Neodymium-Mediated Coordinative Chain Transfer Polymerization of Isoprene in the Presence of External Donors.

Nd-based polydiene elastomers, including NdIR and NdBR, are regarded as indispensable key raw materials in preparing green tires with excellent performance capabilities, but their wide application is still limited by the relative higher cost of Nd precatalysts. Nd-mediated coordinative chain transfer polymerization (CCTP) of diene provides an effective strategy to reduce the precatalyst cost, because this method involves very high atom economy, i.e., each Nd molecule can generate multiple polymer chains. Nevertheless, all possible factors that could influence such CCTP behaviors are still mostly unexplored to date. In this report, the basic chemistry on the influence of external donors on the overall CCTP behaviors of isoprene was established for the first time. It was found that increasing the amount of external donors had a negative influence on the chain transfer efficiencies, resulting in gradually decreasing atom economies. Catalyst addition order studies revealed that the coordination of donors with cationic Nd active species, rather than alkylaluminium CTAs, contributed mostly to such decreased efficiencies. Moreover, it was found that when the ratio of donors and Nd compounds was higher than 1.0, the CCTP behaviors were corrupted, resulting in polymers with broad distributions, as well as resulting in low atom economies; nevertheless, when the ratio was lower than 0.5, the system still displayed CCTP characteristics, implying that the critical ratio for maintaining the CCTP was 0.5. Additionally, when such a ratio was 0.01, the high atom economy was almost the same as donor-free CCTP systems. Detailed kinetic studies at such a ratio demonstrated that the donor-contained system proceeded in a well-controlled manner, as concluded from the good linear relationship between the Mn of the PIps against the polymer yields, as well as the good linearity between the Mn against the (IP)/(Nd) ratios. Such maintained CCTP properties also allowed for seeding two-step polymerizations to prepare diblock copolymers with precisely controlled molecular weights. Expanding the types of donors to more phosphine, oxygen, and nitrogen containing compounds showed that they also affected the CCTP behaviors depending on their steric and electronic properties.

Combination strategy of large interlayer spacing and active basal planes for regulating the microwave absorption performance of MoS2/MWCNT composites at thin absorber level.

Recently, molybdenum disulfide (MoS2)/carbon has become a promising candidate for efficient microwave absorption. However, it is still challenging to simultaneously optimize the synergy of impedance matching and loss capability at the level of a thin absorber. Here, a new adjustment strategy is proposed by changing the concentration of precursor l-cysteine for MoS2/multi-walled carbon nanotubes (MWCNT) composites to unlock the basal plane of MoS2 and expand the interlayer spacing from 0.62 nm to 0.99 nm, leading to improved packing of MoS2 nanosheets and more active sites. Therefore, the tailored MoS2 nanosheets exhibit abundant sulfur-vacancies, lattice-oxygen, more metallic 1T-phase, and higher surface area. Such sulfur-vacancies and lattice-oxygen promote the electronic asymmetric distribution at the solid-air interface of MoS2 crystals and induce stronger microwave attenuation through interface/dipole polarization, which is further verified by first-principles calculations. In addition, the expansion of the interlayer spacing induces more MoS2 to deposit on the MWCNT surface and increases the roughness, improving the impedance matching and multiple scattering. Overall, the advantage of this adjustment method is that while optimizing impedance matching at the thin absorber level, composite still maintains a high attenuation capacity, which means enhancing the attenuation performance of MoS2 itself offsets the weakening of the composite's attenuation ability caused by the decrease in the relative content of MWCNT components. Most importantly, adjusting impedance matching and attenuation ability can be easily implemented by separate control of l-cysteine content. As a result, the MoS2/MWCNT composites achieve a minimum reflection loss value of -49.38 dB and an effective absorption bandwidth of 4.64 GHz at a thickness of only 1.7 mm. This work provides a new vision for the fabrication of thin MoS2-carbon absorbers.

Molecular Dynamic and Dissipative Particle Dynamic Simulation on the Miscibility of NR/CR Blends.

