Highly stable petroleum pitches provide access to the deep glassy state.

Differential scanning calorimetry (DSC) was used to study the fast aging behavior of two petroleum pitch materials despite being only three to five years old. We observe that these highly aromatic pitches with broad distributions of both molecular weight and aromaticity exhibit large enthalpic relaxation endotherms in initial DSC heating scans, and 20-32 °C reductions in the fictive temperature and 0.35-0.87 of θK, which are indicative of aged glasses similar to ultrastable glasses and 20 MA aged amber. Quantifying the degree of thermodynamic stability relative to the Kauzmann temperature vs. the aging time demonstrates that these materials age just as quickly as low fragility metallic glasses. Additionally, we observe that pitches age faster than polymers reported in the literature when compared using down-jump experiments. We hypothesize that the fraction of higher aromaticity of pitch molecules plays a crucial role in faster dynamics. The unique aging behavior and the ability to produce pitches in bulk quantities using pilot-scale equipment, while being possible to tailor their molecular composition, make them a useful material for studying complex aging dynamics in the deep glassy state.

Methanol-Assisted ADMET Polymerization of Semiaromatic Amides.

A method for the acyclic diene metathesis polymerization of semiaromatic amides is described. The procedure uses second-generation Grubbs' catalyst and N-cyclohexyl-2-pyrrolidone (CHP), a high boiling, polar solvent capable of solubilizing both monomer and polymer. The addition of methanol to the reaction was found to significantly increase polymer molar mass although the role of the alcohol is currently not understood. Hydrogenation with hydrogen gas and Wilkinson's catalyst resulted in near-quantitative saturation. All polymers synthesized here exhibit a hierarchical semicrystalline morphology driven by ordering of aromatic amide groups via strong nonbonded interactions. Furthermore, the melting points can be tuned over a >100 °C range by precise substitution at just one of the backbone positions on each mer (<5% of the total).

The effect of pyrolysis on the chemical, thermal and rheological properties of pitch.

Pitch-based carbon fibers are of considerable interest as high-performance materials. There are reports over the last several decades detailing (i) methods of improving pitch-based carbon fiber performance, and (ii) reducing the cost of production via novel processing techniques. However, there remain considerable challenges in producing high-performance pitch-based carbon fibers consistently on an industrial scale. This is arguably due to the difficulty of scaling the melt-spinning process to compensate for variability in pitch feedstock quality and a lack of understanding of processing-structure-performance relationships. This work focuses on the early stages of heat treatment (pyrolysis) of isotropic pitch and its effect on the chemical, thermal, and rheological properties of the pitch, which help determine its processability. More specifically, we quantify significant changes in chemical structure, Mw, Tg, Ts, and shear and extensional rheology as a function of pyrolysis time at 400 °C. The extensional rheology, in particular, shows that the 'stretchability' of the pitch samples strongly depends on pyrolysis severity, and is important for characterizing 'drawability'. Using a novel analysis of the uniaxial stretching kinematics, we show an isothermal 'drawability window' that allows for the largest axial and radial Hencky strains at constant rate. We hypothesize that this extensional drawability window could facilitate the successful processing of pitch into high quality fiber, minimizing the trial-and-error approach currently used in the field.

The Effects of Magnetic Field Alignment on Lithium Ion Transport in a Polymer Electrolyte Membrane with Lamellar Morphology.

The transport properties of block copolymer-derived polymer electrolyte membranes (PEMs) are sensitive to microstructural disorder originating in the randomly oriented microdomains produced during uncontrolled self-assembly by microphase separation. This microstructural disorder can negatively impact performance due to the presence of conductivity-impeding grain boundaries and the resulting tortuosity of transport pathways. We use magnetic fields to control the orientational order of Li-doped lamellar polyethylene oxide (PEO) microdomains in a liquid crystalline diblock copolymer over large length scales (>3 mm). Microdomain alignment results in an increase in the conductivity of the membrane, but the improvement relative to non-aligned samples is modest, and limited to roughly 50% in the best cases. This limited increase is in stark contrast to the order of magnitude improvement observed for magnetically aligned cylindrical microdomains of PEO. Further, the temperature dependence of the conductivity of lamellar microdomains is seemingly insensitive to the order-disorder phase transition, again in marked contrast to the behavior of cylinder-forming materials. The data are confronted with theoretical predictions of the microstructural model developed by Sax and Ottino. The disparity between the conductivity enhancements obtained by domain alignment of cylindrical and lamellar systems is rationalized in terms of the comparative ease of percolation due to the intersection of randomly oriented lamellar domains (2D sheets) versus the quasi-1D cylindrical domains. These results have important implications for the development of methods to maximize PEM conductivity in electrochemical devices, including batteries.

