Accurate additive manufacturing of lightweight and elastic carbons using plastic precursors.

Despite groundbreaking advances in the additive manufacturing of polymers, metals, and ceramics, scaled and accurate production of structured carbons remains largely underdeveloped. This work reports a simple method to produce complex carbon materials with very low dimensional shrinkage from printed to carbonized state (less than 4%), using commercially available polypropylene precursors and a fused filament fabrication-based process. The control of macrostructural retention is enabled by the inclusion of fiber fillers regardless of the crosslinking degree of the polypropylene matrix, providing a significant advantage to directly control the density, porosity, and mechanical properties of 3D printed carbons. Using the same printed plastic precursors, different mechanical responses of derived carbons can be obtained, notably from stiff to highly compressible. This report harnesses the power of additive manufacturing for producing carbons with accurately controlled structure and properties, while enabling great opportunities for various applications.

Mechanically Strong, Freeze-Resistant, and Ionically Conductive Organohydrogels for Flexible Strain Sensors and Batteries.

Conductive hydrogels as promising material candidates for soft electronics have been rapidly developed in recent years. However, the low ionic conductivity, limited mechanical properties, and insufficient freeze-resistance greatly limit their applications for flexible and wearable electronics. Herein, aramid nanofiber (ANF)-reinforced poly(vinyl alcohol) (PVA) organohydrogels containing dimethyl sulfoxide (DMSO)/H2 O mixed solvents with outstanding freeze-resistance are fabricated through solution casting and 3D printing methods. The organohydrogels show both high tensile strength and toughness due to the synergistic effect of ANFs and DMSO in the system, which promotes PVA crystallization and intermolecular hydrogen bonding interactions between PVA molecules as well as ANFs and PVA, confirmed by a suite of characterization and molecular dynamics simulations. The organohydrogels also exhibit ultrahigh ionic conductivity, ranging from 1.1 to 34.3 S m-1 at -50 to 60 °C. Building on these excellent material properties, the organohydrogel-based strain sensors and solid-state zinc-air batteries (ZABs) are fabricated, which have a broad working temperature range. Particularly, the ZABs not only exhibit high specific capacity (262 mAh g-1 ) with ultra-long cycling life (355 cycles, 118 h) even at -30 °C, but also can work properly under various deformation states, manifesting their great potential applications in soft robotics and wearable electronics.

Fibrous Aerogels for Solar Vapor Generation.

Solar-driven vapor generation is emerging as an eco-friendly and cost-effective water treatment technology for harvesting solar energy. Aerogels are solid materials with desirable high-performance properties, including low density, low thermal conductivity, and high porosity with a large internal surface, which exhibit outstanding performance in the area of solar vapor generation. Using fibers as building blocks in aerogels could achieve unexpected performance in solar vapor generation due to their entangled fibrous network and high surface area. In this review, based on the fusion of the one-dimensional fibers and three-dimensional porous aerogels, we discuss recent development in fibrous aerogels for solar vapor generation based on building blocks synthesis, photothermal materials selection, pore structures construction and device design. Thermal management and water management of fibrous aerogels are also evaluated to improve evaporation performance. Focusing on materials science and engineering, we overview the key challenges and future research opportunities of fibrous aerogels in both fundamental research and practical application of solar vapor generation technology.

Biomass-Derived, Highly Conductive Aqueous Inks for Superior Electromagnetic Interference Shielding, Joule Heating, and Strain Sensing.

Conductive composite inks are widely used in various applications such as flexible electronics. However, grand challenges still remain associated with their relatively low electrical conductivity and require heavy use of organic solvents, which may limit their high performance in broad applications and cause environmental concerns. Here, we report a generalized and eco-friendly strategy to fabricate highly conductive aqueous inks using silver nanowires (AgNWs) and biomass-derived organic salts, including succinic acid-chitosan (SA-chitosan) and sebacic acid-chitosan. SA-chitosan/AgNW composite coatings can be prepared by directly casting conductive aqueous inks on various substrates, followed by subsequently heating for cross-linking. The composite coatings exhibit an ultrahigh electrical conductivity up to 1.4 × 104 S/cm, which are stable after being treated with various organic solvents and/or kept at a high temperature of 150 °C, indicating their high chemical and thermal resistance. The flexibility and performance durability of these composite coatings were demonstrated by a suite of characterization methods, including bending, folding, and adhesion tests. Moreover, a high electromagnetic interference shielding (EMI) effectiveness of 73.3 dB is achieved for SA-chitosan/AgNW composite coatings at a thickness of only 10 µm due to the ultrahigh electrical conductivity. Additionally, we further demonstrated that such conductive composite inks can be used for fabricating functional textiles for a variety of applications with high performance, such as EMI shielding, Joule heating, and strain sensing. The robust and highly conductive inks prepared by this simple and environmental-friendly method hold great promise as important material candidates for the potential large-scale manufacturing of flexible and wearable electronics.

