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Supported ionic liquid membranes (SILMs), owing to their capacities in harnessing physicochemical properties of ionic liquid for exceptional CO2 solubility, have emerged as a promising platform for CO2 extraction. Despite great achievements, existing SILMs suffer from poor structural and performance stability under high-pressure or long-term operations, significantly limiting their applications. Herein, a one-step and in situ interfacial polymerization strategy is proposed to elaborate a thin, mechanically-robust, and highly-permeable polyamide armor on the SILMs to effectively protect ionic liquid within porous supports, allowing for intensifying the overall stability of SILMs without compromising CO2 separation performance. The armored SILMs have a profound increase of breakthrough pressure by 105% compared to conventional counterparts without armor, and display high and stable operating pressure exceeding that of most SILMs previously reported. It is further demonstrated that the armored SILMs exhibit ultrahigh ideal CO2/N2 selectivity of about 200 and excellent CO2 permeation of 78 barrers upon over 150 h operation, as opposed to the full failure of CO2 separation performance within 36 h using conventional SILMs. The design concept of armor provides a flexible and additional dimension in developing high-performance and durable SILMs, pushing the practical application of ionic liquids in separation processes.
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Salt scaling poses a significant obstacle to the practical implementation of solar-driven evaporation for desalination. Attempts to mitigate scaling by enhancing mass transfer often lead to a compromise in evaporation efficiency due to associated heat loss. In the present work, a novel seesaw evaporator with a Janus structure to harness scaling for periodic self-descaling is reported. The seesaw evaporators are facilely fabricated by delignifying balsa wood and subsequently single-sided spray-coating it with soot and polydimethylsiloxane (PDMS). This unique Janus structure enables the evaporator to float on the brine while ensuring an ample supply of solution for evaporation. During evaporation, salt ions are transported directionally toward the cocked end of the evaporator to form scaling, triggering the seesaw evaporator to flip once a threshold is reached. The accumulated salts re-dissolve back into the solution. By adjusting the tilt angle, the evaporator can achieve an impressive evaporation rate of up to 2.65 kg m-2 h-1 when evaporating an 8 wt.% NaCl solution. Remarkably, these evaporators maintain a stable evaporation rate during prolonged 120 h operation and produce ≈3.93-6.35 L mâ»2·day⻹ of freshwater from simulated brines when assembled into an evaporation device.
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The interlayer strategy has emerged as an effective approach for modulating the interfacial polymerization process and improving the permeability and selectivity of polyamide membranes. However, the underlying mechanisms by which charged interlayers influence the interfacial polymerization process remain inadequately understood. In this study, we utilized two distinct charged cellulose nanofibers, namely, carboxylated cellulose (â-CNF) and quaternized cellulose ([Formula: see text]-CNF), as interlayers to regulate the interfacial polymerization process. Through simulation results, isothermal titration calorimetry (ITC) and UV tests, we demonstrated that the [Formula: see text]-CNF interlayer, which possesses stronger hydration capability and better piperazine affinity, enhanced the diffusion of piperazine across the reaction interface compared with the â-CNF interlayer. This led to an acceleration of the interfacial polymerization process and the formation of a denser membrane structure. Further investigation revealed that the charged interlayers significantly influenced the surface charging properties of the resulting nanofiltration membranes within a 30 nm range of electrostatic effects. Specifically, the â-CNF interlayer conferred a higher negative charge to the membrane surface, while the [Formula: see text]-CNF interlayer endowed the membranes with a lower surface negative charge. Leveraging these differences, the â-i-TFC membranes exhibited exceptional separation performance for divalent anions, achieving a SO42-/Cl- selectivity of 136. Conversely, the [Formula: see text]-i-TFC membrane demonstrated an enhanced separation of divalent cations, displaying a Mg2+/Na+ selectivity of 3.5. This study lays the groundwork for regulating the surface charging properties of polyamide membranes, offering potential advancements in nanofiltration applications.
