The polyacrylonitrile/polymethyl‐methacrylate (PMMA/PAN) porous fibers, core–shell hollow fibers, and porous thin films are prepared by coaxial electrospinning, single electrospinning, and spin‐coating technologies, respectively. The different morphologies arising from different processes display great influences on their thermal and crystalline properties. The adding of PMMA causes porous structure due to the microphase‐separation structure of immiscible PMMA and PAN phases. The lower weight loss, higher degradation temperature, and glass‐transition temperatures of porous thin films than those of porous fibers and core–shell hollow fibers are obtained, evidencing that the polymer morphologies produced from the different process can efficiently influence their physical properties. The orthorhombic structure of PAN crystals are found in the PMMA/PAN porous thin films, but the rotational disorder PAN crystals due to intermolecular packing are observed in the PMMA/PAN porous fibers and core–shell hollow fibers, indicating that different processes cause different types of PAN crystals.
A gas‐permeable cellulose template for microimprint lithography has been synthesized and characterized for the reduction of template damage and gas trapping caused by solvents and oxygen generated from cross‐linked materials. The 5 μm line‐pattern failure of the microimprinted UV cross‐linked liquid materials with 4.7 wt% acetone as a volatile solvent is solved by using the gas‐permeable cellulose template because of its increased oxygen permeability. The gas‐permeable cellulose template also allows the use of volatile solvents with high coating property and solubility into the microimprinted materials instead of the compounds and plastic resins conventionally used in mold injection.
Superabsorbent hydrogel nanocomposites (SHN) with semi‐interpenetrating polymer network (semi‐IPN) are synthesized by the polymerization of acrylamide monomer in a polyethylene glycol aqueous solution in the presence of the octadecylamine (ODA)‐modified graphene oxide (GO‐ODA) nanosheets. The hydrogel composites are characterized by Fourier transform infrared spectroscopy, thermal gravity analysis, and scanning electron microscopy. The water absorbency of the resulting SHN in distilled water and saline solutions are measured. The results show that doping GO‐ODA nanosheets into hydrogel semi‐IPN would enhance both their salt resistance and water retention. Using a simple freezing‐dry method, porous SHN with macroscopically interconnected pores is prepared, which exhibits excellent separation ability for removal of trace water from oils. Based on their better water absorbency, salt resistance, and excellent oil/water separation ability, the resulting SHN has great potentials in a wide range of applications, for example, oil dehydration, absorption, and separation.
Aerogels have showed tremendous potential applications because of its unique and outstanding properties. Herein, a novel two‐step approach to form self‐assembly nanocomposite aerogels driven by the strong interactions between water‐soluble polyimide (PI) precursor polyamic acid salt (PAAs) and hydroxyl multiwalled carbon nanotubes (MWNTs‐OH) is reported. The PI therein constitutes the framework of the nanocomposite and raises the strength of the cell walls, which endows aerogels with superelasticity and robustness. The MWNTs‐OH is distributed uniformly into water via physical ultrasonic method followed by blending with PAA molecular. During the imidization process, electrically insulating polyamic acid (PAA)/MWNTs‐OH aerogels are converted to conductive PI/MWNTs‐OH nanocomposite aerogels owning to the removal of their oxygenic functional groups of OH functionalized MWNTs. Moreover, adding multi‐walled carbon nanotube (MWNTs) contributes to the reduction of shrinkage notably, which can be evidenced by scanning electron microscopy measurement and density data. The nanocomposite aerogels display a high elastic modulus, high compressive stress, superior robustness, and high stress‐sensitive electrical conductivity. Interestingly, the variation trend of the electric resistance with compressive strain (R /R 0–ε) plots is consistent with the compressive stress–strain (σ–ε) curves, which can be explained by the “interface contact spots” theory. And this finding could facilitate the development of polymer‐based nanocomposite aerogels as elastic conductors for various applications.
Nanofiber‐based hydrocolloid scaffold is prepared by colloid electrospinning of thermoplastic polyurethane (TPU)/sodium carboxymethyl cellulose (S.CMC) in tetrahydrofuran (THF)/dimethylformamide (DMF). The most suitable process of electrospinning for successful formation of fibers is investigated by controlling the concentration of polymeric solution and co‐solvent ratio. In order to accomplish high wettability, the amount of colloid (S.CMC) and the co‐solvent ratio (THF/DMF), which affects the morphology of fibers, are adjusted. Finally, the open wound healing effect is confirmed using nanofiber‐hydrocolloid from in vivo animal studies. A detailed study of the wound healing process is also demonstrated for the first time.