Developing Anisotropy in Self-Assembled Block Copolymers: Methods, Properties, and Applications.

Block copolymers (BCPs) self-assembly has continually attracted interest as a means to provide bottom-up control over nanostructures. While various methods have been demonstrated for efficiently ordering BCP nanodomains, most of them do not generically afford control of nanostructural orientation. For many applications of BCPs, such as energy storage, microelectronics, and separation membranes, alignment of nanodomains is a key requirement for enabling their practical use or enhancing materials performance. This review focuses on summarizing research progress on the development of anisotropy in BCP systems, covering a variety of topics from established aligning techniques, resultant material properties, and the associated applications. Specifically, the significance of aligning nanostructures and the anisotropic properties of BCPs is discussed and highlighted by demonstrating a few promising applications. Finally, the challenges and outlook are presented to further implement aligned BCPs into practical nanotechnological applications, where exciting opportunities exist.

Structure-controlled zwitterionic nanocapsules with thermal-responsiveness.

A facile approach is established to prepare zwitterionic nanocapsules (ZN C s) with controlled diameters and core/shell structures based on an inverse reversible addition-fragmentation transfer (RAFT) miniemulsion interfacial polymerization method. The diameters and core volume fractions of ZNCs can be tuned finely from 61 to 220 nm and from 0.22 to 0.61, respectively. Furthermore, the thermal-responsive property of the prepared zwitterionic nanocapsules was systematically studied relating to core/shell ratios and cross-linking degrees. These ZNCs could be particularly useful in constructing polymeric materials with well-defined nanoporous structures for nano-void membranes, drug delivery devices and catalytic carriers.

Nanovoid Membranes Embedded with Hollow Zwitterionic Nanocapsules for a Superior Desalination Performance.

In order to lower the capital and operational cost of desalination and wastewater treatment processes, nanofiltration (NF) membranes need to have a high water permeation and ionic rejection, while also maintaining a stable performance through antifouling resistance. Recently, Turing-type reaction conditions [ Science 2018, 360, 518-521] and sacrificed metal organic frame (MOF) nanoparticles [ Nat. Commun. 2018, 9, 2004] have been reported to introduce nanovoids into thin-film composite (TFC) polyamide (PA) NF membranes for an improved performance. Herein, we report a one-step fabrication of thin-film nanocomposite membranes (TFNM) with controllable nanovoids in the polyamide layer by introducing hollow zwitterionic nanocapsules (HZNCs) during interfacial polymerization. It was found that embedding HZNCs increases the membrane internal free volume, external surface area, and hydrophilicity, thus enhancing the water permeation and antifouling resistance without trading off the rejection of multivalent ions. For example, water permeation of the NF membranes embedded with about 19.0 wt % of HZNCs (73 L m-2 h-1) increased by 70% relative to the value of the control TFC NF membrane without HZNCs (43 L m-2 h-1). This increase comes while also maintaining 95% rejection of Na2SO4. Further, we also determined the effect of the mass loading of HZNCs on the top surface of the TFC NF membranes on the membrane performance. This work provided a direct and simple route to fabricate advanced desalination membranes with a superior separation performance.

Dynamical Correlations for Statistical Copolymers from High-Throughput Broad-Band Dielectric Spectroscopy.