Natural rubber (NR) exhibits good elasticity, flexural resistance, wear resistance, and excellent mechanical properties, and it has been widely used in aerospace, transportation, medical, and health fields. For NR, however, the resistance to thermal-oxidation and ozone aging is fairly poor. Although aging properties of NR can be significantly improved with the incorporation of chloroprene rubber (CR) according to some references, the miscibility between NR and CR, the morphologies of the binary blends, and so on are revealed ambiguously. In this work, molecular dynamics simulation (MD) and dissipative particle dynamics (DPD) simulation were carried out to predict the compatibility between natural rubber and chloroprene rubber in view of Flory-Huggins parameters. The morphologies of the blends were obtained with the use of the DPD method. The simulation results were furtherly examined by means of Fourier transform infrared spectroscopy (FT-IR) and dynamic mechanical analysis (DMA). It was found that the miscibility between NR and CR is poor. Nevertheless, the miscibility could be improved when the content of CR is 50% or 90%. In addition, spinodal decomposition with a critical temperature of 390 K would take place according to the phase diagram. Microphase structure such as spherical, lamellar, and bicontinuous phases can be found with different contents of CR in the blends with the results of morphologies analysis.

Natural Hollow Fiber-Derived Carbon Microtube with Broadband Microwave Attenuation Capacity.

Constructing hierarchical structures is indispensable to tuning the electromagnetic properties of carbon-based materials. Here, carbon microtubes with nanometer wall thickness and micrometer diameter were fabricated by a feasible approach with economical and sustainable kapok fiber. The carbonized kapok fiber (CKF) exhibits microscale pores from the inherent porous templates as well as pyrolysis-induced nanopores inside the wall, affording the hierarchical carbon microtube with excellent microwave absorbing performance over broad frequency. Particularly, CKF-650 exhibits an optimized reflection loss (RL) of −62.46 dB (10.32 GHz, 2.2 mm), while CKF-600 demonstrates an effective absorption bandwidth (RL < −10 dB) of 6.80 GHz (11.20−18.00 GHz, 2.8 mm). Moreover, more than 90% of the incident electromagnetic wave ranging from 2.88 GHz to 18.00 GHz can be dissipated by simply controlling the carbonization temperature of KF and/or the thickness of the carbon-microtube-based absorber. These encouraging findings provide a facile alternative route to fabricate microwave absorbers with broadband attenuation capacity by utilizing sustainable biomass.

Sustainable Kapok Fiber-Derived Carbon Microtube as Broadband Microwave Absorbing Material.

The design of hierarchical structures from biomass has become one of the hottest subjects in the field of microwave absorption due to its low cost, vast availability and sustainability. A kapok-fiber-derived carbon microtube was prepared by facile carbonization, and the relation between the structure and properties of the carbonized kapok fiber (CKF) was systematically investigated. The hollow tubular structures afford the resulting CKF composites with excellent microwave-absorbing performance. The sample with a 30 wt.% loading of CKF in paraffin demonstrates the strongest microwave attenuation capacity, with a minimum reflection loss of -49.46 dB at 16.48 GHz and 2.3 mm, and an optimized effective absorption bandwidth of 7.12 GHz (10.64-17.76 GHz, 2.3 mm) that covers 34% of the X-band and 96% of the Ku-band. Further, more than 90% of the incident electromagnetic wave in the frequency from 4.48 GHz to 18.00 GHz can be attenuated via tuning the thickness of the CKF-based absorber. This study outlines a foundation for the development of lightweight and sustainable microwave absorbers with a high absorption capacity and broad effective absorption bandwidth.

Effect of Nonisoprene Degradation and Naturally Occurring Network during Maturation on the Properties of Natural Rubber.

It well-known that the superior performance of natural rubber (NR) compared to its synthetic counterpart mainly derives from nonisoprene components and naturally occurring network, which varies during the progress of the maturation and thereby results in technically graded rubber with different properties. However, identifying the roles of these two factors in the forming of excellent performance of NR is still a challenge as they change simultaneously during the maturation process. Here, influences of naturally occurring networking and nonisoprene degradation on the components, structures and properties of NR were systematically investigated by tailored treatments of maturation. It was found that the maturation-induced formation of natural network structure contributes to the increase in initial plastic value, Mooney viscosity and gel content for un-crosslinked NR, while the decomposition of nonisoprene components plays a dominant role in improving the mechanical properties of vulcanized NR. Stress-strain curve and Mooney-Rivlin analysis demonstrate that the biodegradation of the nonisoprene components significantly boost the vulcanization process, which significantly increases the number of chemical cross-link networks and effective cross-link density of the material, greatly improving the mechanical properties of NR vulcanizates. This resulted in the tensile strength of TSR 10CV being able to reach 22.6 MPa, which is significantly improved compared to 15.8 MPa of TSR 3CV. Evidenced by tubular model fitting, the increase in chemical cross-linking points effectively reduces the movable radius of the molecular chain under dynamic loading, making the molecular chain more difficult to move, which suppresses the entropy change under dynamic loading and consequently endows NR excellent dynamic mechanical properties. This resulted in a significant decrease in the temperature rising of TSR 10CV to 3.3 °C, while the temperature rising of TSR 3CV was still as high as 14.5 °C. As a minor factor, the naturally occurring network improves the mechanical properties of vulcanizates in the form of sacrificial bonds.

