Photoembossing is a cost‐effective technique for the production of complex surface relief structures in a photopolymer film, achieved via contact‐mask exposure to UV‐light. Here, photoembossing is explored using interference holography with a CW laser and a nanosecond pulsed laser. It is shown that identical surface relief structures are produced if the photopolymer film is kept in a fixed position. In the case of a moving substrate, relief structures are only obtained with the pulsed laser and the heights of the relief structures and their shape are the same as in the static experiments. This illustrates that photoembossing in combination with pulsed laser interference holography is potentially useful in the production of large area structured films using roll‐to‐roll processes.
Epoxy‐networked materials containing N,N'‐dioctadecylimidazolium iodide are prepared by curing a mixture of DGEBA and different ratios of the ionic liquid with MCDEA at high temperature. The presence of ionic liquid results in an increase of the storage modulus and a decrease of the glass transition temperature, as indicated by DMA. Also, the onset curing temperature decreases as the amount of IL increase indicating that IL also takes part on the curing process. DSC and FTIR analyses confirm that the imidazolium‐based ionic liquid is able to promote the crosslink of the epoxy pre‐polymer without the presence of external curing agent.
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.
The purpose of the present contribution is to provide an efficient method that would help to quantify the orientational levels occurring in polymer/clay dispersions subjected to elongational flow. The extent of internal orientation developed in salt containing montmorillonite/poly(ethylene oxide) gels is investigated, combining shear and elongational rheology methods. Entropic changes indicate that the strength of the transient network present in each gel affects the orientational ability of clay particles and polymer chains. We found that an increased Hencky strain of the hyperbolic die leads to a higher variation of the calculated entropy of the material.
A new melt‐processable PTFE material is presented and characterized that provides new and economical solutions in polymer technology while bridging the gap between perfluorinated PTFE and fluorothermoplastic materials such as perfluoroalkoxy resins. Thermal transitions, MW and MWD, and microstructures of the melt‐processable PTFE materials are investigated and compared to standard PTFE, modified PTFE, and PFA materials. The influence of the polymerization type used for the preparation of the melt‐processable PTFE (emulsion and suspension polymerization) on the MWD and the comonomer distribution are discussed.
This is the first report on a thermoformable bionanocomposite based on a natural nanocrystal and formed by grafting long polymer chains onto the surface of microcrystalline cellulose. For the cellulose nanocrystal‐graft‐poly(ε‐caprolactone), the “graft from” strategy contributed to long and dense “plasticizing” PCL tails onto the CN surface as the key of thermoforming. The grafted PCL chains shielded the hydrophilic surface of CN and, hence, showed high water‐resistance. Moreover, a strategy for developing new bionanocomposite materials based on natural nanocrystals has been presented.
In this study, the sol‐gel transition temperature of a thermosensitive chitosan system was measured using SAOS, in‐real time FTR and multi‐frequency SAOS excitation. From FT analysis, we found that the intensity of the harmonics stayed constant while the chitosan system remained in the solution state, while it increased passed the gelation point. Multi‐frequency SAOS excitation was also carried out using a summation function of sine waves that allowed performing the measurements in the LVR. This last technique could determine the unique (frequency independent) critical sol‐gel transition temperature, and was found to be less tedious than the application of the traditional Chambon and Winter's method.
In this paper, a novel intumescent system including MP as well as PER/TPU which acts as composite charring agent, is adopted to flame‐retarded PP. The encapsulation of charring agent PER by TPU effectively avoids the reaction of PER with MP during the compounding with PP at high temperature and also prevents the leaching out of polar PER from nonpolar PP matrix, thus remarkably enhancing the stability and water‐resistance of the intumescent system. PER and TPU have different but complementary charring mechanisms. So flame‐retarded PP with MP/composite charring agent shows a much better charring performance and flame‐retardancy than MP/PER flame‐retarded PP. The experimental results show that the former can reach UL‐94 V‐0 rating at 1.6 mm thickness at 25 wt.‐% flame retardant loading.
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.
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 effects of process engineering in the fabrication of PHBV, PLA and their blends prepared by melt blending are studied. The elongation of an optimized blend can be improved by 148 and 250% over the virgin PHBV and PLA polymers, respectively. DSC shows that the two polymers are immiscible in blends of any composition. The crystallinity of PHBV is hindered by the presence of PLA. UV‐Vis demonstrates the opacity of the blend with incorporation of PHBV to the PLA phase. The observed tensile modulus of the optimized sample is compared with theoretical values from the rule of mixtures. Gordon‐Taylor's equation is applied on the glass transition temperatures for theoretical modeling to explain the miscibility of the polymers.