Tuning the permselectivity of polymeric desalination membranes via control of polymer crystallite size.

Membrane desalination is a leading technology for treating saline waters to augment fresh water supply. The need for high-performance desalination membranes, particularly with high water/salt selectivity, has stimulated research into the fundamental structure-property-performance relationship of state-of-the-art membranes. In this study, we utilize a facile method for tuning properties of a polymeric desalination membrane to shed light on water and salt transport mechanisms of such membranes. A desalination membrane made of cellulose triacetate is treated in a plasticizer solution, followed by water rinsing. The modified membranes exhibit reduced salt flux without compromising water flux, indicating enhanced water/salt selectivity. An inspection of material characteristics using a model film system reveals a plasticizing-extracting process in changing the polymeric structure, which leads to the reduction of crystallite size in the polymer matrix, consequently affecting the transport properties of the membranes. Our findings highlight the potential of the plasticizing-extracting process in fabricating membranes with desired desalination performance.

Flat Drops, Elastic Sheets, and Microcapsules by Interfacial Assembly of a Bacterial Biofilm Protein, BslA.

Protein adsorption and assembly at interfaces provide a potentially versatile route to create useful constructs for fluid compartmentalization. In this context, we consider the interfacial assembly of a bacterial biofilm protein, BslA, at air-water and oil-water interfaces. Densely packed, high modulus monolayers form at air-water interfaces, leading to the formation of flattened sessile water drops. BslA forms elastic sheets at oil-water interfaces, leading to the production of stable monodisperse oil-in-water microcapsules. By contrast, water-in-oil microcapsules are unstable but display arrested rather than full coalescence on contact. The disparity in stability likely originates from a low areal density of BslA hydrophobic caps on the exterior surface of water-in-oil microcapsules, relative to the inverse case. In direct analogy with small molecule surfactants, the lack of stability of individual water-in-oil microcapsules is consistent with the large value of the hydrophilic-lipophilic balance (HLB number) calculated based on the BslA crystal structure. The occurrence of arrested coalescence indicates that the surface activity of BslA is similar to that of colloidal particles that produce Pickering emulsions, with the stability of partially coalesced structures ensured by interfacial jamming. Micropipette aspiration and flow in tapered capillaries experiments reveal intriguing reversible and nonreversible modes of mechanical deformation, respectively. The mechanical robustness of the microcapsules and the ability to engineer their shape and to design highly specific binding responses through protein engineering suggest that these microcapsules may be useful for biomedical applications.

Controlling orientational order in block copolymers using low-intensity magnetic fields.

The interaction of fields with condensed matter during phase transitions produces a rich variety of physical phenomena. Self-assembly of liquid crystalline block copolymers (LC BCPs) in the presence of a magnetic field, for example, can result in highly oriented microstructures due to the LC BCP's anisotropic magnetic susceptibility. We show that such oriented mesophases can be produced using low-intensity fields (<0.5 T) that are accessible using permanent magnets, in contrast to the high fields (>4 T) and superconducting magnets required to date. Low-intensity field alignment is enabled by the addition of labile mesogens that coassemble with the system's nematic and smectic A mesophases. The alignment saturation field strength and alignment kinetics have pronounced dependences on the free mesogen concentration. Highly aligned states with orientation distribution coefficients close to unity were obtained at fields as small as 0.2 T. This remarkable field response originates in an enhancement of alignment kinetics due to a reduction in viscosity, and increased magnetostatic energy due to increases in grain size, in the presence of labile mesogens. These developments provide routes for controlling structural order in BCPs, including the possibility of producing nontrivial textures and patterns of alignment by locally screening fields using magnetic nanoparticles.

Strong Orientational Coupling of Block Copolymer Microdomains to Smectic Layering Revealed by Magnetic Field Alignment.

