Nanoparticles based on Al(III) and Zr(IV) melamine phosphate and sulfate, respectively, are prepared. Cone calorimeter measurements reveal that compared to an unfilled polyacrylate matrix the polyacrylate‐based nanocomposites containing the novel nanoparticles display significantly improved flame‐retardant properties as evidenced by the corresponding values for the peak heat release rate, the time‐to‐ignition, the values for the peak rate of heat release, the total heat evolved, the time to the CO peak and the CO yield. Concomitantly, the mechanical properties of the acrylate‐based composite coatings, i.e., the Martens and surface hardness, can also be significantly improved.
The microencapsulation of alkaline salt hydrates suitable as inorganic phase change materials (PCMs) via surface Michael‐type addition polymerization of thiols and acrylates is reported. The encapsulation performance depending on the resins' acrylate‐to‐thiol ratio and monomer functionality is investigated, and the best encapsulation performance is found for resin compositions with considerable acrylate excess ratios. The step‐growth nature of the reaction can be substantiated via comparative bulk polymerizations. A multistage encapsulation mechanism is proposed in order to explain the different dependencies on the acrylate to thiol ratio observed in PCM encapsulations in comparison to bulk polymerizations.
The crystallization behavior of poly(L ‐lactide) (PLLA) was investigated in the presence of benzenetricarboxylamide (BTA) derivatives as crystal nucleators. BTA‐cyclohexyl (BTA‐cHe) was the most effective nucleating agent, but induced a complete loss of transparency of the processed material. On the other hand, BTA‐n‐hexyl (BTA‐nHe) enhanced crystallization with little increase in haze. PLLA containing BTA‐cHe enhanced PLLA crystallization in α‐form crystal whereas BTA‐nHe enhanced α′‐form (incomplete α‐form) with forming smaller spherulites. TEM revealed BTA‐nHe had completely dissolved in the PLLA matrix in melt and recrystallized during the thermal annealing process. It was also found that the size of the recrystallized BTA‐nHe was in the nanometer range to effectively nucleate the PLLA crystals.
A photoresponsive fluorinated azobenzene homopolymer is synthesized via TERP. UV irradiation of the surface based on a fluorinated azobenzene homopolymer with micro/nanostructures induces a tunable/switchable water droplet mobility. Water droplets can easily roll off the pristine surface at a small tilt angle (≈14°). The apparent water CA changes from 150 to 135° after UV illumination of the surface. Thus, water drops stick on the surface when the substrate is turned vertically or even upside down, indicating a very high adhesion force. Interestingly, the water droplet rolls off again under visible‐light irradiation. The as‐prepared surface may be useful for applications requiring switchable mobility of water droplets.
Glass fiber biobased composites have been prepared by ROMP of a commercially available vegetable oil derivative possessing an unsaturated bicyclic moiety, and DCPD. The resins and the corresponding composites have been characterized thermophysically and mechanically. Higher DCPD content yields materials with higher glass transition temperatures. Glass fibers significantly improve the tensile modulus of the resin from 28.7 to 168 MPa. These biobased composites utilize only a limited amount of a petroleum‐based monomer, while employing substantial amounts of a renewable resource.
Hybrid organic/inorganic acrylic nanostructured films were prepared by a UV/thermal dual‐curing process. The role of a fluorinated hydroxyl acrylate monomer (AF) as coupling agent was investigated. Increased Tg values and modulus of the dual‐cured films were achieved by increasing the TEOS inorganic precursor. The coupling agent deeply modified the surface properties of the cured films: the formation of hybrid films characterized by high hydrophobicity together with an increase on surface hardness was achieved. TEM analysis clearly evidenced the reducing of the nanosize dimensions of the inorganic silica domains by increasing the coupling agent content in the photocurable formulation.