Synthesis of PNIPAAm-g-P4VP Microgel as Draw Agent in Forward Osmosis by RAFT Polymerization and Reverse Suspension Polymerization to Improve Water Flux.

Microgels have unique and versatile properties allowing their use in forward osmosis areas as a draw agent. In this contribution, poly(4-vinylpyridine) (P4VP) was synthesized via RAFT polymerization and then grafted to a poly(N-Isopropylacrylamide) (PNIPAAm) crosslinking network by reverse suspension polymerization. P4VP was successfully obtained by the quasiliving polymerization with the result of nuclear magnetic resonance and gel permeation chromatography characterization. The particle size and particle size distribution of the PNIPAAm-g-P4VP microgels containing 0, 5, 10, 15 and 20 wt% P4VP were measured by means of a laser particle size analyzer. It was found that all the microgels were of micrometer scale and the particle size was increased with the P4VP load. Inter/intra-molecular-specific interactions, i.e., hydrogen bond interactions were then investigated by Fourier infrared spectroscopy. In addition, the water flux measurements showed that all the PNIPAAm-g-P4VP microgels can draw water more effectively than a blank PNIPAAm microgel. For the copolymer microgel incorporating 20 wt% P4VP, the water flux was measured to be 7.48 L∙m-2∙h-1.

Biodegradable Natural Rubber Based on Novel Double Dynamic Covalent Cross-Linking.

In this paper, biodegradable epoxidized natural rubber containing cyclic carbonate groups (CNR) was prepared by the reaction between epoxidized natural rubber (ENR) and carbon dioxide. Dynamic disulfide bonds and a boronic ester structure were successfully constructed and then the cross-linking network was formed by the thermally initiated "click" reaction between thiol groups of the cross-linker and the residual epoxy groups of ENR. As a result of the exquisite double dynamic covalent structure, the material exhibits high self-healing efficiency. Moreover, by virtue of the cyclic carbonate structure of the CNR, the natural rubber was confirmed to be biodegradable according to the biodegradable measurement. To the best of our knowledge, natural rubber with biodegradable and self-healing characteristics was obtained for the first time.

Polydopamine-Coated Natural Rubber Sponge for Highly Efficient Vapor Generation.

The global water crisis is becoming more and more serious, and solar steam generation has recently been investigated for clean water production and wastewater treatment. However, the efficiency of solar vapor transfer is still low. It is a great challenge to find photothermal materials which simultaneously have high energy transfer efficiency, facile production, and are low cost. To address this, we propose a method which is simple, low cost and suitable for large-scale preparation to fabricate the photothermal materials based on using recycled natural rubber sponge (NRS) coated with polydopamine (PDA). X-ray photoelectron spectroscopy analysis confirmed that when the PDA coated the surface of the NRS, the hydrophilicity of the sponge was significantly improved. Scanning electron microscopy characterization showed that the PDA-coated natural rubber sponge (PNRS) maintained the porous 3D skeleton of the pristine sponge. As a result, PNRS exhibits excellent photothermal properties, a very high evaporation rate of 1.35 kg m-2 h-1, and an energy transfer efficiency of 84.6% can be achieved under a light intensity of 1 sun (1 kW m-2). It is worth noting that the vapor generation of PNRS is still at a high level with 1.06 and 1.09 kg m-2 h-1 in the corrosive liquids of 1 M H2SO4 and 0.5 M NaOH, respectively. The photothermal materials based on using recycled NRS have good application prospects in seawater desalination and the purification of wastewater, which also provides a new method for the recycling of waste NRS.

