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At least 919 records · Page 51

Synthesis of Flexible Polyamide Aerogels Cross-Linked with a Tri-Isocyanate

A new series of flexible polyamide (PA) aerogels was synthesized using terephthaloyl chloride (TPC), 2,2′-dimethylbenzidine (DMBZ) and cross-linked with an inexpensive, commercially available tri-isocyanate (Desmodur N3300A) at polymer concentrations of 6–8 wt.% total solids and repeating units, n, from 30 to 60. The cross-linked DMBZ-based polyamide aerogels obtained, after supercritically drying using liquid CO 2 , had shrinkages of 19–27% with densities ranging from 0.12 g/cm 3 to 0.22 g/cm 3 , porosity and surface areas up to 91% and 309 m 2 /g, respectively, and modulus values ranging from 20.6 to 109 MPa. Evidence suggests that a higher flexibility could be achieved using DMBZ in the polyamide backbone with N3300A as a cross-linker, when compared to previously reported TPC-mPDA-BTC PA aerogels, N3300A-polyimide aerogels, and N3300-reinforced silica aerogels.

aerogels↗

Biogenic Straw Aerogel Thermal Insulation Materials

Biogenic wheat straw is a carbon-storing building insulation material. However, the enzymatic hydrolysis ratio of its cellulose is relatively low due to the presence of hemicellulose and lignin hindering its thermal insulation performance. In this work, we report aerogel and straw composites with thermal conductivity of 35 mW m –1 K –1 , while high cellulose fiber conversion in straw is obtained by using a hybrid mechanical and chemical process. Furthermore, we show that the in-situ cellulose-reinforced silica aerogel nanocomposites exhibit an optimal thermal conductivity of 32 mW m –1 K –1 by using 50 wt% of aerogel. Moreover, the hydrophobic aerogel-cellulose composites show a low density, high porosity (90 %), high compression modulus (1.9 MPa), superhydrophobicity, and superior reusability. This work provides a cost-effective and facile method to manufacture biogenic composites from agriculture waste materials, promising for carbon-sequestration building insulation applications.

36 MATERIALS SCIENCE↗

Effect of Zn Addition on Phase Evolution in AlCrFeCoNiZn High–Entropy Alloy

The addition of Zn to AlCrFeCoNi high-entropy alloy (HEA) poses intriguing questions as to how it would affect phase evolution. Herein, the phase evolution in AlCrFeCoNiZn is studied using a combination of experimental techniques (X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, and differential scanning calorimetry) and computational (density-functional theory [DFT], calculation of phase diagrams, and machine-learning) methods. Mechanically alloyed and spark-plasma-sintered AlCrFeCoNiZn assumes a metastable single-phase, body-centered-cubic (BCC) structure that undergoes diffusion-controlled phase separation upon subsequent heat treatment to form separate (Al, Cr)-rich, (Fe, Co)-rich, and (Zn, Ni)-rich phases. The formation of (Al, Cr)-rich phase, not reported previously in AlCrFeCoNi-based HEAs, is attributed to strong clustering tendency of Cr–Zn and Cr–Ni pairs, combined with the strong ordering of Zn–Ni pair, driving out Cr that in turn combines with Al to form a (Al, Cr)-rich phase. In the DFT results, the formation of thermodynamically stable L1 2 phase is shown wherein Cr–Fe–Zn [Al–Ni-Co] preferably occupy1a (000) [3c (0 ½ ½)] positions. Furthermore, the sluggish diffusional transformation to L1 2 phase from BCC precursors is attributed to the small stacking-fault energy of AlCrFeCoNiZn. The equilibrated HEA exhibits a high microhardness of 8.24 GPa with an elastic modulus of 184 GPa.

36 MATERIALS SCIENCE↗

Tacky Elastomers to Enable Tear-Resistant and Autonomous Self-Healing Semiconductor Composites

Mechanical failure of π-conjugated polymer thin films is unavoidable under cyclic loading conditions, due to intrinsic defects and poor resistance to crack propagation. Here, the first tear-resistant and room-temperature self-healable semiconducting composite is presented, consisting of conjugated polymers and butyl rubber elastomers. This new composite displays both a record-low elastic modulus (<1 MPa) and ultrahigh deformability with fracture strain above 800%. More importantly, failure behavior is not sensitive to precut notches under deformation. Autonomous self-healing at room temperature, both mechanical and electronic, is demonstrated through the physical contact of two separate films. The composite film also shows device stability in the ambient environment over 5 months due to much-improved barrier property to both oxygen and water. Butyl rubber is broadly applicable to various p-type and n-type semiconducting polymers for fabricating self-healable electronics to provide new resilient electronics that mimic the tear resistance and healable property of human skin.