A novel CMRF is synthesized from modified silicone oil, containing composite polyurethane microsphere additives, and surface‐coated iron particles. The CMRF is designed to act as a liquid spring with controllable damping properties in a damper system. The fluid compressibility is characterized by force/displacement measurements. The addition of composite polyurethane‐microspheres increases the strength and compressibility of the fluid. It also decreases the concentration of iron particles needed in order to achieve the same yield stress as commercially available MRF. Surface coating surface of the iron particles with poly(2,3,4,5,6‐pentafluorostyrene) via RAFT provides dispersion stability.
A recently developed electrohydrodynamic printing method is described that can be used to create ordered structures and complex patterns using coarse processing needles and two polymeric materials. The results highlight the method's potential for direct 3D writing of biomedical polymers and composites for a variety of biomedical applications.
Chemical and mechanical experiments are reported to elucidate the macroscopic effects of crosslinker length and composition on the thermomechanical response of acrylate‐based SMPs. To this end, EGA‐based formulations underwent a battery of basic tests which revealed that by increasing crosslinker chain length, polymer Tg can be decreased but there will be increases in compliance, step recoverability, and damping in a glassy state. Addition of methacrylate groups can cause increases in swelling, Tg, storage modulus in shorter chains, and greater damping at a rubbery state. All tested polymers exhibited mild hydrophilicity. PEGDA formulations exhibited good recoverability and could be an option for vascular applications.
A dual‐cure latex is prepared by mixing an amide‐functionalized latex with a latex that has both acetoacetoxy and unsaturated acrylic functionalities. The amide‐functionalized latex provides a thermal cure with the acetoacetoxy groups of the other latex via Michael addition. The partially polymerized triacrylates in the acrylate‐functionalized latex provide active sites for photocuring. Thermoset latex films are prepared by blending amide‐ and acrylate‐functionalized latexes in varying amounts. The effect of the photosensitizer (camphorquinone) concentration on thermal and mechanical properties is studied. The highest tensile modulus and elongation is observed in a 50:50 wt% amide/acrylate‐functionalized latex blend.
A novel technique is described that uses stretching‐controlled thermal micromolding with etched metal surfaces as templates for the mass‐production of superhydrophobic polymer films. First, the metal surface is etched and then used as a template to thermally replica‐mold the polymer (e.g., polyethylene). The resulting film surfaces exhibited stable superhydrophobicity with water contact angles >150° and sliding angles ≈7°. SEM imaging demonstrates that the microstructure on the superhydrophobic surface is formed by stretching from the microholes of the template during separation. This technique can be easily combined with melt‐flow casting for manufacturing superhydrophobic polymer surfaces on a large scale.
The electrospinnability of hordein and gliadin from acetic acid solutions is demonstrated and compared to that of zein. The relation between protein conformations in solution and the properties of post‐spun fibers are studied by means of CD, FTIR, TEM, DLS, viscosity measurements, SEM, and mechanical testing. The results show that both electrospinnability of the proteins and mechanical properties of post‐spun fibers are significantly influenced by solution protein conformations. Ultrafine fibers are fabricated at optimized concentrations, while large compact aggregates caused by hydrophobic interactions have a negative effect on the formation of continuous protein fibers. Moreover, hordein fibers show a lower cytotoxicity than gliadin and zein fibers.
Based on an in situ template method, branched phosphazene‐containing nanotubes were synthesized via a controlled two‐step adding technique of acid acceptors. Structural and morphological characterizations of the as‐synthesized products were performed by SEM, TEM, EDX and FTIR. The results showed that the branched nanotubes were had inner and outer diameters of 8 and 50–150 nm, respectively. In addition, a formation mechanism for the nanostructures was proposed.
The surface of natural Brazilian amazonic fibers (curauá, Ananas erectifolius) was modified with polyaniline nanoparticles, through in situ preparation of polyaniline nanoparticles in presence of the curauá fibers. This allowed for a significant increase in the electrical conductivity of the fibers (≈2 500 times). As the electrical resistivity of the modified fibers is a function of the applied external pressure, the produced composites can be used as a cheap pressure‐sensing material. The modified materials were also characterized by FT‐IR, XPS and SAXS, and the obtained results were used to explain some of the observed characteristics of the materials.