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Hydrogels, water-saturated polymer networks find widespread use in soft robotics, biomedical, pharmaceutical and food industries. Both solid and water constituents of hydrogels are sensitive to external stimuli such as temperature, humidity, osmolarity, and light. For instance, common hydrogels swell or shrink in the presence of chemical potential gradient between the sample and surrounding environment. Corresponding changes in internal water content lead to significant changes in mechanical properties of hydrogels. Besides, internal stresses build up if the gel samples are constrained during swelling or dehydration. In the present research, we utilize modal analyses technique on drying hydrogels to identify dehydration-induced changes in elastic moduli and internal stresses. In particular, natural frequencies and damping ratios of the first two axisymmetric transverse vibration modes are measured on clamped gelatin disks using non-contact laser vibrometry at various water loss states. Experimental modal frequencies are then compared to the predictions of a pre-stressed thick plate model. The evolutions of elastic moduli and internal stresses for water losses up to 80% are identified. The broadband loss capacity of gelatin is also determined from the measured modal damping ratios. Highly transient mechanical response observed on the gelatin disks further demonstrates the need for non-contact and rapid mechanical characterization of hydrogels. As illustrated in this work, vibration and wave-based techniques are promising candidates to fulfill that need.
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The performance and phase-separated microstructures of epoxy asphalt binders greatly depend on the concentration of epoxy resin or bitumen. In this paper, the effect of the epoxy resin (ER) concentration (10-90%) on the viscosity, thermo-mechanical properties, and phase-separated morphology of warm-mix epoxy asphalt binders (WEABs) was investigated using the Brookfield rotational viscometer, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and laser scanning confocal microscopy (LSCM). Due to the high reactivity of epoxy resin, the viscosity of WEABs increases with time. Furthermore, the initial viscosity of WEABs decreases with the ER concentration. Depending on the ER concentration, the viscosity-time behavior of WEABs is divided into three stages: slow (10-40%), fast (50-80%), and extremely slow (90%). In the slow stage, the viscosity slightly increases with the ER concentration, while the fast stage shows an opposite trend. DSC and DMA results reveal that WEABs with 10-80% ER exhibit two glass transition temperatures (Tgs) for cured epoxy resin and bitumen. Moreover, the Tgs of epoxy resin and bitumen increase with the ER concentration. However, WEAB with 90 % ER has only one Tg. LSCM observation shows that phase separation occurs in all WEABs. For WEABs containing 10-40% ER, spherical epoxy particles act as the discontinuous phase and disperse in the continuous bitumen phase. However, in WEABs with 50-90% ER, phase inversion takes place. Contrarily, bitumen particles disperse in the continuous epoxy phase. The damping properties of WEABs with the continuous epoxy phases increase with the ER concentration, while the crosslinking density shows an opposite trend. The occurrence of phase inversion results in a sharp increase in the tensile strength of WEABs. For WEABs with the continuous epoxy phases, the elongation at break increases with the ER concentration. The toughness first increases and then decreases with the ER concentration. A maximum toughness value shows at 70% ER.
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The application of hydrogel coatings to surface-modified metallic materials has gained considerable attention in engineering practice such as water-oil separation. However, the low coating adhesion and poor coating stability restrict its application. In this study, to obtain special wettability and durable filter materials, polyacrylamide (PAM)/sodium alginate (SA) xerogel particles were first prepared and adhered to a stainless steel screen by using an epoxy resin as a linker. Subsequently, the xerogel particles of the screen rehydrates in water to form a PAM-SA double-network hydrogel. The results show that the screen modified by PAM-SA xerogel of 20-30 µm particle size and a linker concentration of 0.1 g/mL resulted in a chimeric structure and subsequently transformed a uniform double-network hydrogel coating in water. According to the experimental results, the rough hydrogel coating exhibits superhydrophilicity and superoleophobicity under water; in particular, it has excellent wear resistance as well as physical and chemical stability. Under gravity-driven action, the PAM-SA-modified screen demonstrates high separation efficiency values of up to 99% in separating a wide range of oil/water mixtures and maintaining a water flux of (2-6) × 104 L·m-2·h-1. There was no significant reduction in efficiency of separation and water flux after 10 cycles, indicating that the PAM-SA-modified screen is capable of offering outstanding separation performance and durability. Moreover, the hydrogel-modified screen demonstrated corrosion and swelling resistance in some extreme environments, paving a way for practical applications in water treatment. The novel hydrogel-coating-modified screen with ease of preparation holds great promise for oil/water separation and other engineering applications.