A self‐cleaning membrane that periodically rids itself of attached cells to maintain glucose diffusion could extend the lifetime of implanted glucose biosensors. Herein, we evaluate the functionality of thermoresponsive double network (DN) hydrogel membranes based on poly(N‐isopropylacrylamide) (PNIPAAm) and an electrostatic co‐monomer, 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS). DN hydrogels are comprised of a tightly crosslinked, ionized first network [P(NIPAAm‐co‐AMPS)] containing variable levels of AMPS (100:0–25:75 wt% ratio of NIPAAm:AMPS) and a loosely crosslinked, interpenetrating second network [PNIPAAm]. To meet the specific requirements of a subcutaneously implanted glucose biosensor, the volume phase transition temperature is tuned and essential properties, such as glucose diffusion kinetics, thermosensitivity, and cytocompatibility are evaluated. In addition, the self‐cleaning functionality is demonstrated through thermally driven cell detachment from the membranes in vitro.
Development of natural polymer biobased materials that are light responsive is very useful for industrial production and our lives for a sustainable world. In this work, on the basis of the strong hydrogen bonding interaction between cellulose chains and conjugated dye molecules, fluorescent cellulose biobased plastics are fabricated successfully by hot‐pressing rhodamine B‐loaded and/or fluorescein‐loaded cellulose hydrogels, which are prepared in an aqueous 4.6 wt% LiOH/15 wt% urea solution pre‐cooled to –12 °C. The experimental results indicate that the fluorescent dye molecules are tightly fixed into the cellulose matrix through the capturing of cellulose to the hydroxyl and amino groups of rhodamine B and fluorescein. The fluorescent cellulose biobased plastics exhibit good thermal stability, excellent mechanical properties, and photoluminescence properties, with a significant fluorescent signal under UV fluorescent light. It is not hard to imagine that the RhB/cellulose biobased plastic (RhCBP) and fluorescein/cellulose biobased plastic (FCBP) thin belts or pieces could be easily embedded into paper during production because of the same cellulose component. Therefore, paper including a few of these fluorescent cellulose biobased plastics would be a good candidate for making anti‐counterfeiting banknotes.
A self‐healing polysaccharide hydrogel based on dynamic covalent enamine bonds has been prepared with a facile, cost‐effective, and eco‐friendly way. The polysaccharide hydrogel is obtained by mixing cellulose acetoacetate (CAA) aqueous solution with chitosan aqueous solution under room temperature. CAA is synthesized by reaction of cellulose with tert‐butyl acetoacetate (t‐BAA) in ionic liquid 1‐allyl‐3‐methylimidazolium chloride (AMIMCl). The structure and properties of CAA are characterized by FT‐IR, NMR, and solubility measurements. The results demonstrate that CAA possesses water solubility with a degree of substitution (DS) about 0.58–1.11. The hydrogel shows an excellent self‐healing behavior without other external stimuli and good stability under physiological conditions. Furthermore, the polysaccharide hydrogel exhibits pH responsive properties.
Hydrophobic and super‐hydrophobic materials have many important applications, but most of the artificially hydrophobic and super‐hydrophobic surfaces suffer from poor durability. Herein, a facile method is reported to fabricate robust hydrophobic and super‐hydrophobic polymer films through backfilling the silica colloidal crystal templates with the mixture of fluoropolymer, thermoset hydroxyl acrylate resins, and curing agent. After removal of the template, 3D ordered porous structures are obtained. The obtained polymer films have not only excellent hydrophobic or super‐hydrophobic properties but also good stability against temperatures, acids, and alkalis. Dual ordered porous structure can obviously enhance the hydrophobicity of polymer films compared to unitary one.
Three different dopants are used to fabricate electrospun dopants/polystyrene (dopants/PS) composite fibers from PS solution and PS sol. The relative humidity and the influence of the dopants on the morphologies, diameter, porous structures, and dopant distribution of electrospun PS fibers are investigated. Compared to those obtained from PS solution, electrospun dopants/PS composite fibers from PS sol with hollow‐porous and multichannel hollow‐porous structures present significant advantages due to the multi‐stage degree of interfacial structure and diversity of the internal environment. In comparison to coaxial electrospun PS fibers, the electrospun dopants/PS composite fibers from PS sol obtained in one step have an improved yield and a simplified technological process simultaneously, leading to significant competitiveness in fields such as catalysis, fluidics gas storage, and sensing.
