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.
Polyimides function under high‐temperature sliding. The available literature explains transitions in friction and wear mainly by mechanical effects, such as influences of normal load, sliding velocity and humidity on polymer transfer to steel counterfaces. Theoretical models are evaluated for sintered and thermoplastic polyimides. Tribologists have been interested in tribochemical and tribophysical reactions in the sliding interface for about 25 years. Reactions such as hydrolysis, imidisation and/or degradation occur as a function of sliding temperature and are reviewed in this paper. An overview of polyimide synthesis and degradation is presented, while new insights in sliding mechanisms are obtained from a detailed study of Raman spectroscopy on worn polymer surfaces.
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.
A new technique for design and preparation of self‐reinforced starch films is introduced. The films were based on a high‐amylose corn starch that was chemically modified in different ways. Hydroxypropylation was used to decrease gelatinization temperature and improve processability. The reinforcing component consisted of cross‐linked starch granules, where the crosslinking increased granule thermal stability and moisture resistance. Distribution of the cross‐linked starch was imaged by CLSM, and the matrix/particle interface was studied by SEM. Modulus and tensile properties of the starch film were increased by about 30 and 20%, respectively, after addition of rigid cross‐linked starch particles. A perfect interface between matrix and reinforce agent was obtained.
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.
The electrospinning method was used to fabricate nanostructures of Nafion‐poly(vinyl alcohol) (PVA) and Nafion‐poly(ethylene oxide) (PEO). Depending on the ratio between the two polymers, nanospheres and/or nanofibers could be obtained in a reproducible manner. The Nafion‐PVA mats were found to be more conductive than the Nafion‐PEO ones, possibly because of their better mechanical properties when swollen by water. The fiber morphology was always found to be more conductive than the sphere morphology. However, all electrospun mats presented ionic conductivities slightly lower than extruded Nafion 115 or Nafion‐PVA cast films.
A PVK/MWNT nanocomposite coating on stainless steel is developed and tested for antimicrobial and anticorrosion properties. The coating is prepared via electrochemical deposition onto SS surfaces and is monitored using cyclic voltammetry. High‐resolution XPS measurements of the C 1s and N 1s regions are used to estimate the film composition. AFM shows a homogeneous thin film of several µm thickness with well‐defined globular domains. The bactericidal functionality of the electrodeposited film is demonstrated by its antibacterial activity against Escherichia coli, even with low MWNT loading (≈6%). The excellent anticorrosion property of the coating is demonstrated after 7 d of exposure to NaCl (0.5 M ) solution.
Novel silver/polymer composites based on thiol‐ene chemistry are prepared by an in situ bottom‐up approach. The in situ synthesis of silver particles inside the polymer matrix is achieved in one pot by photoreduction reaction in presence of a silver precursor and the concurrent crosslinking reaction. XPS analysis confirms the formation of silver particles; TEM morphological investigation shows a very good dispersion and distribution of the nanometric silver particles within the thiol‐ene network. Antimicrobial properties of the photocured hybrids are also evaluated.
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 novel mesoporous material (“nanopaper”) prepared from template‐synthesized, polyelectrolyte‐stabilized polymer nanotubes is reported. The stacked network of completely collapsed, flat nanotubes forms the porous structure, which has a water‐vapor permeability that can be tuned by the stabilizer. The transport mechanism is elucidated based on microscopy, thermal analysis, spectroscopy characterization, and mass‐transfer theory. The results suggest that the nanotube surface plays a key role in the through‐film transport process. This effect vanishes in the more open films formed from micro‐fibrillated cellulose having similar fibril diameters. Nanopaper mechanical properties are also reported. With a pore structure and functionality that can be varied, nanopaper is a promising functional membrane.
Reproducible and controllable hydrophilic layers were grafted on macroporous PP membranes by surface initiated grafting. Two methods were adopted, i.e., through adsorption of or entrapping the photo‐initiator on the membrane surface. The latter method yielded longer grafted chains under otherwise identical conditions. Depending on monomer solution composition, brush layers or network‐like structures were grafted onto the entire membrane surface without significant loss of water flux. The influence of the structure of grafted layers on water permeation, protein adsorption, and protein microfiltration fluxes was investigated. It was found that membranes grafted with network‐like structures have the best performance.
Improving the conductivity of electrospinning solutions is often achieved by adding small amounts of conductive additives. HMIMCl, a room temperature ionic liquid, and TEBAC, a quaternary ammonium salt, were added to polylactic acid in chloroform and their effects on solution properties, electrospinning, and fiber properties were investigated. Both additives increased the conductivity which decreased the fiber diameter, but differences were observed on the fiber dispersity and fiber morphology. The conductive solutions caused fiber backbuilding with aggregation and fiber fusion. Reasons for the differences in fiber diameter and fiber morphology are discussed.
In order to enhance the molecular orientation of electrospun nanofibers, a novel collection technique is proposed and applied to the spinning of polyethylene from high temperature solution. The technique makes use of a parallel‐electrode collector that acts before solidification of the fiber occurs. The resulting multiple‐necking morphology is composed of fine nanofibrils with very small diameter and narrow size distribution. The crystalline orientation of the nanofibrils was analyzed by TED. The formation mechanism of the nanofibrils is discussed. The strong elongational effect of the electric‐field‐induced stretching force in the parallel‐electrode collector is demonstrated by the orientational analysis and by observation of the multiple‐necking morphology.
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.
The impact of the deformation conditions, specifically the temperature, on the shape‐memory behavior and characteristics of epoxy SMPs is studied. By simply varying the temperature during deformation (i.e., the programming step of the SM effect), the ultimate strain of the formulated epoxy was improved three‐ to five‐fold, thereby providing for an increased range of reachable deformation strains during SM thermo‐mechanical cycling. This research unveils newly developed epoxy‐based SMPs with improved deformability range and high strength with intrinsically good thermal and chemical stability.
Thermo‐responsive PNIPAAm/PLLA nanofibrous films with tunable surface morphologies and better biocompatibility were prepared by electrospinning technique. The electrospun composite films possessed a “bead‐on‐string” structure. The wettability of nanofibrous films was observed by water CA measurements. The results showed that the electrospinning process and addition of PLLA did not change the thermo‐sensitivity of PNIPAAm. The wettability of electrospun PNIPAAm/PLLA composite films could switch from superhydrophilic to superhydrophobic when the temperature increased from 20 to 50 °C. Electrospinning is a promising way to create stimuli‐responsive surfaces with potential application in the design and tactics of controllable drug delivery system.
Both α‐cyclodextrin and linear dextrin are used to prepare biocomposites with poly(3,4‐ethylenedioxythiophene). Materials are prepared electrochemically in aqueous solution. Comparison with the pure polymer indicates that the electroactivity and electrostability decrease with the incorporation of the dextrins while the electrical conductivity is retained. The different properties of the two biocomposites suggest that the linear dextrin is mainly located at the surface, whereas the cyclodextrin is homogeneously distributed in the polymeric matrix. Cell adhesion and proliferation assays indicate that the cellular activity is significantly higher in the dextrin‐containing biocomposites.
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.
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.
