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Marine biofouling, resulting from the adhesion of marine organisms to ship surfaces, has long been a significant issue in the maritime industry. In this paper, we focused on utilizing soft and hydrophilic hydrogels as a potential approach for antifouling (AF) coatings. Acrylic acid (AA) with a polyelectrolyte effect and N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium betaine (SBMA) with an antipolyelectrolyte effect were selected as monomers. By adjusting the monomer ratio, we were able to create hydrogel coatings that exhibited low swelling ratio in both fresh water and seawater. The Al(OH)3 nanoparticle, as a physical cross-linker, provided better mechanical properties (higher tensile strength and larger elongation at break) than the chemical cross-linker through the dynamic coordination bonds and plentiful hydrogen bonds. Additionally, we incorporated trehalose into the hydrogel, enabling the repair of the hydrogel network through covalent-like hydrogen bonding. The zwitterion compound SBMA endowed the hydrogel with excellent AF performance. It was found that the highest SBMA content did not lead to the best antibacterial performance, as bacterial adhesion quantity was also influenced by the charge of the hydrogel. The hydrogel with appropriate SBMA content being close to electrical neutrality exhibits the strongest zwitterionic property of PSBMA chains, resulting in the best antibacterial adhesion performance. Furthermore, the pronounced hydrophilicity of SBMA enhanced the lubrication of the hydrogel surface, thereby reducing the friction resistance when applied to the hull surface during ship navigation.
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Cellulose was extracted from coconut shell powder (CSP) as a renewable biomass resource and utilized as a reinforcing material in poly(lactic acid)/poly(butylene succinate) (PLA/PBS) solvent casting films. The extraction process involved delignification and mercerization of CSP. Microscopic investigation of the extracted microfibers demonstrated a reduction in diameter and a rougher surface characteristic compared to the raw CSP. The cellulose prepared in this study exhibited improved thermal stability and higher crystallinity (54.3%) compared to CSP. The morphology of the cycrofractured surface, thermal analysis, mechanical property, and UV transmittance of films were measured and compared. Agglomeration of 3 wt.% of cellulose was observed in PLA/PBS films. The presence of cellulose higher than 1 wt.% in the PLA/PBS decreased the onset decomposition temperature and maximum decomposition temperature of films. However, the films loading 3 wt.% of cellulose had a higher char formation (5.47%) compared to neat PLA/PBS films. The presence of cellulose promoted the formation of non-uniform crystals, while cellulose had a slightly negative impact on crystallinity due to the disruption of polymer chains at lower cellulose content (0.3, 0.5 wt.%). The mechanical strength of PLA/PBS films decreased as the cellulose content increased. Moreover, PLA/PBS film with 3 wt.% of cellulose appeared to show a 3% and 7.5% decrease in transmittance in UVC (275 nm) and UVA (335 nm) regions compared to neat PLA/PBS films while maintaining a certain transparency.
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Electromagnetic interference (EMI) shielding materials with stretchability are important for developing wearable and flexible appliances. Herein, lithium bis(trifloromethanesulfonyl)imide (Li-TFSI)-doped poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and carboxylated styrene-butadiene rubber (XSB) latex are used to prepare stretchable EMI shielding composite films of 0.2 mm in thickness. In these films, the doped PEDOT:PSS nanoparticles form tenuous conductive pathways between the hexagonally packed latex particles, resulting in higher EMI shielding efficiency (EMI SE) compared with the films containing traditional dopant ethylene glycol. For the purpose of stretchable EMI shielding, the films containing 6 wt % PEDOT:PSS and 6 wt % Li-TFSI demonstrate EMI SE of 50 and 30 dB (12.4 GHz) at 0 and 100% strains, respectively, being the highest values among the reported shielding composites except for those using liquid metal as the filler. The investigation also provides a simple and environmentally friendly preparation method being highlighted for the development of lightweight stretchable EMI shielding materials for applications in flexible electronics in the near future.
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With commercial electronics transitioning toward flexible devices, there is a growing demand for high-performance polymers such as poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS). Previous breakthroughs in promoting the conductivity of PEDOT:PSS, which mainly stem from solvent-treatment and transfer-printing strategies, remain as inevitable challenges due to the inefficient, unstable, and biologically incompatible process. Herein, a scalable fabrication of conducting PEDOT:PSS inks is reported via a metastable liquid-liquid contact (MLLC) method, realizing phase separation and removal of excess PSS simultaneously. MLLC-doped inks are further used to prepare ring-like films through a compromise between the coffee-ring effect and the Marangoni vortex during evaporation of droplets. The specific control over deposition conditions allows for tunable ring-like morphologies and preferentially interconnected networks of PEDOT:PSS nanofibrils, resulting in a high electrical conductivity of 6,616 S cm-1 and excellent optical transparency of the film. The combination of excellent electrical properties and the special morphology enables it to serve as electrodes for touch sensors with gradient pressure sensitivity. These findings not only provide new insight into developing a simple and efficient doping method for commercial PEDOT:PSS ink, but also offer a promising self-assembled deposition pattern of organic semiconductor films, expanding the applications in flexible electronics, bioelectronics as well as photovoltaic devices.