Using synchrotron‐radiation X‐rays for nanoscale computed tomography (X‐ray nano‐CT), the structure and corresponding reinforcement effects of carbon black (CB) filler at various amounts in natural rubber (NR) are studied during cyclic loading. All structural parameters of the CB filler, which are extracted from X‐ray images—such as the destruction and reconstruction ratios of the aggregates and the network connectivity, show a transition point with the CB content at around 30 phr (phr = parts by weight per hundred parts of rubber). When the CB content is above the transition point, the effective volume fraction exceeds the percolation threshold, and a stress‐bearing filler network can form; this network can effectively transmit the external stress to the entire sample and abruptly enhance the reinforcement factor. Below the percolation threshold, the CB filler is mainly disconnected aggregates, where its reinforcement of the rubber matrix can be mainly described by the volume‐filling effect. Using the dynamic cluster–cluster aggregation (CCA) model, calculations of the mechanical properties related to the CB content suggest that the network structure plays a major role in the reinforcement of the NR.
Interfacial polymerization of dopamine and terephtaloyl chloride is performed on a porous crosslinked polyacrylonitrile support membrane. The resulting polymer layer has a smooth surface and is ultrathin (about 5 nm). The chemical nature of the interfacially polymerized layer is characterized by Fourier transform infrared spectroscopy and by X‐ray photoelectron spectroscopy. The thin‐film composite membrane is stable in aggressive solvents like dimethylformamide (DMF) and the membrane shows high solvent permeances combined with a molecular weight cut‐off below 800 g mol‐1. The remarkable stability in DMF, the ease of preparation as well as the extremely thin and smooth selective layer make this new type of bioinspired membrane attractive for solvent resistant nanofiltration.
Microcapsules containing an ionic liquid (IL) are potential candidate materials for preparing in situ self‐lubricating composites with excellent tribological properties. 1‐ethyl‐3‐methylimidazolium bis[(trifluoromethyl) sulfonyl]imide ([EMIm]NTf2) IL encapsulated polysulphone microcapsules are synthesized. The mean diameter and wall thickness are about 128 μm and 10 μm, respectively. Microcapsules have excellent thermal stability, with a thermal degradation onset temperature of 440 °C compared to traditional lubricants‐loaded microcapsules. In situ self‐lubricating composites are prepared by incorporating the IL‐encapsulated microcapsules into epoxy matrix. When the concentration of the IL microcapsules is 20 wt%, the frictional coefficient and specific wear rate of composites are reduced by 66.7% and 64.9% under low sliding velocity and middling applied load conditions, respectively, as compared to the neat epoxy. The tribological behavior of the self‐lubricating composites is further assessed in different applied load and sliding velocity conditions. The in situ self‐lubricating mechanism of composites is proposed.
Adsorption of a typical example of a new class of amino cellulose, namely 6‐deoxy‐6‐(2‐aminoethyl)amino cellulose at different pH‐values and in the presence of electrolytes, onto cellulose model substrates is studied with surface plasmon resonance and quartz crystal microbalance with dissipation monitoring. Unexpectedly, adsorption is consistently higher at a higher pH‐value of 10, indicating that solubility and interactions between amine moieties and cellulose are more important than electrostatic interactions. The findings are highly relevant for the process to modify material surfaces with amino cellulose in water‐based systems as a universal tool for changing the surface properties and chemistry. Potential applications for an antimicrobial all biobased material could be found, e.g., as medical textiles or in the biotechnology sector.
Pollution control has become increasingly important in recent years. Heavy metal ions, proteins, and dyes are frequently found in wastewater because of their extensive industrial applications. In this study, pH, temperature, and magnetic triple‐responsive poly(N‐isopropylacrylamide‐co‐methacrylic acid) porous microspheres doped with magnetite nanoparticles as a new type of smart adsorbents are used to remove the aforementioned pollutants. The pH‐ and temperature‐responsiveness of these microspheres realizes tunable adsorption toward Cu(II). Simultaneously, the microspheres exhibit good adsorption capability to lysozyme and basic fuchsine. Microsphere‐adsorbing pollutants are easlily separated from wastewater by applying an external magnetic field to reuse the microspheres.