We elucidate the roles of the isotropic-nematic (I-N) and nematic-smectic A (N-SmA) transitions in the magnetic field directed self-assembly of a liquid crystalline block copolymer (BCP), using in situ X-ray scattering. Cooling into the nematic from the disordered melt yields poorly ordered and weakly aligned BCP microdomains. Continued cooling into the SmA, however, results in an abrupt increase in BCP orientational order with microdomain alignment tightly coupled to the translational order parameter of the smectic layers. These results underscore the significance of the N-SmA transition in generating highly aligned states under magnetic fields in these hierarchically ordered materials.

NANOPARTICLES. Production of amorphous nanoparticles by supersonic spray-drying with a microfluidic nebulator.

Amorphous nanoparticles (a-NPs) have physicochemical properties distinctly different from those of the corresponding bulk crystals; for example, their solubility is much higher. However, many materials have a high propensity to crystallize and are difficult to formulate in an amorphous structure without stabilizers. We fabricated a microfluidic nebulator that can produce amorphous NPs from a wide range of materials, even including pure table salt (NaCl). By using supersonic air flow, the nebulator produces drops that are so small that they dry before crystal nuclei can form. The small size of the resulting spray-dried a-NPs limits the probability of crystal nucleation in any given particle during storage. The kinetic stability of the a-NPs­on the order of months­is advantageous for hydrophobic drug molecules.

Shear-accelerated crystallization in a supercooled atomic liquid.

A bulk metallic glass forming alloy is subjected to shear flow in its supercooled state by compression of a short rod to produce a flat disk. The resulting material exhibits enhanced crystallization kinetics during isothermal annealing as reflected in the decrease of the crystallization time relative to the nondeformed case. The transition from quiescent to shear-accelerated crystallization is linked to strain accumulated during shear flow above a critical shear rate γ̇(c)≈0.3 s(-1) which corresponds to Péclet number, Pe∼O(1). The observation of shear-accelerated crystallization in an atomic system at modest shear rates is uncommon. It is made possible here by the substantial viscosity of the supercooled liquid which increases strongly with temperature in the approach to the glass transition. We may therefore anticipate the encounter of nontrivial shear-related effects during thermoplastic deformation of similar systems.

Nanoimprinting sub-100 nm features in a photovoltaic nanocomposite using durable bulk metallic glass molds.

The use of bulk metallic glass (BMG) for the nanoimprint of high-aspect-ratio (>3) features into functional polymers is investigated. To accomplish this, the most critical aspect is the successful demolding of the imprinted polymer. By fluorosilane functionalization of the BMG surface and optimization of processing temperature, high aspect pore features down to 45 nm diameters are introduced into the surface of two organic photovoltaic systems: poly(3-hexylthiophene-2,5-diyl) (P3HT) and 1:1 mixtures of P3HT with Phenyl-C61-butyric acid methyl ester (PCBM). The crystallinity of P3HT demands higher forming temperatures and pressures that are difficult to obtain with conventional soft nanoimprint lithography molds. The ability to accommodate a wide range of processing conditions and the low cost of fabricating molds with nanometer-scale features point to the large potential of nanotextured BMGs as an economical and scalable imprint material for high-resolution applications.

Magnetic Alignment of Block Copolymer Microdomains by Intrinsic Chain Anisotropy.

We examine the role of intrinsic chain susceptibility anisotropy in magnetic field directed self-assembly of a block copolymer using in situ x-ray scattering. Alignment of a lamellar mesophase is observed on cooling across the disorder-order transition with the resulting orientational order inversely proportional to the cooling rate. We discuss the origin of the susceptibility anisotropy, Δχ, that drives alignment and calculate its magnitude using coarse-grained molecular dynamics to sample conformations of surface-tethered chains, finding Δχ≈2×10^{-8}. From field-dependent scattering data, we estimate that grains of ≈1.2 µm are present during alignment. These results demonstrate that intrinsic anisotropy is sufficient to support strong field-induced mesophase alignment and suggest a versatile strategy for field control of orientational order in block copolymers.

Thermally switchable aligned nanopores by magnetic-field directed self-assembly of block copolymers.