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The composition of Pseudostellaria heterophylla (Tai-Zi-Shen, TZS) is greatly influenced by the growing area of the plants, making it significant to distinguish the origins of TZS. However, traditional methods for TZS origin identification are time-consuming, laborious, and destructive. To address this, two or three TZS accessions were selected from four different regions of China, with each of these resources including distinct quality grades of TZS samples. The visible near-infrared (Vis/NIR) and short-wave infrared (SWIR) hyperspectral information from these samples were then collected. Fast and high-precision methods to identify the origins of TZS were developed by combining various preprocessing algorithms, feature band extraction algorithms (CARS and SPA), traditional two-stage machine learning classifiers (PLS-DA, SVM, and RF), and an end-to-end deep learning classifier (DCNN). Specifically, SWIR hyperspectral information outperformed Vis/NIR hyperspectral information in detecting geographic origins of TZS. The SPA algorithm proved particularly effective in extracting SWIR information that was highly correlated with the origins of TZS. The corresponding FD-SPA-SVM model reduced the number of bands by 77.2% and improved the model accuracy from 97.6% to 98.1% compared to the full-band FD-SVM model. Overall, two sets of fast and high-precision models, SWIR-FD-SPA-SVM and SWIR-FD-DCNN, were established, achieving accuracies of 98.1% and 98.7% respectively. This work provides a potentially efficient alternative for rapidly detecting the origins of TZS during actual production.
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The rheological behavior of polyvinyl alcohol (PVA) aqueous solution is crucial to optimizing the processing technology and performance of PVA products. In this paper, the dynamic rheological behavior of PVA aqueous solution was investigated in detail. PVA solution with a concentration of 10 wt% showed unnormal rheological behaviors, that is, the liquid-like behavior in the high frequency (ω) region and the solid-like behavior in the low ω region. A storage modulus (G') plateau appears in the relatively low ω region as a gel with a network structure. Different from conventional hydrogel, this plateau has a low modulus, and the corresponding size of the relaxation unit is estimated to be 554 nm, being higher than the size of a whole PVA chain. It is believed that the network mesh is formed by the intermolecular hydrogen bonding interactions among PVA chains. The relaxation time of these meshes is longer than the reptation time of a PVA chain. Based on the relaxation spectrum and calculation analysis, it is found that the destruction of intermolecular hydrogen bonds, such as by heating up, adding sodium dodecyl sulfate, and shear operation, will make the relaxation unit (mesh) larger and lead to the left shift of the intersection of G' and loss modulus (Gâ³). In a PVA solution with a high concentration, multiple meshes of various sizes could be formed and thus generate multiple relaxation peaks. The large-sized meshes mainly contribute to the left shift of the intersection of G' and Gâ³, and the small-sized meshes contribute to the high plateau modulus. The results in this paper offer a new angle to analyze polymer solutions with strong intermolecular interaction.
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The evolution of the morphology/structure and the nonlinear viscoelasticity of rubber blends under large amounts of strain are key scientific issues for the design and manufacture of rubber blends. The rheological responses of natural rubber/styrene-butadiene rubber (NR/SBR) blends are traced over a wide range of blend compositions to gain an insight into the effect of blend morphology on their nonlinear viscoelasticity. We also prepare NR + SBR physical blends without melt mixing to distinguish the contributions of composition and blend morphology to the viscoelastic response. The microscopic heterogeneous gel-like structure of NR/SBR blends may remarkably weaken their strain softening and improve their modulus hysteretic recovery under large strain, which may be attributed to the heterogeneous microscopic deformation for the NR and SBR phases. Furthermore, additional elastic contribution resulted from the increasing interfacial energy of domain deformation. This may provide some new insights into the effect of blend morphology on the Payne effect of rubber blends.