The copolymerization of lauryl lactam (LL) with ε‐caprolactam (ε‐CL) initiated by the latent, CO2‐protected N‐heterocyclic carbene‐based initiators 1,3‐dicyclohexyl‐3,4,5,6‐tetrahydropyrimidinium carboxylate ( 6‐Cy‐CO2 ), and 1,3‐dimethyl‐3,4,5,6‐tetrahydropyrimidinium carboxylate ( 6‐Me‐CO2 ) has been explored. The temperature‐dependent exchange of the protecting group in 6‐Cy‐CO2 and 6‐Me‐CO2 with 13C‐labeled CO2 is studied to gain knowledge about the onset of CO2 release from the carbene. Under exclusion of moisture, a storable batch containing 75 wt% ε‐CL, 25 wt% LL, and another 5 wt% 6‐Cy‐CO2 can be prepared. This batch is successfully used in the in situ melt spinning of poly(ε‐CL)‐co‐poly(LL)‐based single‐filament fibers.
Colloidal assemblies of inorganic nanoparticles dispersed in liquid media hold particular promise for the creation of a unique class of functional materials with innovative applications. In the present report, “compound‐eye”‐like core–shell and Janus‐type silica and amino‐terminated 1,2‐polybutadiene (PB‐NH2) and polystyrene (PS) composite microspheres are successfully prepared by simply mixing an aqueous dispersion of silica particles into a tetrahydrofran (THF) solution of PB‐NH2, and PB‐NH2 and PS blends, followed by evaporation of the THF. This co‐precipitation process provides a new approach for producing organic–inorganic composite particles without the need for surface modification of the inorganic nanoparticles.
Mechanically robust and self‐healing rubbers are highly desired to satisfy the increasing demand of high‐performance smart tires and related materials. Herein, a self‐healing rubber nanocomposite with enhanced mechanical and self‐healing performance based on Diels–Alder chemistry has been investigated. The furfuryl grafted styrene‐butadiene rubber and furfuryl terminated MWCNT (MWCNT‐FA) are reacted with bifunctional maleimide to form a covalently bonded and reversibly cross‐linked rubber composite. Obvious reinforcing effect is obtained at high cross‐linking density. Over 200–300% increase in the Young's modulus and toughness can be achieved in the rubber nanocomposites with 5 wt% MWCNT‐FA. Meanwhile, the healing efficiency increased with MWCNT‐FA content. MWCNT‐FA plays dual roles of effective reinforcer and a kind of healant.
Blends of polyamide 12 and small amounts (0.15–1 wt%) of the excimer‐forming fluorescent dye 1,4‐bis(α‐cyano‐4‐octadecyloxystyryl)‐2,5‐dimethoxybenzene (C18‐RG) are produced by melt‐processing. While green monomer fluorescence from well‐individualized chromophores is observed at low dye concentration (0.15%), higher dye concentrations lead to aggregation of the dye so that the emission characteristics are dominated by red excimer fluorescence. Upon mechanical deformation of samples with appropriately selected dye content (0.25 wt%), a pronounced mechanochromic effect can be observed, which manifests itself through a mechanically induced transformation from excimer‐dominated to monomer‐rich emission. The monomer to excimer emission ratio IM/IE is increased by a factor of up to 2 in a step‐wise manner when samples are uniaxially deformed past the yield point.
Using a technique called solution blow spinning, polyurethane–carbon nanotube‐based composite nanofibers are fabricated. These composite nanofibers exhibit uniform diameter, even with increasing polyurethane density, with the use of a dual‐solvent mixture during spinning. It is possible to produce the fibers at a high production rate even after the addition of a large amount of carbon nanotubes with a uniform size distribution of 300–400 nm. In addition, for composites with 3 wt% carbon nanotubes, the tensile strength, elongation, and elastic strain energy increase to 102, 166, and 167%, respectively, compared to pure PU nanofibers. The thermal stability improves as well. The prepared composite nanofibers could potentially be used as an inter‐reinforcing agent in carbon‐fiber‐reinforced plastics and as a buffer, and in the biomedical field.
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