Lightweight and broadband 2D MoS2 nanosheets/3D carbon nanofibers hybrid aerogel for high-efficiency microwave absorption.

Three-dimensional (3D) porous molybdenum disulfide nanosheets/carbon nanofibers (MoS2/CNF) hybrid aerogels were synthesized by using solvothermal method and following carbonization, where two-dimensional (2D) MoS2 nanosheets were homogenously in-situ grown on the interconnected CNF skeleton derived from bacterial cellulose, forming a hierarchical porous structure. This unique heterogeneous structure of the MoS2/CNF hybrid aerogels were conducive to electromagnetic loss, including conduction, polarization, multi-scatterings, and reflections, thus resulting in a balanced impedance matching and microwave attenuation capacity. It was found that the resulted MoS2/CNF hybrid aerogels demonstrate excellent microwave absorbing performance when the only 5.0 wt% fillers were loaded in paraffin. Particularly, MoS2/CNF-2-900 hybrid aerogel displayed an effective absorption bandwidth of 5.68 GHz and minimum reflection loss (RLmin) value of -36.19 dB at a thickness of 2.0 mm. As the thickness increases to 4.4 mm, the RLmin value of MoS2/CNF-2-900 hybrid aerogel reaches -48.53 dB. Electromagnetic loss mechanism analysis indicates that such improved microwave attenuation is attributed to proper component, multiple heterogenous interface and hierarchical porous structures. All the results in this work pave the avenue for the development of ultralight microwave absorber with high absorption capacity as well as broad effective absorption bandwidth.

Nanoporous Boron Nitride Aerogel Film and Its Smart Composite with Phase Change Materials.

With the advent of the 5G era, electronic systems have become more and more powerful, miniaturized, integrated ,and intelligent. The thermal management of electronic systems requires more efficiency and multiple functions for their practical applications, especially for the portable 5G electronic devices of the future, as the undesired heat can cause thermal discomfort or even thermal injury to people who use these electronic devices. Herein, two thermal management strategies based on boron nitride (BN) aerogel films have been proposed and demonstrated for portable devices. First, a flexible BN aerogel film with high porosity (>96%), large specific surface area (up to 982 m2 g-1), and controllable thickness (in the range from 50 to 200 µm) was fabricated via molecular precursor assembly, sublimation drying, and pyrolysis reaction in sequence. The resulting BN aerogel film individuals, serving as a thermal insulation protecting layer in portable electronics, can significantly reduce heat transfer from electronics to skin. Second, BN phase change composite films, made by dipping BN aerogel films into the melts of the organic phase change materials (e.g., paraffin), can effectively cool the portable electronics as the organic phase change materials filled in the aerogel matrix can serve as a smart thermal-regulator to absorb the undesired heat via solid-liquid phase transition. These two typical strategies of the flexible BN aerogel film-directed thermal management could assist in efforts to miniaturize, integrate, and intelligentialize portable 5G electronic devices in the future.

Photocatalytic degradation of methylene blue by a cocatalytic PDA/TiO2 electrode produced by photoelectric polymerization.

This study reports a new method for photocatalysts to degrade organic dyes on organic semiconductors. A novel strategy is reported to form TiO2 nanorod (NR)/polydopamine (PDA) electrodes with a photoelectric polymerization strategy for PDA (pep-PDA) to produce cocatalytic electrodes. Amperometric i-t curves and UV-vis diffuse reflectance spectra were recorded and showed that compared with traditional self-polymerization (sp-PDA) and electropolymerization (ep-PDA), TiO2 NR/pep-PDA exhibited an enhanced photocatalytic activity under visible light. As expected, TiO2 NR/pep-PDA showed a significant improvement for the degradation of methylene blue (MB) under visible light, which can be attributed to the strong absorption of PDA in the visible light region and the more complete and uniform coverage of the TiO2 NRs by the pep-PDA film. This study not only proposes a novel and highly efficient way to load PDA on TiO2 NRs but also provides useful insights for the loading of other photocatalysts on organic semiconductors to degrade organic dyes.

Multifunctional Aramid Nanofiber/Carbon Nanotube Hybrid Aerogel Films.

