (unblended) or α < 1 counterparts because of the more central distribution of the homopolymer. This result, paired with NR data that suggested even salt concentrations across the POEM domains, implied that there was a higher salt concentration in the homopolymer POEM-rich regions in the dry brush blend than in the wet brush blend. Furthermore, using 7Li solid-state nuclear magnetic resonance spectroscopy, we found a temperature corresponding to a transition in lithium mobility (T Li mobility) that was a function of blend type. T Li mobility was found to be 39 °C above T g in all cases. Interestingly, the ionic conductivity of the blended BPs was highest in the α > 1 composites, even though these composites had higher T gs than the α < 1 composites, demonstrating that homopolymer-rich conducting pathways formed in the α > 1 assemblies had a larger influence on conductivity than the greater lithium ion mobility in the α < 1 blends.

Stability of the A15 phase in diblock copolymer melts

The self-assembly of block polymers into well-ordered nanostructures underpins their utility across fundamental and applied polymer science, yet only a handful of equilibrium morphologies are known with the simplest AB-type materials. Here, we report the discovery of the A15 sphere phase in single-component diblock copolymer melts comprising poly(dodecyl acrylate)-block-poly(lactide). A systematic exploration of phase space revealed that A15 forms across a substantial range of minority lactide block volume fractions (fL = 0.25 - 0.33) situated between the σ-sphere phase and hexagonally close-packed cylinders. Self-consistent field theory rationalizes the thermodynamic stability of A15 as a consequence of extreme conformational asymmetry. The experimentally observed A15-disorder phase transition is not captured using mean-field approximations but instead arises due to composition fluctuations as evidenced by fully fluctuating field-theoretic simulations. This combination of experiments and field-theoretic simulations provides rational design rules that can be used to generate unique, polymer-based mesophases through self-assembly.

Nanoscale 3D ordered polymer networks

Structures having nanoscale 3D geometries are valuable as multifunctional materials, where multi-continuous microphases can synergistically influence mechanical, optical, transport and other properties. Such very high interface surface to volume ratio structures occur in a variety of materials including natural materials such as butter fly wings and sea urchin exoskeletons and in synthetic self-assembled structures such as surfactant/water systems and block polymers. Quantitative morphological characterization of such complex geometric structures is quite challenging. Unit cell sizes range from 10–300 nm with corresponding feature sizes on the 2–50 nm scale. Since these nanoscale network structures are bicontinuous, when one constituent is removed, the structure is still self supporting. Removal of one component produces a nanoporous material that may be in-filled with another component, or the surfaces of the nanopores can be coated with ultra-thin layers by atomic layer deposition to offer multifunctional capabilities. Due to the ability to individually tailor the properties of the network(s) and matrix, for example, to create strong dielectric or impedance contrast, such spatially periodic structures are excellent for the interference of waves (electromagnetic for photonic applications and acoustic for phononic applications) that can lead to bandgaps and hence the control of wave propagation in the material. This mini-review will focus on networks formed by bottom up self assembly of block polymers. In addition to structural issues, we emphasize the special physical properties related to bi- or tri-continuous networks.

Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush.

Grafting density is an important structural parameter that exerts significant influences over the physical properties of architecturally complex polymers. In this report, the physical consequences of varying the grafting density (z) were studied in the context of block polymer self-assembly. Well-defined block polymers spanning the linear, comb, and bottlebrush regimes (0 ≤ z ≤ 1) were prepared via grafting-through ring-opening-metathesis polymerization. ω-Norbornenyl poly(d,l-lactide) and polystyrene macromonomers were copolymerized with discrete comonomers in different feed ratios, enabling precise control over both the grafting density and molecular weight. Small-angle X-ray scattering experiments demonstrate that these graft block polymers self-assemble into long-range-ordered lamellar structures. For 17 series of block polymers with variable z, the scaling of the lamellar period with the total backbone degree of polymerization (d* ∼ Nbbα) was studied. The scaling exponent α monotonically decreases with decreasing z and exhibits an apparent transition at z ≈ 0.2, suggesting significant changes in the chain conformations. Comparison of two block polymer systems, one that is strongly segregated for all z (System I) and one that experiences weak segregation at low z (System II), indicates that the observed trends are primarily caused by the polymer architectures, not segregation effects. A model is proposed in which the characteristic ratio (C∞), a proxy for the backbone stiffness, scales with Nbb as a function of the grafting density: C∞ ∼ Nbbf(z). The scaling behavior disclosed herein provides valuable insights into conformational changes with grafting density, thus introducing opportunities for block polymer and material design.

Effects of Tailored Dispersity on the Self-Assembly of Dimethylsiloxane–Methyl Methacrylate Block Co-Oligomers

The effect of dispersity on block polymer self-assembly was studied in the monodisperse limit using a combination of synthetic chemistry, matrix-assisted laser desorption ionization spectroscopy, and small-angle X-ray scattering. Oligo(methyl methacrylate) (oligoMMA) and oligo(dimethylsiloxane) (oligoDMS) homopolymers were synthesized by conventional polymerization techniques and purified to generate an array of discrete, semidiscrete, and disperse building blocks. Coupling reactions afforded oligo(DMS-MMA) block polymers with precisely tailored molar mass distributions spanning single molecular systems (Đ = 1.0) to low-dispersity mixtures (Đ ≈ 1.05). Discrete materials exhibit a pronounced decrease in domain spacing and sharper scattering reflections relative to disperse analogues. The order-disorder transition temperature (TODT) also decreases with increasing dispersity, suggesting stabilization of the disordered phase, presumably due to the strengthening of composition fluctuations at the low molar masses investigated.