A method that combines UV irradiation and pausing was developed to manipulate the regularity and the length scales of the morphology generated by phase separation in full‐interpenetrating polymer networks of polystyrene and poly(methyl methacrylate). Upon increasing the pause time of photopolymerization and photo‐crosslink processes, the morphology gradually changes from hexagonal‐like packing to random structures. The width of the loss tan δ obtained for these phase‐separated materials changes with the morphological regularity, suggesting a potential technique for fabrication of mechanical bandgap materials.
Native and nucleated PHB has been melt‐spun and the properties of the resulting fibers have been investigated. Biocompatible nucleating agents such as HAP and THY were compared to BN as a reference material. DSC was used to investigate the non‐isothermal crystallization kinetics as a function of processing temperature and cooling rate. It was found that particularly the choice of process temperature can ensure sufficient primary crystallization of native PHB: heating not higher than 10–15 K above the melting temperature induced a favorable crystallization behavior of native PHB. Thus, melt spinning at low process temperatures without additives was demonstrated to be the key to the formation of well‐defined hollow PHB fibers.
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.
A detailed finite‐element analysis of possible influences on the stiffness reduction of layered laminates due to tolerable IFF has been carried out and the IFF accumulation has been calculated. It is shown that both the transverse Young modulus and the in‐plane shear modulus are degraded independently with increasing IFF density. The calculations show that the thickness of the layer affected by IFF has only a minor influence on the resulting degradation. In addition, it has been shown that the IFF accumulation can be calculated by applying the Puck criterion on the numerically calculated stresses.
Composites containing 50 wt.‐% fly ash in a PP homopolymer were prepared via batch mixing and compression moulding. The following coupling agents were evaluated: Lubrizol Solplus C800, N,N′‐(1,3‐phenylene)dimaleimide, γ‐methacryloxypropyltrimethoxysilane and maleic‐anhydride‐grafted PP. At the filler level investigated, C800 gave the best balance of composite strength and toughness. In the latter case filler‐matrix adhesion appeared weaker relative to γ‐MPS, BMI and m‐PP, all of which gave excessively strong filler‐matrix adhesion leading to a reduction in composite toughness. The unexpected weakness of the C800/fly ash interaction may be related to removal of surface calcium ions from the fly ash via reaction of a single calcium ion with two C800 molecules.
A reversible stress‐induced phase transition occurs by stretching syndiotactic copolymers of propene and 1‐butene with 1‐butene content higher than 70 mol‐%. It involves a non‐standard mode of distortion of the crystalline lattice in a direction transverse, rather than parallel, to the applied tensile stress. We demonstrate that this distortion reflects conformational and crystallographic restraints on the slip processes involved at high deformations. This transition plays an important role in the elasticity of this novel class of thermoplastic elastomers, which show rigidity and mechanical strength two orders of magnitude higher than those of conventional elastomers.
Chitosan‐functionalized graphene oxides (FGOCs) were successfully synthesized. FGOCs were found to significantly improve the solubility of the GO in aqueous acidic media. The presence of organic groups was confirmed by means of XPS and TGA. Restoration of the sp2 carbon network and exfoliation of graphene sheets were confirmed by Raman spectroscopy, UV‐visible spectroscopy and WAXD. The SEM and AFM investigations of the resultant FGOCs showed that most of the graphene sheets were individual and few were layered. Controlled release behavior of Ibuprofen and 5‐fluorouracil was then investigated. We found that FGOCs are a promising new material for biological and medical applications.
A process we term “natural fiber welding” is demonstrated by which loose fibers are transformed to create a congealed network using an IL solvent. Several examples are discussed that include cellulosic and protein‐based materials. SEM shows the fusion of fibers upon treatment. XRD and FT‐IR spectroscopy of cellulosic materials show that significant amounts of the native polymer structure are retained after the process is completed. Data suggest that material at the fiber exterior is preferentially transformed while material in the fiber core is left in the native state. Data also demonstrate that the amount of material modified can be tailored by control of variables such as the IL solvent concentration, the process temperature, and the processing time.