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Thin-film-composite (TFC) nanofiltration membranes have found wide uses in environment remediation and industrial separation. There is a growing trend to avoid the use of organic solvents and toxic chemicals during membrane fabrication. Therefore, the aqueous fabrication of TFC membranes receives considerable interest as a green and sustainable process. However, it remains challenging to construct a defect-free and ultrathin film in a homogeneous aqueous phase without the assistance of an interface. The contra-diffusion process provides a special "interface" to confine the film formation within a narrow space by regulating the competition between precursor diffusion and interfacial reactions. Herein, Fe3+/tannic acid (TA) TFC membranes were fabricated by a contra-diffusion process. The effects of fabrication parameters on the Fe3+/TA TFC membrane microstructure and performance were also investigated. The negatively charged membrane performs a competitive Na2SO4 rejection of 95.6% with a permeation flux of 44.3 L m-2 h-1 under 0.6 MPa as well as more than 99.5% rejection to several anionic dyes. The as-prepared membranes perform superior nanofiltration performance compared to other reported Fe3+/TA-based membranes, owing to the thin and defect-free selective layers by self-regulation. Moreover, the membranes exhibit stable rejection during a long-term nanofiltration test.
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Electronic nose (E-nose), a kind of instrument which combines with the gas sensor and the corresponding pattern recognition algorithm, is used to detect the type and concentration of gases. However, the sensor drift will occur in realistic application scenario of E-nose, which makes a variation of data distribution in feature space and causes a decrease in prediction accuracy. Therefore, studies on the drift compensation algorithms are receiving increasing attention in the field of the E-nose. In this paper, a novel method, namely Wasserstein Distance Learned Feature Representations (WDLFR), is put forward for drift compensation, which is based on the domain invariant feature representation learning. It regards a neural network as a domain discriminator to measure the empirical Wasserstein distance between the source domain (data without drift) and target domain (drift data). The WDLFR minimizes Wasserstein distance by optimizing the feature extractor in an adversarial manner. The Wasserstein distance for domain adaption has good gradient and generalization bound. Finally, the experiments are conducted on a real dataset of E-nose from the University of California, San Diego (UCSD). The experimental results demonstrate that the effectiveness of the proposed method outperforms all compared drift compensation methods, and the WDLFR succeeds in significantly reducing the sensor drift.
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Polydopamine-based chemistry has been employed for various surface modifications attributed to the advantages of universality, versatility, and simplicity. Co-deposition of polydopamine (PDA) with polyethyleneimine (PEI) has then been proposed to realize one-step fabrication of functional coatings with improved morphology uniformity, surface hydrophilicity, and chemical stability. Herein, we report the co-deposition kinetics related to the solution composition with different dopamine/PEI ratios, PEI molecular weights, dopamine/PEI concentrations, and the substrate surface with varying chemistry and wettability. The addition of PEI to dopamine solution suppresses the precipitation of PDA aggregates, resulting in an expanded time window of steady co-deposition compared with that of PDA deposition. Low-molecular-weight PEI at low concentration accelerates the co-deposition process, while high-molecular-weight PEI and high concentration of either PEI or dopamine/PEI are detrimental to the co-deposition efficiency. Meanwhile, the surface morphology and chemical composition of the co-deposition coatings can be regulated by the solution conditions during co-deposition. Moreover, obvious deviations in the co-deposition rate and the amount of substrates bearing various functional groups, such as alkyl, phenyl, hydroxyl, and carboxyl, are revealed, which are quite different from PDA deposition. The initial adsorption rates further reflect the change in interactions between the aggregates and these substrates caused by PEI, which follows the sequence of carboxyl > hydroxyl > alkyl > phenyl. These results provide deep insights into the PDA/PEI co-deposition process on various substrates.