Manipulating the ABCs of self-assembly via low-χ block polymer design

Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χij). In this article, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χAC [Formula: see text] 0), promotes organization into a unique mixed-domain lamellar morphology, which we designate LAMP Transmission electron microscopy indicates that LAMP exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM3) with ABCB periods. Complementary small-angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations and predicts that LAMP is thermodynamically stable below a critical χAC, above which LAM3 emerges. Both experiments and theory expose close analogies to ABA' triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. These conclusions provide fresh opportunities for block polymer design with potential consequences spanning all self-assembling soft materials.

Spectroscopic investigation on chirality transfer in additive-driven self-assembly of block polymers

Chiral supramolecules prepared by the additive-driven self-assembly of block copolymers provide a facile method to construct helical nanostructures. In this study, we investigated the chiral transfer from chiral tartaric acid to poly(styrene)-b-poly(ethylene oxide) using small-angle X-ray scattering, transmission electron microscopy, circular dichroism, and vibrational circular dichroism. The results showed that the chirality was transferred to both the segments of block copolymer irrespective of the interaction with the chiral additives and formation of helical phase structure. However, the chirality transfer was carried out using different methods: for poly(ethylene oxide) segments, the chirality transfer was carried out via direct hydrogen bond formation; for polystyrene segments, the chirality transfer was carried out via the cooperative motion of block copolymers during the thermal annealing.

A Reactive Platform Approach for the Rapid Synthesis and Discovery of High χ/Low N Block Polymers

We report a reactive polymer platform for the rapid discovery of strongly segregated diblock polymers that microphase separate into well-defined morphologies with sub-5 nm features. Our strategy employs reactive poly(styrene-block-2-vinyl-4,4-dimethylazlactone) (SV) polymers with low degrees of polymerization (N), in which the V blocks undergo selective and quantitative reactions with functional primary amines, to identify new poly(acrylamides) that are highly immiscible with poly(styrene) and induce block polymer self-assembly. Using a combination of optical birefringence and small-angle X-ray scattering (SAXS), we characterize a library of 17 block polymers produced by amine functionalization of four parent SV diblocks synthesized by sequential RAFT polymerizations. We demonstrate that V block functionalization with hydroxy- and methoxy-functional amines yields diblocks that order into lamellar mesophases with half-pitches as small as 3.8 nm. Thus, this azlactone-based reactive molecular platform enable...

High χ-Low N Block Polymers: How Far Can We Go?

Block polymers incorporating highly incompatible segments are termed "high χ" polymers, where χ is the Flory-Huggins interaction parameter. These materials have attracted a great deal of interest because low molar mass versions allow for the formation of microphase-separated domains with very small (<10 nm) feature sizes useful for nanopatterning at these extreme dimensions. Given that well-established photolithographic techniques now face difficult challenges of implementation at scales of 10 nm and below, the drive to further develop high χ block polymers is motivated by trends in the microelectronics industry. This Viewpoint highlights our perspective on this niche of block polymer self-assembly. We first briefly review the relevant recent literature, exploring the various block polymer compositions that have been specifically designed for small feature size patterning. We then overview the now standard method for the benchmarking χ values between different pairs of polymers and the consequences of low N and high χ on the thermodynamic aspects of microphase separation. Finally, we comment on restrictions going forward and offer our perspective on the future of this exciting area of block polymer self-assembly.

Hierarchically porous polymers from hyper-cross-linked block polymer precursors.

We report synthesis of hierarchically porous polymers (HPPs) consisting of micropores and well-defined 3D continuous mesopores by combination of hyper-cross-linking and block polymer self-assembly. Copolymerization of 4-vinylbenzyl chloride (VBzCl) with divinylbenzene (DVB) in the presence of polylactide (PLA) macro-chain-transfer agent produced a cross-linked block polymer precursor PLA-b-P(VBzCl-co-DVB) via reversible addition-fragmentation chain transfer polymerization. A nanoscopic bicontinuous morphology containing PLA and P(VBzCl-co-DVB) microdomains was obtained as a result of polymerization-induced microphase separation. While a basic treatment of the precursor selectively removed PLA to yield a reticulated mesoporous polymer, hyper-cross-linking of the precursor by FeCl3 generated micropores in the P(VBzCl-co-DVB) microdomain via Friedel-Crafts alkylation and simultaneously degraded PLA to produce the HPP containing micropores in the mesoporous framework. The mesopore size of the HPP could be precisely controlled from 6 to 15 nm by controlling the molar mass of PLA. We demonstrate acceleration in adsorption rate in the HPP compared to a hyper-cross-linked microporous polymer.