A scalable approach for developing large area polymer films, with stimuli responsive vertically aligned nanopores is reported. Magnetic fields are used to create highly aligned hexagonally packed block copolymer cylindrical microdomains with order parameters exceeding 0.95. Selective etch removal of material yields nanoporous films which demonstrate reversible pore closure on heating.

Directed self-assembly of block copolymers: a tutorial review of strategies for enabling nanotechnology with soft matter.

Self-assembly of soft materials is broadly considered an attractive means of generating nanoscale structures and patterns over large areas. However, the spontaneous formation of equilibrium nanostructures in response to temperature and concentration changes, for example, must be guided to yield the long-range order and orientation required for utility in a given scenario. In this review we examine directed self-assembly (DSA) of block copolymers (BCPs) as canonical examples of nanostructured soft matter systems which are additionally compelling for creating functional materials and devices. We survey well established and newly emerging DSA methods from a tutorial perspective. Special emphasis is given to exploring underlying physical phenomena, identifying prototypical BCPs that are compatible with different DSA techniques, describing experimental methods and highlighting the attractive functional properties of block copolymers overall. Finally we offer a brief perspective on some unresolved issues and future opportunities in this field.

Molecular Design of Liquid Crystalline Brush-Like Block Copolymers for Magnetic Field Directed Self-Assembly: A Platform for Functional Materials.

We report on the development of a liquid crystalline block copolymer with brush-type architecture as a platform for creating functional materials by magnetic-field-directed self-assembly. Ring-opening metathesis of n-alkyloxy cyanobiphenyl and polylactide (PLA) functionalized norbornene monomers provides efficient polymerization yielding low polydispersity block copolymers. The mesogenic species, spacer length, monomer functionality, brush-chain length, and overall molecular weight were chosen and optimized to produce hexagonally packed cylindrical PLA domains which self-assemble and align parallel to an applied magnetic field. The PLA domains can be selectively removed by hydrolytic degradation resulting in the production of nanoporous films. The polymers described here provide a versatile platform for scalable fabrication of aligned nanoporous materials and other functional materials based on such templates.

Monoliths of semiconducting block copolymers by magnetic alignment.

Achieving highly ordered and aligned assemblies of organic semiconductors is a persistent challenge for improving the performance of organic electronics. This is an acute problem in macromolecular systems where slow kinetics and long-range disorder prevail, thus making the fabrication of high-performance large-area semiconducting polymer films a nontrivial venture. Here, we demonstrate that the anisotropic nature of semiconducting chromophores can be effectively leveraged to yield hierarchically ordered materials that can be readily macroscopically aligned. An n-type mesogen was synthesized based on a perylene diimide (PDI) rigid core coupled to an imidazole headgroup via an alkyl spacer. Supramolecular assembly between the imidazole and acrylic acid units on a poly(styrene-b-acrylic acid) block copolymer yielded self-assembled hexagonally ordered polystyrene cylinders within a smectic A mesophase of the PDI mesogen and poly(acrylic acid). We show that magnetic fields can be used to control the alignment of the PDI species and the block copolymer superstructure concurrently in a facile manner during cooling from a high-temperature disordered state. The resulting materials are monoliths, with a single well-defined orientation of the semiconducting chromophore and block copolymer microdomains throughout the sample. This synergistic introduction of both functional properties and the means of controlling alignment by supramolecular attachment of mesogenic species to polymer backbones offer new possibilities for the modular design of functional nanostructured materials.

Order-disorder transition and alignment dynamics of a block copolymer under high magnetic fields by in situ x-ray scattering.

We examine the influence of magnetic fields on the order-disorder transition (ODT) in a liquid crystalline block copolymer. This is motivated by a desire to understand the dynamics of microstructure alignment during field annealing as potentially dictated by selective destabilization of nonaligned material. Temperature resolved scattering across the ODT and time-resolved measurements during isothermal field annealing at sub-ODT temperatures were performed in situ. Strongly textured mesophases resulted in each case but no measurable field-induced shift in T(ODT) was observed. This suggests that selective melting does not play a discernable role in the system's field response. Our data indicate instead that alignment occurs by slow grain rotation within the mesophase. We identify an optimum subcooling that maximizes alignment during isothermal field annealing. This is corroborated by a simple model incorporating the competing effects of an exponentially decreasing mobility and divergent, increasing magnetic anisotropy on cooling below T(ODT). The absence of measurable field effects on T(ODT) is consistent with estimates based on the relative magnitudes of the field interaction energy and the enthalpy associated with the ODT.