36 MATERIALS SCIENCE↗

Autonomous Self-Healing Elastomers with Unprecedented Adhesion Force

Self-healable elastomers are extremely attractive due to their ability to prolong product lifetime. An additional function that could further expand their applications is strong adhesion force to clean and dusty surfaces. This study reports a series of autonomous self-healable and highly adhesive elastomers (ASHA-Elastomer) that are fabricated via a simple, efficient, and scalable process. The obtained elastomers exhibit outstanding mechanical properties with elongation at break up to 2102% and toughness (modulus of toughness) of 1.73 MJ m -3 . The damaged ASHA-Elastomer can autonomously self-heal with full recovery of functionalities, and the healing process is not affected by the presence of water. The elastomers are found to possess an ultrahigh adhesion force up to 3488 N m -1 , greatly outperforming previously reported self-healing adhesive elastomers. Furthermore, the adhesion force of the ASHA-Elastomer is negligibly affected by dust on the surface, in stark contrast with regular adhesive polymers that have adhesion strengths extremely sensitive to dust. The successful development of high-toughness, autonomous self-healable, and ultra-adhesive elastomers will enable a wide range of applications with enhanced longevity and versatility, including their use in sealants, adhesives, and stretchable devices.

36 MATERIALS SCIENCE↗

Metal–Ligand Based Mechanophores Enhance Both Mechanical Robustness and Electronic Performance of Polymer Semiconductors

The backbone of diketopyrrolopyrrole-thiophene-vinylene-thiophene-based polymer semiconductors (PSCs) is modified with pyridine (Py) or bipyridine ligands to complex Fe(II) metal centers, allowing the metal–ligand complexes to act as mechanophores and dynamically crosslink the polymer chains. Here, mono- and bi-dentate ligands are observed to exhibit different degrees of bond strengths, which subsequently affect the mechanical properties of these Wolf-type-II metallopolymers. The counter ion also plays a crucial role, as it is observed that Py-Fe mechanophores with non-coordinating BPh 4 – counter ions (Py-FeB) exhibit better thin film ductility with lower elastic modulus, as compared to the coordinating chloro ligands (Py-FeC). Interestingly, besides mechanical robustness, the electrical charge carrier mobility can also be enhanced concurrently when incorporating Py-FeB mechanophores in PSCs. This is a unique observation among stretchable PSCs, especially that most reports to date describe a decreased mobility when the stretchability is improved. Next, it is determined that improvements to both mobility and stretchability are correlated to the solid-state molecular ordering and dynamics of coordination bonds under strain, as elucidated via techniques of grazing-incidence X-ray diffraction and X-ray absorption spectroscopy techniques, respectively. This study provides a viable approach to enhance both the mechanical and the electronic performance of polymer-based soft devices.

36 MATERIALS SCIENCE↗

Shape Persistent, Highly Conductive Ionogels from Ionic Liquids Reinforced with Cellulose Nanocrystal Network

Abstract Shape‐persistent, conductive ionogels where both mechanical strength and ionic conductivity are enhanced are developed using multiphase materials composed of cellulose nanocrystals and hyperbranched polymeric ionic liquids (PILs) as a mechanically strong supporting network matrix for ionic liquids with an interrupted ion‐conducting pathway. The integration of needlelike nanocrystals and PIL promotes the formation of multiple hydrogen bonding and electrostatic ionic interaction capacitance, resulting in the formation of interconnected networks capable of confining a high amount of ionic liquid (≈95 wt%) without losing its self‐sustained shape. The resulting nanoporous and robust ionogels possess outstanding mechanical strength with a high compressive elastic modulus (≈5.6 MPa), comparable to that of tough, rubbery materials. Surprisingly, these rigid materials preserve the high ionic conductivity of original ionic liquids (≈7.8 mS cm −1 ), which are distributed within and supported by the nanocrystal network‐like rigid frame. On the one hand, such stable materials possess superior ionic conductivities in comparison to traditional solid electrolytes; on the other hand, the high compression resistance and shape‐persistence allow for easy handling in comparison to traditional fluidic electrolytes. The synergistic enhancement in ion transport and solid‐like mechanical properties afforded by these ionogel materials make them intriguing candidates for sustainable electrodeless energy storage and harvesting matrices.