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This paper proposes a way for drift compensation in electronic noses (e-nose) that often suffers from uncertain and unpredictable sensor drift. Traditional machine learning methods for odor recognition require consistent data distribution, which makes the model trained with previous data less generalized. In the actual application scenario, the data collected previously and the data collected later may have different data distributions due to the sensor drift. If the dataset without sensor drift is treated as a source domain and the dataset with sensor drift as a target domain, a domain correction based on kernel transformation (DCKT) method is proposed to compensate the sensor drift. The proposed method makes the distribution consistency of two domains greatly improved through mapping to a high-dimensional reproducing kernel space and reducing the domain distance. A public benchmark sensor drift dataset is used to verify the effectiveness and efficiency of the proposed DCKT method. The experimental result shows that the proposed method yields the highest average accuracies compared to other considered methods.
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We experimentally investigate the second-harmonic generation of a high-order Laguerre-Gaussian (LG) mode under the quasi-phase-matching (QPM) configuration. First, we introduce a simple method to observe the azimuthal (l) and radial (p) indices of the high-order LG modes. Based on the astigmatic transformation technique, l and p are revealed in the number of dark stripes of the converted pattern in the focal plane. Then, using this efficient method of measurement, we demonstrate in experiments a second-harmonic LG mode with its radial and azimuthal indices being twice those of the inputted fundamental wave through QPM in a periodically poled KTP crystal. Our results provide a feasible way to obtain simultaneously the LG modes with larger radial and azimuthal indices.
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Janus membranes are an emerging class of materials having opposing properties at an interface. This structure results in selective and often novel transport characteristics. In this Minireview, a definition of the Janus membrane, beyond merely asymmetric materials, is introduced and common fabrication strategies are outlined. Also presented are current and potential applications in directional transport, switchable permeation, and performance optimization with detailed mechanisms.
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Zwitterionic materials have received great attention because of the non-fouling property. As a result of the electric neutrality of zwitterionic polymers, their layer-by-layer (LBL) assembly is generally conducted under specific conditions, such as very low pH values or ionic strength. The formed multilayers are unstable at high pH or in a high ionic strength environment. Therefore, the formation of highly stable multilayers of zwitterionic polymers via the LBL assembly process is still challenging. Here, we report the LBL assembly of poly(sulfobetaine methacrylate) (PSBMA) with a polyphenol, tannic acid (TA), for protein-resistant surfaces. The assembly process was monitored by a quartz crystal microbalance (QCM) and variable-angle spectroscopic ellipsometry (VASE), which confirms the formation of thin multilayer films. We found that the (TA/PSBMA)n multilayers are stable over a wide pH range of 4-10 and in saline, such as 1 M NaCl or urea solution. The surface morphology and chemical composition were characterized by specular reflectance Fourier transform infrared spectroscopy (FTIR/SR), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Furthermore, (TA/PSBMA)n multilayers show high hydrophilicity, with a water contact angle lower than 15°. A QCM was used to record the dynamic protein adsorption process. Adsorption amounts of bovine serum albumin (BSA), lysozyme (Lys), and hemoglobin (Hgb) on (TA/PSBMA)20 multilayers decreased to 0.42, 52.9, and 37.9 ng/cm(2) from 328, 357, and 509 ng/cm(2) on a bare gold chip surface, respectively. In addition, the protein-resistance property depends upon the outmost layer. This work provides new insights into the LBL assembly of zwitterionic polymers.