New dibenzoylgermanium derivatives are synthesized starting from various dithioacetal protected benzaldehydes by a coupling reaction with different dialkyldichlorogermanes and subsequent oxidative cleavage of the protecting group. The synthesized germanium compounds show a significantly stronger blue light absorption than camphorquinone. During irradiation, the dibenzoylgermanium derivatives undergo photodecomposition under formation of radicals. Therefore, the different dibenzoylgermanium derivatives are used as amine‐free visible‐light photoinitiators for dental cements and composites. Composites based on the different dibenzoylgermanes are storage‐stable and show a significantly improved bleaching behavior over composites with CQ/amine photoinitiators.
Composites of PUR and IL were prepared and specific conductivities and Shore A hardness were determined. IL were based on 1‐alkyl‐3‐methylimidazolium salts with counterions BF, PF, triflate, or ethylsulfate. Presence of IL increased the conductivity by five orders of magnitude. Variation of alkyl chain length and nature of counterions only had little effect on the conductivity. Presence of IL had a plasticizing effect, which was most pronounced for the IL with dodecyl groups and PF as counterion. In broadband dielectric measurements, the complex conductivity showed a characteristic dispersion that is caused by the interplay between (hopping) transport of charge carriers and electrode polarization.
A new, nickel‐coated graphite resistance‐change‐based method for gel‐point determination for epoxy‐based thermoset resins is presented and compared with DSC and rheological methods. Gelation times determined by this new method are in very good agreement with conventional techniques; this new method is potentially simpler and less time consuming than existing ones.
The synthesis of PMMA‐based nanoparticles (NPs) covalently labeled with a fluorescent dye is investigated for imaging applications such as cell uptake and biodistribution. Batch emulsion polymerization (BEP) and monomer‐starved semi‐batch emulsion polymerization (MSSEP) are adopted using SDS. Fluorescent properties are added to these NPs using Rhodamine‐B (RhB) as a fluorescent dye covalently bonded to 2‐hyroxyethyl‐acrylate. The resulting HEMA‐RhB monomer is copolymerized with MMA via BEP and MSSEP to synthesize fluorescent NPs. Subsequently, SDS is substituted with a biocompatible surfactant, Tween80, through ionic‐exchange resins. ζ‐Potential measurements confirmed the complete surfactant exchange that leads to biocompatible fluorescent NPs with tunable size and narrow size distribution.
This paper investigates the effect of both the clay loading and the monomer feed rate on the morphology and properties of poly(styrene‐co‐butyl acrylate)‐clay nanocomposites prepared in emulsion polymerization. Analysis by X‐ray diffraction (XRD) and transmission electron microscopy (TEM) of the nanocomposites prepared by batch polymerization showed that the polymer clay nanocomposites (PCNs) with 1–3 wt.‐% clay loading resulted in intercalated structures, while exfoliated structures were obtained at 10 wt.‐% clay loading. The polymerization was also carried out with semi‐batch polymerization. The morphology, thermal stability, and mechanical properties of nanocomposites obtained were found to be more strongly dependent on the clay/polymer ratio than the monomer feed rate.
In this paper, the preparation of polymer/silica nanocomposite particles in a convenient one‐step process, via in situ miniemulsion polymerization and the sol‐gel technique, is described. The products were characterized using differential scanning calorimetry, transmission electron microscopy, and dynamic light scattering. Moreover, the effects of various reaction parameters, including the content of silica and the concentrations of sodium dodecyl sulfate and potassium persulfate, on the particle size and size distribution were also investigated. It is shown that polymer/silica hybrid nanocomposite particles were successfully synthesized in one step by this novel technique.