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Carbon black (CB) and silica (Sil) as rubber reinforcement have raised environmental concerns for being high resources consumptive and less susceptible towards biodegradability. Cellulose nanocrystal (CNC) has demonstrated great potentials for use as biodegradable nanofillers in rubber nanocomposites while evaluation of its environmental impacts with optimal end-of-life (EOL) choices is not carried out. To simulate realistic EOL, thermo-oxidative aging and soil burial aging behaviors of rubber nanocomposites with 33.3% filler were performed. The environmental weathering performance modeled with the help of life cycle assessment (LCA) illustrates increased biodegradation susceptibility with partial replacement of CB or Sil with CNC in the nanocomposites, hence promoting the environmental solutions for waste minimalization by enhancing the biodegradability potentials. In terms of LCA, the CNC incorporation contributes more to the environmental impacts in manufacturing but greatly lowers the EOL choices, by reducing the global warming potential values.
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Nanocompuestos , Nanopartículas , Animales , Celulosa/química , Estadios del Ciclo de Vida , Nanocompuestos/química , Nanopartículas/química , Goma , Dióxido de Silicio , Suelo , HollínRESUMEN
Layered double hydroxides (LDHs) have attracted much attention in supercapacitors because of the high specific surface area and theoretical capacitance. However, the bad cycling stability has always been their Achilles' heel that restrains their further application. In this paper, a small amount of unactive and single-valence element zinc, which has no contribution to the capacitance of electrodes, was first doped into NiCo-LDHs through two consecutive electrodeposition processes only within 30 min. With a polyaniline (PANI) nanolayer as the interlayer, an ultrathin NiCoZn-LDH nanoplate network was well-anchored on the carbon cloth surface. The slight Zn2+ doping dramatically enhanced the cycling performance of LDHs with little capacitance decay. Zn2+ doping enhanced the cyclic structural stability of NiCoZn-LDHs, while the PANI layer strengthened the interface interaction between LDHs and the current collector. By controlling the doping content of Zn2+ at 2.9%, the composite electrode achieved the best performance with a high specific capacitance of 1749 F g-1 and an ultralong life span with 89% capacitance retention after 40,000 charge-discharge cycles. This work offers a novel strategy to fast build LDH-based supercapacitors with both high specific capacitance and cycling performance.
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Although hydrogels exhibit excellent low frictional behavior, their friction coefficients cannot meet the requirements for biology, especially at low sliding velocities. Inspired by the natural lubrication mechanism from animals, plants, or even microorganisms, a nonionic surfactant, Tween 80, was introduced into a biofriendly poly(vinyl alcohol) (PVA) hydrogel to construct a composite hydrogel with ultralubrication. Such a combination endows PVA hydrogels with an ultralow coefficient of friction (10-3 to 10-4) under an extremely low sliding velocity (0.01 mm/s). Tween 80 micelles and aggregates, together with hydrophobic molds, induce rough surfaces and high carbon contents on the surface of the hydrogel, promoting excellent lubrication behavior of the composite hydrogel. In addition to the desirable lubrication, this environmentally friendly composite hydrogel also exhibited excellent flexibility at subzero temperatures, tensile properties, and good recyclability. Additionally, the method of introducing Tween 80 into hydrogels to reduce friction is also effective in chemically crosslinked double-network hydrogels.
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Hidrogeles/química , Lubricantes/química , Polisorbatos/química , Alcohol Polivinílico/química , Tensoactivos/química , Ensayo de Materiales , Docilidad , Resistencia a la Tracción , HumectabilidadRESUMEN
Cellulosic nanofillers are sustainable replacements of synthetic fillers while the agglomeration limits their potentials in high-performance rubber bionanocomposites. Herein, we investigate the effects of ionic liquid (IL) on cellulose nanocrystal and cellulose nanofibril filled natural rubber (NR) compounds and vulcanizates. The results indicate that IL improves the dispersion of cellulosic nanofillers, crosslinking density of NR matrix and mechanical strength of the vulcanizates. Invesigations of viscoelastic rheological behaviors show amplitude of Payne effect faints in compounds and raises relatively in vulcanizates with the increment of cellulosic nanofillers and IL.
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Nanoparticles reinforce rubbers and enhance Payne effect for the compounds experiencing large amplitude oscillatory shear deformation. Herein the effects of silica and cellulose nanocrystals on the Payne effect of natural rubber compounds are investigated by stress decomposition methods for clarifying the elastic and viscous nonlinearities varying with filler content and composition. The Payne effect is in general characterized by intercycle strain softening and shear thinning behaviors and intracycle hardening and thinning behaviors at high strain (strain rate) amplitudes while the filler influences the behaviors markedly at intermediate strain (rate) amplitudes. Especially, the addition of cellulose nanocrystals in the silica filled compounds improves the elastic nonlinearity and greatly weakens the viscous nonlinearity, providing a perspective on understanding the Payne effect for manufacturing high-performance rubber materials.