Assuntos
Metacrilatos/química , Taninos/química , Adsorção , Materiais Biocompatíveis/química , Hemoglobinas/química , Microscopia de Força Atômica , Muramidase/química , Espectroscopia Fotoeletrônica , Técnicas de Microbalança de Cristal de Quartzo , Soroalbumina Bovina/química , Espectroscopia de Infravermelho com Transformada de Fourier , Propriedades de SuperfícieRESUMO
We present a novel approach to fabricate endogenous slippery lubricant-infused porous surfaces (eSLIPS) at room temperature using an evaporation-induced phase separation process. The ternary coating system, comprising ethylene-propylene copolymer, caprylyl methicone, and n-hexane, forms a porous structure in situ infiltrated with lubricant, resulting in surfaces with remarkable anti-fouling and anti-icing properties.
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Waterborne polyurethane asphalt emulsion (WPUA) is an environmentally friendly bituminous material, whose performance is highly dependent on the phase structure of the continuous phase. In this paper, WPUAs in the vicinity of phase inversion were prepared using waterborne polyurethane (WPU) and asphalt emulsion. The chemical structures, thermal stability, dynamic mechanical properties, phase-separated morphology and mechanical performance of WPUAs were studied. Fourier-transform infrared (FTIR) spectra revealed that there are no -NCO bonds in either the pure WPU or WPUAs. Moreover, the preparation of WPUA is a physical process. The addition of WPU weakens the thermal stability of asphalt emulsion. WPU improves the storage modulus of asphalt emulsion at lower and higher temperatures. The glass transition temperatures of the WPUA films are higher than that of the pure WPU film. When the WPU concentration increases from 30 wt% to 40 wt%, phase inversion occurs; that is, the continuous phase shifts from asphalt to WPU. The WPUA films have lower tensile strength and toughness than the pure WPU film. However, the elongations at break of the WPUA films are higher than that of the pure WPU film. Both the tensile strength and toughness of the WPUA films increase with the WPU concentration. Due to the occurrence of phase inversion, the elongation at break, tensile strength and toughness of the WPUA film containing 30 wt% WPU are increased by 29%, 250% and 369%, respectively, compared to the film with 40 wt% WPU.
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Soft ionic conductors have emerged as a powerful toolkit to engineer transparent flexible intelligent devices that go beyond their conventional counterparts. Particularly, due to their superior capacities of eliminating the evaporation, freezing and leakage issues of the liquid phase encountered with hydrogels, organohydrogels and ionogels, the emerging solid-state, liquid-free ion-conducting elastomers have been largely recognized as ideal candidates for intelligent flexible devices. However, despite their extensive development, a comprehensive and timely review in this emerging field is lacking, particularly from the perspective of design principles, advanced manufacturing, and distinctive applications. Herein, we present (1) the design principles and intriguing merits of solid-state, liquid-free ion-conducting elastomers; (2) the methods to manufacture solid-state, liquid-free ion-conducting elastomers with preferential architectures and functions using advanced technologies such as 3D printing; (3) how to leverage solid-state, liquid-free ion-conducting elastomers in exploiting advanced applications, especially in the fields of flexible wearable sensors, bioelectronics and energy harvesting; (4) what are the unsolved scientific and technical challenges and future opportunities in this multidisciplinary field. We envision that this review will provide a paradigm shift to trigger insightful thinking and innovation in the development of intelligent flexible devices and beyond.
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Porous substrates act as open "interfacial reactors" during the synthesis of polyamide composite membranes via interfacial polymerization. However, achieving a thin and dense polyamide nanofilm with high permeance and selectivity is challenging when using a conventional substrate with uniform wettability. To overcome this limitation, we propose the use of Janus porous substrates as confined interfacial reactors to decouple the local monomer concentration from the total monomer amount during interfacial polymerization. By manipulating the location of the hydrophilic/hydrophobic interface in a Janus porous substrate, we can precisely control the monomer solution confined within the hydrophilic layer without compromising its concentration. The hydrophilic surface ensures the uniform distribution of monomers, preventing the formation of defects. By employing Janus substrates fabricated through single-sided deposition of polydopamine/polyethyleneimine, we significantly reduce the thickness of the polyamide nanofilms from 88.4 to 3.8 nm by decreasing the thickness of the hydrophilic layer. This reduction leads to a remarkable enhancement in water permeance from 7.2 to 52.0 l/m2·h·bar while still maintaining ~96% Na2SO4 rejection. The overall performance of this membrane surpasses that of most reported membranes, including state-of-the-art commercial products. The presented strategy is both simple and effective, bringing ultrapermeable polyamide nanofilms one step closer to practical separation applications.