Broad-band dielectric spectroscopy (BDS) provides a powerful method of characterizing relaxation dynamics in diverse materials. Here we describe and employ a novel instrument for high-throughput broad-band dielectric spectroscopy (HTBDS) that accelerates this capability, enabling simultaneous measurements of 48 samples. This capability is based around a coaxial switching system for rapid scanning between multiple samples on the same sample stage, coordinated with shared environmental control. We validate the instrument by measuring dielectric response in three polymers, distributed across 48 sample sites, and comparing results to measurements via a standard BDS instrument. Results are found to be reproducible and are in agreement with relaxation times from traditional BDS. We then employ HTBDS to establish mixing rules for glass transition temperatures, kinetic fragility indices, and segmental stretching exponents in a series of acrylate copolymers, a matter of considerable technological interest in a variety of technological applications. Results are consistent with the empirical Fox rule for the glass transition temperature Tg averaging in polymer blends, while they reveal a linear mixing rule for kinetic fragility indices. Finally, we test several proposed correlations between these distinct dynamical properties. These results demonstrate that HTBDS enables measurements of polymer relaxation at a throughput approximately 10 times higher than that of standard BDS approaches, opening the door to high-throughput materials design of dynamic response across a broad range of frequencies.

Oxygen sensitive polymeric nanocapsules for optical dissolved oxygen sensors.

Immobilization of the oxygen-sensitive probes (OSPs) in the host matrix greatly impacts the performance and long-term usage of the optical dissolved oxygen (DO) sensors. In this work, fluorescent dyes, as the OSPs, were encapsulated with a crosslinked fluorinated polymer shell by interfacial confined reversible addition fragmentation chain transfer miniemulsion polymerization to fabricate oxygen sensitive polymeric nanocapsules (NCs). The location of fluorescent dyes and the fluorescent properties of the NCs were fully characterized by fourier transform infrared spectrometer, x-ray photoelectron spectrometer and fluorescent spectrum. Dye-encapsulated capacity can be precisely tuned from 0 to 1.3 wt% without self-quenching of the fluorescent dye. The crosslinked fluorinated polymer shell is not only extremely high gas permeability, but also prevents the fluorescent dyes from leakage in aqueous as well as in various organic solvents, such as ethanol, acetone and tetrahydrofuran (THF). An optical DO sensor based on the oxygen sensitive NCs was fabricated, showing high sensitivity, short response time, full reversibility, and long-term operational stability of online monitoring DO. The sensitivity of the optical DO sensor is 7.02 (the ratio of the response value in fully deoxygenated and saturated oxygenated water) in the range 0.96-14.16 mg l-1 and the response time is about 14.3 s. The sensor's work curve was fit well using the modified Stern-Volmer equation by two-site model, and its response values are hardly affected by pH ranging from 2 to 12 and keep constant during continuous measurement for 3 months. It is believed that the oxygen sensitive polymeric NCs-based optical DO sensor could be particularly useful in long-term online DO monitoring in both aqueous and organic solvent systems.

Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties.

Crystal orientation in semi-crystalline polymers tends to enhance their performance, such as increased yield strength and modulus, along the orientation direction. Zone annealing (ZA) orients the crystal lamellae through a sharp temperature gradient that effectively directs the crystal growth, but the sweep rate (VZA) of this gradient significantly impacts the extent of crystal orientation. Here, we demonstrate rotational zone annealing (RZA) as an efficient method to elucidate the influence of VZA on the crystal morphology of thin films in a single experiment using isotactic poly(1-butene), PB-1, as a model semi-crystalline polymer. These RZA results are confirmed using standard, serial linear ZA to tune the structure from an almost unidirectional oriented morphology to weakly oriented spherulites. The overall crystallinity is only modestly changed in comparison to isothermal crystallization (maximum of 55% from ZA vs. 48% for isothermal crystallization). However, the average grain size increases and the spherulites become anisotropic from ZA. Due to these structural changes, the Young's modulus of the oriented films, both parallel and perpendicular to the spherulite orientation direction, is significantly increased by ZA. The modulus does become anisotropic after ZA due to the directionality in the crystal structure, with more than a threefold increase in the modulus parallel to the orientation direction for the highest oriented film in comparison to the modulus from isothermal crystallization. RZA enables rapid identification of conditions to maximize orientation of crystals in thin polymer films, which could find utility in determining conditions to improve crystallinity and performance in organic electronics.

Controlled Directional Crystallization of Oligothiophenes Using Zone Annealing of Preseeded Thin Films.

