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.
In this work, anisotropic conductive film (ACF) is fabricated by shear‐flow induced assembly. It is found that an appropriate content of carbonaceous filler is needed for forming well‐ordered parallel vorticity‐aligned stripes and the content depends on the category of the filler. Interestingly, the lowest aspect ratio carbon black (CB) with lowest electrical conductivity is the best candidate for fabricating ACF. The film with CB stripes shows excellent conductive anisotropy: the electrical resistivity in the direction parallel to the CB stripes is almost eight orders of magnitude lower than that in the perpendicular direction. The formation mechanism of the vorticity‐aligned stripe is also investigated by the rheological measurement and the study of morphological evolution. It is found that the coalescence of dispersed phase or aggregates dominates the formation and growth of the stripe and negative value of the first normal stress difference drives the stripe to align along the vorticity direction.
Thermoset elastomers represent a class of polymers for a wide range of biomedical applications. Crosslinking density of thermoset elastomers is considered as an important parameter. In this study, semiquantitative Fourier transform infrared (FTIR) analysis is developed as a novel method to determine crosslinking density of poly (ester amide) thermoset elastomers. Poly(1,3‐diamino‐2‐hydroxypropane‐co‐polyol sebacate) (APS) is an example of poly(ester amide) thermoset elastomer. Polyethylene glycol (PEG) has been recently incorporated into APS polymer structure to obtain novel PEGylated APS‐based elastomers with tunable properties. The crosslinking densities of different APS and APS‐co‐PEG films are determined by the theory of rubber elasticity and FTIR. These results show that the intensity ratios between amide and carbonyl peak correlate well with the calculated crosslinking density from the elastic modulus. Thus, semiquantitative FTIR analysis offers a direct, facile, and less variable method to determine the crosslinking density and guide the consistent synthesis of poly(ester amide) thermoset elastomers.
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.
Light triggered soft actuator in aqueous media has applications in operating underwater objects, creating liquid flow, and adjusting reaction velocity, etc. Here, composites prepared from commercial materials, poly[ethylene‐ran‐(vinyl acetate)] (EVA) and aniline black (AB), are reported as one cost efficient material for preparing such actuator, where EVA and AB work respectively as shape‐memory polymer matrix and near‐infrared light triggered photothermal filler. Upon irradiation, the temperature of the composites increases greatly with light power density and AB content. Light‐induced shape‐memory effect (SME) with recovery ratio >98%, temperature‐memory effect (TME), and reversible bidirectional shape‐memory effect (rbSME) of the prepared composites in air are realized. Higher light power density is required to trigger the shape recovery in aqueous media, while good SME, TME, and rbSME are also achieved. Releasing device and gripper are used to indicate the feasibility of the composites as light triggered soft underwater actuators.
Graphene has resulted in significant research effort to generate polymer nanocomposites with improved mechanical, thermal as electrical properties as compared to pure polymers. A large number of studies have been undertaken using different graphene derivatives, filler loadings, synthesis methods, and so on to obtain optimum filler dispersion as well as filler–matrix interactions, which are crucial for achieving significant enhancement in the properties, especially at low filler fraction. This review summarizes the mechanical and thermal properties of numerous studies carried out for the property enhancements of commercially relevant thermosetting materials such as epoxy, polyurethane, natural rubber, melamine formaldehyde, phenol formaldehyde, silicones, vinyl ester, cyanate ester, and unsaturated polyester resin.
The previously introduced process for enzyme‐mediated in situ synthesis and deposition of eumelanin is investigated with covalent immobilization of the tyrosinase. It results in a monolayer structure of non‐coalesced melanin particles, with a film thickness of 5–8 nm. The reaction is self‐terminating due to overlay of the enzymes with particles. The melanin particles are rodlike with lengths down to 6 nm. Isolated melanin structures of such small size have not been observed before and might be a kind of protoparticle in the supramolecular buildup of melanin oligomers. Utilization of melanin particles with such small size can enable nanotechnological applications in the areas of bioelectronics and biosensors.
Rubber materials filled with reinforcing fillers display nonlinear rheological behavior at small strain amplitudes below γ0 < 0.1. Nevertheless, rheological data are analyzed mostly in terms of linear parameters, such as shear moduli (G′, G″), which loose their physical meaning in the nonlinear regime. In this work styrene butadiene rubber filled with carbon black (CB) under large amplitude oscillatory shear (LAOS) is analyzed in terms of the nonlinear parameter I3/1. Three different CB grades are used and the filler load is varied between 0 and 70 phr. It is found that I3/1(φ) is most sensitive to changes of the total accessible filler surface area at low strain amplitudes (γ0 = 0.32). The addition of up to 70 phr CB leads to an increase of I3/1(φ) by a factor of more than ten. The influence of the measurement temperature on I3/1 is pronounced for CB levels above the percolation threshold.
The introduction of nanodiamond particles (NDs) in silane‐crosslinked polyethylene is found to lead to a notable and systematic deformation of the polymer unit cell. X‐ray diffraction evidence of the existence of a modified crystalline structure in the bulk of the polymer due to the presence of NDs is reported here for the first time. The covalent bonding between NDs and the surrounding macromolecular chains may support that the excessive local stress field ultimately distorts the polymer conformation, yielding a new distorted but still crystalline interface. Supporting data from solid‐state NMR experiments confirm the existence of a modified crystalline interface of about 1–2 nm in all the nanocomposite materials.