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Fine design of surface charge properties of polyamide membranes is crucial for selective ionic and molecular sieving. Traditional membranes face limitations due to their inherent negative charge and limited charge modification range. Herein, we report a facile ionic liquid-decoupled bulk/interfacial diffusion strategy to elaborate the double charge flips of polyamide membranes, enabling on-demand transformation from inherently negative to highly positive and near-neutral charges. The key to these flips lies in the meticulous utilization of ionic liquid that decouples intertwined bulk/interfacial diffusion, enhancing interfacial while inhibiting bulk diffusion. These charge-tunable polyamide membranes can be customized for impressive separation performance, for example, profound Cl-/SO42- selectivity above 470 in sulfate recovery, ultrahigh Li+/Mg2+ selectivity up to 68 in lithium extraction, and effective divalent ion removal in pharmaceutical purification, surpassing many reported polyamide nanofiltration membranes. This advancement adds a new dimension to in the design of advanced polymer membranes via interfacial polymerization.
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It is particularly essential to analyze the complex crosslinked networks within polyamide membranes and their correlation with separation efficiency for the insightful tailoring of desalination membranes. However, using the degree of network crosslinking as a descriptor yields abnormal analytical outcomes and limited correlation with desalination performance due to imperfections in segmentation and calculation methods. Herein, we introduce a more rational parameter, denoted as harmonic amide bond density (HABD), to unravel the relationship between the crosslinked networks of polyamide membranes and their desalination performance. HABD quantifies the number of distinct amide bonds per unit mass of polyamide, based on a comprehensive segmentation of polyamide structure and consistent computational protocols derived from X-ray photoelectron spectroscopy data. Compared to its counterpart, HABD overcomes the limitations and offers a more accurate depiction of the crosslinked networks. Empirical data validate that HABD exhibits the expected correlation with the salt rejection and water permeance of reverse osmosis and nanofiltration polyamide membranes. Notably, HABD is applicable for analyzing complex crosslinked polyamide networks formed by highly functional monomers. By offering a powerful toolbox for systematic analysis of crosslinked polyamide networks, HABD facilitates the development of permselective membranes with enhanced performance in desalination applications.
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By mimicking in vivo bionic microenvironment and promoting osteogenic differentiation, the hybrid organic-inorganic nanofibrous membranes provide promising potential for guided bone regeneration (GBR) in the treatment of clinical bone defects. To develop a degradable and osteogenic membrane for GBR by combining the natural biomacromolecule silk fibroin (SF) and gelatine with the bioactive nano hydroxyapatite (nHA), the anhydride-modified gelatine-nano hydroxyapatite (GelMA-nHA) composites were synthesized in situ and introduced into silk fibroin to prepare nanofibrous membranes with different ratios using electrospinning and photocrosslinking. The nanofibrous membranes, particularly those with a mass ratio of 7:2:1, were found to exhibit satisfactory elongation at break up to 110 %, maintain the nanofibrous structure for up to 28 days, and rapidly form bone-like apatite within 3 days, thus offering advantages when it comes to guided bone regeneration. In vitro cell results showed that the SF/GelMA/nHA membranes had excellent biocompatibility and enhanced osteogenic differentiation of hBMSCs. In vivo studies revealed that the hybrid composite membranes can improve bone regeneration of critical-sized calvarial defects in rat model. Therefore, the novel hybrid nanofibrous membrane is proposed to be a alternative candidate for creating a bionic microenvironment that promotes bone regeneration, indicating their potential application to bone injury treatment.