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In this paper we designed greener rubber nanocomposites exhibiting high crosslinking density, and excellent mechanical and thermal properties, with a potential application in technical fields including high-strength and heat-resistance products. Herein 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc) ionic liquid was combined with silane coupling agent to formulate the nanocomposites. The impact of [EMIM]OAc on silica dispersion in a nitrile rubber (NBR) matrix was investigated by a transmission electron microscope and scanning electron microscopy. The combined use of the ionic liquid and silane in an NBR/silica system facilitates the homogeneous dispersion of the silica volume fraction (φ) from 0.041 to 0.177 and enhances crosslinking density of the matrix up to three-fold in comparison with neat NBR, and also it is beneficial for solving the risks of alcohol emission and ignition during the rubber manufacturing. The introduction of ionic liquid greatly improves the mechanical strength (9.7 MPa) with respect to neat NBR vulcanizate, especially at high temperatures e.g., 100 °C. Furthermore, it impacts on rheological behaviors of the nanocomposites and tends to reduce energy dissipation for the vulcanizates under large amplitude dynamic shear deformation.
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Creating long-lived topological textured liquid crystals (LCs) in confined nonspherical space is of significance in both generations of structures and fundamental studies of topological physics. However, it remains a great challenge due to the fluid character of LCs and the unstable tensional state of transient nonspheres. Here, we realize a rich series of topological textures confined in nonspherical geometries by drop impact assembly (DIA) of graphene oxide (GO) aqueous LCs. Various highly curved nonspherical morphologies of LCs were captured by gelator bath, generating distinct out-of-equilibrium yet long-lived macroscopic topological textures in 3D confinement. Our hydrodynamic investigations on DIA processes reveal that the shear-thinning fluid behavior of LCs and the arrested GO alignments mainly contribute to the topological richness in DIA. Utilizing the shaping behavior of GO LCs compared to other conventional linear polymers such as alginate, we further extend the DIA methodology to design more complex yet highly controllable functional composites and hybrids. This work thus reveals the potential to scale production of uniform yet anisotropic materials with rich topologic textures and tailored composition.
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Ultrasensitive and flexible pressure sensors that can perceive and respond to environmental stimuli have attracted considerable attention due to their potential applications in wearable electronics and electronic skin devices. Here, we report a simple and low-cost strategy to fabricate high-performance pressure sensors via constructing a unique conductive/insulating/conductive sandwich-like porous structure (SPS). Interpenetration of the conductive graphene network throughout the porous insulating interlayer produces a highly efficient transition from the non-conductive to the conductive state. Consequently, the SPS sensors exhibit an extreme resistance-switching behavior (resistance change of >105 at 30 kPa), high sensitivity (â¼0.67 kPa-1, <1.5 kPa), fast response/recovery time (â¼10 and â¼16 ms) and outstanding mechanical stability. Such SPS pressure sensors are applicable for detecting various mechanical deformation modes (press, bend and torsion) and different stress/strain levels (from gait feature, finger/wrist/elbow movement to breathing monitoring and real-time pulse wave), providing a new concept of device design for wearable electronic applications.
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Biological fouling, where marine microorganisms attach densely to various submerged surfaces, has been a serious economic problem worldwide. Different from most antifouling approaches based on stiff and solid materials or coatings, a soft and wet coating composed of zwitterionic polymer was prepared in this paper. With the combination of the anti-polyelectrolyte effect of poly-N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium betaine (PSBMA) and the typical polyelectrolyte effect of polyacrylic acid (PAA), a bicomponent hydrogel coating with weak swelling in saline solution was achieved, which could avoid peeling from solid substrates. The bicomponent hydrogel coating showed strong tensile properties and good compression performance and slipperiness. Although the large Young's modulus of the coating relatively weakens the drag reduction effect, entering the mixed lubrication region in low sliding rate is easy and a low friction coefficient at a high rate could thus be obtained. With the aid of silane coupling agent and weak deformation in water and saline solution, the hydrogel coating could be bound tightly on solid surfaces. After strong sandy water abrasion, the bicomponent hydrogel coating could maintain its original state without any cracks and peeling. The hydrogel coating exhibits good anti-bacterial adhesion and anti-protein adsorption. The bicomponent zwitterionic hydrogel coating reported here provides a new strategy for marine antifouling and drag reduction studies.