Lee, Hansol↗

Photo-Curing 3D Printing of Thermosetting Sacrificial Tooling for Fabricating Fiber-Reinforced Hollow Composites

Carbon fiber-reinforced hollow composites play a vital role in lightweighting modern cars and aircrafts. Fabrication of such hollow composites with seamless internal finish requires sacrificial tooling that can be used under pressure and high temperature. For the very first time, high performance sacrificial tooling that can be used to fabricate fiber-reinforced hollow composites is produced using photocuring 3D printing technology. This is achieved by developing UV-curable resins containing highly soluble yet hydrolysable acetal acrylate cross-linker and hydrophilic 4-acryloylmorpholine monomer. It is found that the cross-linker content greatly affects the printing speed. Further, the widely adopted UV post-curing method is found to have negligible impact on improving the thermal-mechanical properties of printed structures. Additionally, after thermal post-treatment, printed sacrificial tooling exhibits a heat deflection temperature of 112 °C at 0.455 MPa and an average coefficient of linear thermal expansion of 59 ppm °C -1 between 30 and 100 °C. As a result, printed tooling enables fabrication of carbon fiber-reinforced hollow composites with complex geometry, which shows a tensile strength of 802 MPa and an elastic modulus of 50.2 GPa.

36 MATERIALS SCIENCE↗

Stretchable and Self‐Healable Semiconductive Composites Based on Hydrogen Bonding Cross‐linked Elastomeric Matrix

Abstract Semiconductors with both high stretchability and self‐healing capability are highly desirable for various wearable devices. Much progress has been achieved in designing highly stretchable semiconductive polymers or composites. The demonstration of self‐healable semiconductive composite is still rare. Here, an extremely soft, highly stretchable, and self‐healable hydrogen bonding cross‐linked elastomer, amide functionalized‐polyisobutylene (PIB‐amide) is developed, to enable a self‐healable semiconductive composite through compounding with a high‐performance conjugated diketopyrrolopyrrole (DPP‐T) polymer. The composite, consisting of 20% DPP‐T and 80% PIB‐amide, shows record high crack‐onset strain (COS ≈1500%), extremely low elastic modulus (E≈1.6 MPa), and unique ability to spontaneously self‐heal atroom temperature within 5 min. Unlike previous works, these unique composite materials also show strain‐independent charge mobility. An in‐depth morphological study based on multi‐model techniques indicate that all composites show blending ratio‐ and stretching‐independent fibril‐like aggregation due to the strong hydrogen bond in elastomer to enable the unique stable charge mobility. This study provides a new direction to develop highly healable and electronically stable semiconductive composite and will enable new applications of stretchable electronics.

Chemistry↗

Highly Deformable Rigid Glassy Conjugated Polymeric Thin Films

Wearable devices benefit from the use of stretchable conjugated polymers (CPs). Traditionally, the design of stretchable CPs is based on the assumption that a low elastic modulus (E) is crucial for achieving high stretchability. However, this research, which analyzes the mechanical properties of 65 CP thin films, challenges this notion. It is discovered that softness alone does not determine stretchability; rather, it is the degree of entanglement that is critical. This means that rigid CPs can also exhibit high stretchability, contradicting conventional wisdom. To inverstigate further, the mechanical behavior, electrical properties, and deformation mechanism of two model CPs: a glassy poly(3-butylthiophene-2,5-diyl) (P3BT) with an E of 2.2 GPa and a viscoelastic poly(3-octylthiophene-2,5-diyl) (P3OT) with an E of 86 MPa, are studied. Ex situ transmission X-ray scattering and polarized UV–vis spectroscopy revealed that only the initial strain (i.e., <20%) exhibits different chain alignment mechanisms between two polymers, while both rigid and soft P3ATs showed similarly behavior at larger strains. In conclusion, by challenging the conventional design metric of low E for high stretchability and highlighting the importance of entanglement, it is hoped to broaden the range of CPs available for use in wearable devices.