Magnetic Field Alignment of a Diblock Copolymer Using a Supramolecular Route.

Large-area uniform magnetic alignment of a self-assembled diblock copolymer has been achieved by the selective sequestration of rigid moieties with anisotropic diamagnetic susceptibility within one block of the system. The species is based on a biphenyl core and is confined in the acrylic acid domains of a poly(styrene-b-acrylic acid) block copolymer by hydrogen bonding between an imidazole headgroup and the acrylic acid units. Microphase separation produces hierarchically ordered systems of smectic layers within lamellae and smectic layers in the matrix surrounding hexagonally packed poly(styrene) cylinders, as a function of imidazole/acrylic acid stoichiometry. The magnetic field aligns the smectic layers as well as the block copolymer superstructure in a manner dependent on the anchoring condition of the biphenyl species at the block copolymer interface. Surprisingly, this is found to depend on the composition of the system. This approach is synergistic with recent efforts to engineer functional supramolecular block copolymer assemblies based on rigid chromophores. It offers a facile route to large area control of microstructure as required for full exploitation of functional properties in these systems.

Side-chain liquid crystalline polymer networks: exploiting nanoscale smectic polymorphism to design shape-memory polymers.

Herein, we investigate the influence of nanoscale smectic polymorphism within end-on fixed side-chain liquid crystalline polymer networks (SCLCNs) on macroscopic shape-memory and actuation properties. We have synthesized a series of SCLC-type linear (TP-n) and cross-linked random terpolymers (XL-TP-n) with varying length of flexible methylene spacers (n = 5, 10, and 15) between polynorbornene main-chain and cholesteryl ester side-chains. Thermal and mechanical analyses by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) confirm a glass transition (T(g)), a clearing temperature (T(cl)), and a network structure in the XL-TP-n. Detailed structural investigation conducted using wide-angle and small-angle X-ray scattering (WAXS and SAXS) at room temperature proves self-assembled smectic A (SmA) polymorphism of the XL-TP-n which evolves from non-interdigitated bilayer (SmA(2)) for n = 5 to mixed layers of monolayer-like highly interdigitated layer (SmA(1)) and SmA(2) for n = 10 and to SmA(1) for n = 15. In addition, TP10 at temperatures above 60 °C interestingly shows transformation of SmA structure from mixed layer (SmA(1) + SmA(2)) to interdigitated structure (SmA(d)). The SmA polymorphism developed in TP-n during shape-memory cycles (SMCs) significantly impacts the ultimate strain responses. A mechanism for the unique interdigitation-based thermostrictive behavior is proposed. More importantly, this new actuation mechanism observed in these XL-TP-n can be exploited to develop intelligent thermal actuators.

Anisotropic ionic conductivity in block copolymer membranes by magnetic field alignment.

The self-assembly of diblock copolymers provides a convenient route to the formation of mechanically robust films with precise and tunable periodic arrangements of two physically demixed but chemically linked polymeric materials. Chemoselective transport membranes may be realized from such films by selective partitioning of an active species into one of the polymer domains. Here, lithium ions were selectively sequestered within the poly(ethylene oxide) block of a liquid crystalline diblock copolymer to form polymer electrolyte membranes. Optimization of the membrane conductivity mandates alignment of self-assembled structures such that conduction occurs via direct as opposed to tortuous transport between exterior surfaces. We show here that magnetic fields can be used in a very simple and scalable manner to produce highly aligned hexagonally packed cylindrical microdomains in such membranes over macroscopic areas. We systematically explore the dependence of the ionic conductivity of the membrane on both temperature and magnetic field strength. A surprising order of magnitude increase in conductivity relative to the nonaligned case is found in films aligned at the highest magnetic field strengths, 6 T. The conductivity of field aligned samples shows a nonmonotonic dependence on temperature, with a marked decrease on heating in the proximity of the order-disorder transition of the system before increasing again at elevated temperatures. The data suggest that domain-confined transport in hexagonally packed cylindrical systems differs markedly in anisotropy by comparison with lamellar systems.