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Hydrogel films have promising applications in medical dressings, flexible electronics, etc. However, it is challenging to fabricate ultrathin hydrogel films with high toughness and controllable thickness. Here, we report a facile approach to prepare tough physical hydrogel films by spin-coating of a poly(acrylic acid-co-acrylamide) (P(AAc-co-AAm)) solution and subsequent gelation in FeCl3 solution to form carboxyl-Fe3+ coordination complexes. The thickness of the obtained gel films, ranging from several to hundreds of micrometers, was easily tunable by adjusting the spin conditions and polymer concentration. The thus obtained hydrogel films showed excellent mechanical properties, with tensile breaking strengths of 0.6-14.5 MPa, breaking strains of 140-840%, Young's moduli of 0.1-61.7 MPa, and tearing fracture energies of 300-1300 J m-2. Based on this approach, responsive tough hydrogel films can also be prepared by spin-coating of a poly(acrylic acid-co-N-isopropylacrylamide) (P(AAc-co-NIPAm)) solution. The obtained gel films showed a fast response (<60 s) and a large output force (â¼0.2 MPa) triggered by a concentrated saline solution, making them an ideal material in the design of chemomechanical devices. Furthermore, a bilayer hydrogel film was fabricated by two-step spin-coating of P(AAc-co-NIPAm) and P(AAc-co-AAm) solutions, which showed reversible bending deformation under external stimuli. This simple yet effective approach should be applicable to other systems to prepare versatile hydrogel films with tunable thickness and promising applications in diverse areas.
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Molecular weight strongly influences the molecular dynamics and rheological responses of nanocomposites, which is far from being well understood. Herein molecular dynamics and rheological behaviors of hydrophilic fumed silica filled unentangled polypropylene glycol (PPG) were investigated as a function of weight averaged molecular weight (M w) of PPG and volume fraction (∅) of silica. It is shown that M w does not affect the glassy layers surrounding the nanoparticles and the segmental dynamics of the mobile PPG phase. On the other hand, the mobile PPG phase in the highly filled nanocomposites exhibits an abnormal "more fragile" to "stronger" transition with increasing M w. The reinforcement and thinning behaviors are stronger in lower-M w nanocomposites with the "more fragile" mobile PPG phase. The results suggest that reinforcement of nanocomposites affects the dynamic fragility of the mobile phase of the matrix.
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There is substantial progress along with giant debate in reinforcement mechanisms in relation to structured filler network and heterogeneously retarded polymer dynamics, while the dissipation behaviors have never been clarified for nanoparticle filled polymers. Herein dynamic rheological behaviors of silica filled natural rubber were investigated. Master curves of linear rheology in the hydrodynamic regime and those of the nonlinear Payne effect at a predetermined frequency were created, disclosing a leading role of dynamically retarded bulk rubbery phase to the hydrodynamic regime and a leading role of molecular disentanglement in the bulk phase to the Payne effect. The methodology is able to account for both reinforcement and dissipation of the compounds as a function of filler content. Furthermore, a frequency-dependent hydrodynamic to non-hydrodynamic transition is revealed, revealing the importance of the relaxation of chains in the bulk phase to both reinforcement and dissipation of the compounds. It is suggested that the dynamics of the bulk phase play a critical role for the rheology in the hydrodynamic regime while the fractal filler aggregates become dominative only in the terminal non-hydrodynamic regime where the bulk phase relaxes sufficiently.
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Immobilized polymer fractions have been claimed to be of vital importance for sol-gel transitions generally observed in nanoparticle dispersions but remain a matter of debate regarding mechanism and difficulty for prediction. Here we investigate the immobilized layer structures of trifunctionality polyether polyol (PPG) near the surfaces of hydrophilic and hydrophobic fumed silica (FS) nanoparticles to reveal the role of surface chemistry on the molecular dynamics and sol-gel transitions of the dispersions. Using modulated differential scanning calorimetry, we measure the specific heat capacity during glass transition and the enthalpy during cold-crystallization. Comparing with hydrophobic FS that forms a fully immobilized (glassy) layer, we find that hydrophilic FS immobilizes more PPG, forming a partially immobilized outer layer being unable to crystallize next to the inner glassy layer. By correlating the thickness of the glassy layer with half of the minimum spacing between nanoparticles, we directly evidence the percolation of this layer along the nearest neighbor nanoparticles responsible for the sol-gel transition. Using effective volume fraction including the glassy layer, we successfully construct master curves of relative viscosity of both hydrophilic and hydrophobic FS dispersions, pointing to a common sol-gel transition mechanism mediated by the surface chemistry.