Silicone materials are widely used in many fields such as electrical or food industries and their consumption is constantly growing. They are generally cured by vulcanization reaction for long time at high temperatures which requires high energy consumption. The possibility to achieve the polymerization of silicone rubbers by UV‐activation promotes the reduction of both time and temperature leading to an impressive energy saving. Indeed, this process is more than 30 times faster than the thermal one. Moreover, the properties of the two resulting materials are comparable, indicating that the low time of UV‐activated hydrosilation reaction is suitable for the formation of crosslinked silicone polymers.
In this study, the synergistic effect of functionalized carbon nanotubes (fCNT) and micron‐sized rubber particles in improving the thermomechanical properties of epoxy resin is demonstrated. fCNT is mixed with carboxyl‐terminated butadiene acrylonitrile toughened epoxy (CTBNTE) by ultrasonication followed by the addition of curing agent and mixing with planetary shear mixer. A significant improvement is noticed in fracture toughness (≈ 200%) and thermal stability (≈ 12 °C) of fCNT‐filled CTBNTE system but only a marginal improvement in fracture toughness and thermal stability of pristine CNT‐filled CTBNTE relative to epoxy. Dispersion of fCNT is better than pristine CNT in the epoxy matrix. Scanning electron microscope (SEM) images of fractured surface of fCNT‐filled CTBNTE reveal plastic deformation zone, stress whitening, and overall rougher surface compared to pristine CNT‐filled CTBNTE. The findings of our work show promise for use of fCNT in conjunction with a rubber toughener as filler for improving the properties of epoxy resin for advanced structural applications.
The water sorption and diffusion in (reduced) graphene oxide‐alginate composites of various compositions is analyzed. Water sorption of sodium alginate can be significantly reduced by the inclusion of graphene oxide sheets due to the formation of an extensive hydrogen bonding network between oxygenated groups. Crosslinking alginate with divalent metal ions and the presence of reduced graphene oxide can further improve the swelling resistance due to the strong interactions between metal ions, alginate, and filler sheets. Depending on conditions and composition, the overall water barrier properties of alginate composites improve upon (reduced) graphene oxide filling, making them attractive for moisture barrier coating applications. Water sorption kinetics in all alginate composites indicate a non‐Fickian diffusion process that can be accurately described by the Variable Surface Concentration model. In addition, the water barrier properties of sodium alginate‐graphene oxide composites can be adequately predicted using a simple model that takes the orientational order of filler sheets and their effective aspect ratio into account.
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.
Dopamine is a molecule that facilitates biomineralization, and it is used to prepare electropolymerization‐induced polydopamine (PDA). For the first time, dopamine is used for template‐free electrochemical polymerization to form biocompatible polypyrrole (PPy) nanofiber coatings on bone implants. Dopamine monomers are electropolymerized to PDA chains affixed to biomedical titanium after the nanomicelles are tuned to self‐assemble by triggering the potential, resulting in nanofiber formation. Dopamine serves as a dopant to induce the formation of conductive PPy nanofibers and as a promoter to accelerate biomineralization, cell proliferation, and adhesion.
A new facile approach for the fabrication of polymer‐Ag honeycomb film is reported. A polymer‐Ag+ honeycomb thin film is obtained by casting a CHCl3 solution of a functional graft copolymer on aqueous silver nitrate solution, leading to metal complexation induced phase separation at the air/water interface. The film is reduced by UV irradiation to give a polymer‐Ag honeycomb film with regular morphology. Pyrolysis of the film gives a translucent Ag honeycomb film.
A conjugated polymer, poly(9,9‐bis(6‐bromohexyl)‐9H‐fluorene‐alt‐1,4‐phenylene), is synthesized, converted to nanoparticles via a nanoprecipitation process, and utilized to fabricate thin films including conjugated polymer nanoparticles. The nanoparticles with surface bromides can be conjugated with an amine‐functionalized dendrimer via a nucleophilic coupling reaction. Thus, when microliter solutions of the particulates are dragged at a constant velocity on substrates alternately in a layer‐by‐layer manner, thin films composed of the nanoparticles and dendrimers can be successfully built up on the substrates. Our results suggest a methodology to control the deposition of thin films bearing conjugated polymer nanoparticles while minimizing processing time and decreasing material consumption.
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.
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.
A 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO)‐triazine based anhydride (2,4,6‐tris‐(DOPO‐methylformatephthalic anhydride‐phenoxy)‐1,3,5‐triazine (TDA)) is synthesized and used as a halogen‐free flame retardant co‐curing agent for diglycidyl ether of bisphenol A/methylhexahydrophthalic anhydride (DGEBA/MHHPA) system. The conjugation of anhydride group is increased by the utilization of TDA, leading to the reduction in the curing activation energy. The cured epoxy resin passes V‐0 rating of UL 94 test with the limiting oxygen index of 32.7 vol% when the phosphorus content is only 1.5 wt%. The flame‐retarding action of triazine ring and DOPO moiety is investigated by the residue analysis and the characterization of pyrolysis gas. Due to the presence of bulky aromatic subunits in the molecular structure of TDA, the flame‐retarded epoxy resins maintain the high glass transition temperature of DGEBA/MHHPA. Besides, the moisture absorption is diminished following the usage of TDA.
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.
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