36 MATERIALS SCIENCE↗

High‐Pressure Synthesis of Ultra‐Incompressible, Hard and Superconducting Tungsten Nitrides

Abstract Transition metal nitrides, particularly those of 5 d metals, are known for their outstanding properties, often relevant for industrial applications. Among these metal elements, tungsten is especially attractive given its low cost. In this high‐pressure investigation of the W–N system, two novel ultra‐incompressible tungsten nitride superconductors, namely W 2 N 3 and W 3 N 5 , are successfully synthesized at 35 and 56 GPa, respectively, through a direct reaction between N 2 and W in laser‐heated diamond anvil cells. Their crystal structure is determined using synchrotron single‐crystal X‐ray diffraction. While the W 2 N 3 solid's sole constituting nitrogen species are N 3‐ units, W 3 N 5 features both discrete N 3‐ as well as N 2 4‐ pernitride anions. The bulk modulus of W 2 N 3 and W 3 N 5 is experimentally determined to be 380(3) and 406(7) GPa, and their ultra‐incompressible behavior is rationalized by their constituting WN 7 polyhedra and their linkages. Importantly, both W 2 N 3 and W 3 N 5 are recoverable to ambient conditions and stable in air. Density functional theory calculations reveal W 2 N 3 and W 3 N 5 to have a Vickers hardness of 30 and 34 GPa, and superconducting transition temperatures at ambient pressure (50 GPa) of 11.6 K (9.8 K) and 9.4 K (7.2 K), respectively. Additionally, transport measurements performed at 50 GPa on W 2 N 3 corroborate with the calculations.

Chemistry↗

Thermoplastic Elastomers and Their Physical Gels Electrospun into Tunable Microfibrous Nonwoven Mats: Structure Formation and Property Enhancement

Abstract Thermoplastic elastomers (TPEs) based on styrenic block copolymers constitute excellent examples of self‐networking macromolecules that are employed in a wide range of contemporary technologies as molded parts. In such applications, these TPEs exist as dense (nonporous) films or other shapes. Here, it is first demonstrated that a series of commercial TPEs possessing comparable compositions can be electrospun from solution to form microfibers that are arranged into nonwoven mats that are breathable. An important consideration for microfiber formation is the copolymer molecular weight, which regulates i) the viscosity of the parent solution prior to electrospinning, ii) the ability of these copolymers to self‐assemble during electrospinning, iii) the microfiber morphology, and iv) the mechanical properties of the resultant microfibers. The addition of a midblock‐selective aliphatic oil to these TPEs yields thermoplastic elastomer gels (TPEGs), wherein the copolymer morphology and mechanical properties become highly composition‐tunable. Electrospinning TPEGs from a binary oil+solvent solution introduces a micelle inversion mechanism that begins with an oil‐rich micellar core and ends with a styrene‐rich micellar core, required for network stabilization, as the solvent dries during microfiber solidification. This work has implications for the production of controllably low‐modulus microfibrous materials possessing modestly improved toughness but exceptional extensibility and enhanced optical transparency.

Shamsi, Mohammad↗

Mechanically Reinforced Pseudosolid Polyelectrolyte Membranes via Layer-by-Layer Assembly for High-Performing Lithium-Metal Batteries

Ionogels are emerging as high-potential pseudosolid electrolytes for lithium-metal batteries (LMBs), leveraging their intrinsic high ionic conductivity from entrapped ionic liquid (IL) electrolytes. However, their practical application is hindered by poor mechanical strength stemming from the confinement of ILs within a polymer matrix. To address this challenge, the formation of conformal polyion coatings with functional groups is reported to be relevant to LMBs’ application on ionogels, utilizing a layer-by-layer (LbL) assembly strategy. Here, this approach significantly enhances the mechanical strength (Young's modulus and tensile strength) and electrochemical performance of ionogels, owing to the tailored interface modifications introduced by functional groups’ specific conformal polyion coatings. The core of this methodology leverages the inherent ionic structure of ionogels to enable facile interface modification through Coulombic interactions between polyanions and polycations. These conformally coated interface functionalized membranes show improved electrochemical performance when integrated with cathode materials such as LiFePO 4 (LFP) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) in an LMB configuration, underscoring their potential for robust, high-conductivity, pseudosolid membranes for LMB applications. These innovative pseudosolid membranes offer improved mechanical and electrochemical properties, leading to higher battery efficiency and safety, making them promising candidates for next-generation LMB technology.

25 ENERGY STORAGE↗