We demonstrate a simple route to directionally grow crystals of oligothiophenes, based on 2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene with degrees of polymerization of 2 (BTTT-2) and 4 (BTTT-4) via zone annealing (ZA) of preseeded films. ZA of spun-cast films of BTTT-2 does not yield highly aligned crystals. However, if the film is oven-annealed briefly prior to ZA, highly aligned crystals that are millimeters in length can be grown, whose length depends on the velocity of the ZA front. The precrystallized region provides existing nuclei that promote crystal growth and limit nucleation of new crystals in the melted region. Aligned crystals of BTTT-2 can be obtained even when the moving velocity for ZA is an order of magnitude greater than the crystal growth rate. The relative nucleation rate to the crystallization rate for BTTT-4 is greater than that for BTTT-2, which decreases the length over which BTTT-4 can be aligned to ∼500 µm for the conditions examined. The temperature gradient and moving velocity of ZA enable control of the length of the aligned crystalline structure at the macroscale.

Nanoporous block copolymer films using highly selective solvents and non-solvent extraction.

Nanoporous block copolymer thin films are fabricated by selective solvent swelling of the majority phase and subsequent rapid extraction with a miscible non-solvent (water). Selection of the initial solvent provides a facile route to tune the porosity of the films. Poly(butylnorbornene)-block-poly(hydroxyhexafluoroisopropyl norbornene) (BuHFA) is used to generate these porous thin films due to its high Tg (>300 °C) and the selectivity of primary alcohols towards poly(hydroxyhexafluoroisopropyl norbornene) (pHFANB) to enable a relatively environmentally benign process. As the solvent quality for the HFA increases from ethanol to isopropanol to n-butanol, the porosity of the film developed by water extraction increases up to 69%. Aqueous mixtures of ethanol provide an addition handle to tune the porosity between 10 and 54%. These nanoporous films are robust with the porosity nearly unchanged after extended heating at 160 °C. Their elastic moduli are investigated using surface wrinkling and the modulus, E, scales with the film density, ρ, as E ∼ ρ(2.2), which is similar to cellular solids. The nanopores are templated by the self-assembled structure of the block copolymer, so these coatings are transparent despite the high porosity. These thin films act as anti-reflective coatings for glass slides. Spin coating provides a coating on both sides and processing to generate 55% porosity leads to an increase in transmittance from approximately 92% to 99.1% (average for the full range of visible light). A maximum transmittance of 99.8% is found at 523 nm. This methodology is simple and highly tunable; extension to other block copolymer systems is likely possible if sufficient solubility contrast between segments exists.

Impact of Nanostructure on Mechanical Properties of Norbornene-based Block Copolymers under Simulated Operating Conditions for Biobutanol Membranes.

The structure and mechanical properties of a novel block copolymer (BCP) system with T(g)'s for both segments exceeding 300 °C, poly(butylnorbornene)-block-poly(hydroxyhexafluoroisopropyl norbornene) (BuNB-b-HFANB), are investigated as a function of processing conditions used for solvent vapor annealing (SVA). Solvent selection impacts long-range order markedly, but unexpectedly vertical orientation of cylinders are preferred over a wide range of solubility parameters, as determined by atomic force microscopy and grazing incidence small-angle X-ray scattering. The mechanical properties (elastic modulus, fracture strength, and onset fracture strain) are dependent upon the long-range order induced during SVA and determined using the combination of surface wrinkling and cracking. The modulus and fracture strength of the films increase from 1.44 GPa and 12.1 MPa to 1.77 GPa and 17.5 MPa, respectively, whereas the onset fracture strain decreases from 1.6% to approximately 0.6% as the ordering is improved. The polarity difference in the segments of the BCP is attractive for membrane separations, especially butanol-water. For biobutanol recovery, the titers are typically <3 wt % butanol; exposure of the BCP membrane to aqueous 1 wt % butanol decreases the elastic modulus to approximately 0.90 GPa, irrespective of the morphology, despite the high T(g) of both segments and limited swelling (5.0 wt %). Correspondingly, the onset fracture strain of these swollen films is estimated to increase significantly to 6-7%. These results indicate that operating conditions impact the mechanical performance of BCP membranes more than their morphology despite the high T(g) of the neat copolymer. Wrinkling and cracking provide a facile route to test the mechanical properties of membranes under simulated operando conditions.

Bicontinuous mesoporous carbon thin films via an order-order transition.

Bicontinuous mesoporous carbon films are fabricated by cooperative self-assembly of phenolic resin and amphiphilic triblock copolymer via an order-order transition from cylinders to gyroid. The film morphology is strongly influenced by the details of processing, including age of the resol, resol : template ratio, and the solvent vapor annealing process.