Lightweight, robust, and thin aerogel films with multifunctionality are highly desirable to meet the technological demands of current society. However, fabrication and application of these multifunctional aerogel films are still significantly underdeveloped. Herein, we demonstrate a multifunctional aerogel film composed of strong aramid nanofibers (ANFs), conductive carbon nanotubes (CNTs), and hydrophobic fluorocarbon (FC) resin. The obtained hybrid aerogel film exhibits large specific surface area (232.8 m2·g-1), high electrical conductivity (230 S·m-1), and excellent hydrophobicity (contact angle of up to 137.0°) with exceptional Joule heating performance and supreme electromagnetic interference (EMI) shielding efficiency. The FC coating renders the hydrophilic ANF/CNT aerogel films hydrophobic, resulting in an excellent self-cleaning performance. The high electrical conductivity enables a low-voltage-driven Joule heating property and an EMI shielding effectiveness (SE) of 54.4 dB in the X-band at a thickness of 568 µm. The specific EMI SE is up to 33528.3 dB·cm2·g-1, which is among the highest values of typical metal-, conducting-polymer-, or carbon-based composites. This multifunctional aerogel film holds great promise for smart garments, electromagnetic wave shielding, and personal thermal management systems.

A Dual-Surface Amidoximated Halloysite Nanotube for High-Efficiency Economical Uranium Extraction from Seawater.

By chemical cross-linking the amidoxime group onto dual-surfaces of natural ore materials, namely halloysite nanotubes (HNTs), an efficient adsorbent, AO-HNTs, is developed. AO-HNTs show high uranium adsorption capacity of 456.24 mg g-1 in 32 ppm uranium-spiked simulated seawater. In natural seawater, AO-HNTs reach the high uranium extraction capacity of 9.01 mg g-1 after 30 days' field test. The dual-surface amidoximated hollow nanotubular AO-HNTs exhibit more coordination active sites for uranium adsorption, which is attributed to the high and fast uranium adsorption capacity. Because of the stable natural ore structure, AO-HNTs also show long service life. Benefiting from the low cost of HNTs, the cost for uranium extraction from seawater is close to the uranium price in the spot uranium market, suggesting that AO-HNTs could be used for economical extraction of uranium from the oceans.

Graphene networks and their influence on free-volume properties of graphene-epoxidized natural rubber composites with a segregated structure: rheological and positron annihilation studies.

Epoxidized natural rubber-graphene (ENR-GE) composites with segregated GE networks were successfully fabricated using the latex mixing combined in situ reduced technology. The rheological behavior and electrical conductivity of ENR-GE composites were investigated. At low frequencies, the storage modulus (G') became frequency-independent suggesting a solid-like rheological behavior and the formation of GE networks. According to the percolation theory, the rheological threshold of ENR-GE composites was calculated to be 0.17 vol%, which was lower than the electrical threshold of 0.23 vol%. Both percolation thresholds depended on the evolution of the GE networks in the composites. At low GE concentrations (<0.17 vol%), GE existed as individual units, while a "polymer-bridged GE network" was constructed in the composites when GE concentrations exceeded 0.17 vol%. Finally, a "three-dimensional GE network" with percolation conductive paths was formed with a GE concentration of 0.23 vol%, where a remarkable increase in the conductivity of ENR-GE composites was observed. The effect of GE on the atom scale free-volume properties of composites was further studied by positron annihilation lifetime spectroscopy and positron age momentum correlation measurements. The motion of ENR chains was retarded by the geometric confinement of "GE networks", producing a high-density interfacial region in the vicinity of GE nanoplatelets, which led to a lower ortho-positronium lifetime intensity and smaller free-volume hole size.

Donor-acceptor conjugated polymers based on a pentacyclic aromatic lactam acceptor unit for polymer solar cells.

A series of donor­acceptor (D­A) conjugated polymers P1­P4 was synthesized by copolymerization of a novel pentacyclic aromatic lactam acceptor unit, thieno[20,30:5,6]pyrido[3,4-g]thieno[3,2-c]-isoquinoline-5,11(4H,10H)-dione (TPTI), with a donor unit, benzo-[1,2-b:4,5-b0]dithiophene (BDT) or dithieno[3,2-b:20,30-d]silole (DTS). The effect of the donor units and the side chains on TPTI on polymer properties and solar cell performance was investigated. Bulk heterojunction solar cells based on P1 and PC71BM afforded the highest power conversion efficiency (PCE) of 5.30%.