Poly(amide‐imide) resins are versatile high‐performance polymers used as primary electrical insulation. They can be synthesized by three well‐established methods, of which only two are commercially exploited. Outstanding characteristics include high thermal performance, chemical and abrasion resistance, and low coefficient of friction. Other industries also rely on these same properties for use as coatings, extrusion resins and films. Recent developments are discussed and future trends/product offerings are reviewed. Developments include corona‐resistant enamels, self‐lubricated and high‐abrasion‐resistance coatings. The hybrid automobile industry offers opportunities for further innovations in primary electrical coatings.
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 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.
Co‐solvents can minimize two of the major problems associated with the use of ionic liquids (ILs) as solvents for homogeneous derivatization of cellulose: high viscosity and limited miscibility with non‐polar reagents or reaction products. Thus, the effects of 18 solvents and 3 binary solvent mixtures on cellulose solutions in three ILs were systematically studied with respect to the solution phase behavior. The applicable limits of these mixtures were evaluated and general guidelines for the use of co‐solvents in cellulose chemistry could be advanced: Appropriate co‐solvents should have $E_{{\rm T}}^{{\rm N}} $ values (normalized empirical polarity) > 0.3, very low “acidity” (α < 0.5), and relatively high “basicity” (β ≥ 0.4). Moreover, novel promising co‐solvents and binary co‐solvent mixtures were identified.
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.
A method of manufacturing free‐standing, micrometer‐scale honeycomb polyetherimide films is reported for the first time. Films are manufactured with a dip‐coating technique under water‐assisted self‐assembly. It is shown that the addition of poly(organosilane/siloxane)s and poly(ethylene glycol) allows the formation of regular honeycomb patterns. The films demonstrated the high thermal stability inherent for polyetherimide. The wetting properties of films are reported. The presence of nanopores was revealed with SEM imaging of the films. The makeup of the films allows their use as asymmetric membranes for reverse osmosis and ultrafiltration.
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 physical model of dart impact tests of film manufactured from semi‐crystalline polyethylene resins is developed. The models treat the dart impact tests as a special case of the standard high‐speed stress/strain measurement performed on a polymer sample with a linearly changing cross section. They describe the dart impact strength as a complex function of the parameters that characterize the stress‐strain curve of the resin: stresses and strains at the yield, necking and breaking points. The models correctly predict the range of the dart impact strength (ASTM D1709, ISO 7765) and are suitable for semi‐quantitative characterization and ranking of linear low density polyethylene resins for film applications.
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.
Two organically modified (Cloisite® 30B and 10A) and one unmodified clay (Cloisite® Na) were added to a resol‐type phenolic prepolymer. The modified montmorillonites showed a better dispersion in the prepolymer. The dispersion of the clay, the chemical structure as well as the thermal degradation behavior of the cured polymer and nanocomposites were studied. It was observed that the addition of Cloisite® Na leads to enhanced crosslinking of the cured polymer, leading to a higher activation energy for thermal degradation. The resol with Cloisite® 10A contained a higher percentage of voids, which seems to be one of the major factors that reduce hardness and adhesive strength when the nanocomposite was applied to a metal substrate.
The preparation of nanofibrillar composite (NFC) materials using single‐polymer nanofibrils as starting materials is described. Such a possibility is offered by (i) the concept of polymer/polymer NFCs, which have recently been manufactured and represent a further development in the field of microfibril‐reinforced composites, and (ii) the opportunity to isolate neat nanofibrils through selective dissolving of the second blend component. The resulting nanofibrillar single‐polymer composites are characterized by superior mechanical properties (the tensile modulus and strength are improved up to 350%), competing with glass‐fiber‐reinforced PET.
SSP of PET has been thoroughly investigated under the regimes of chemical reaction and particle diffusion control. However, the majority of industrial PET plants operate under conditions of surface by‐product diffusion control, mainly due to recycling cycles of the carrier gas. The presence of residual volatile by‐products in the carrier gas (especially water) may affect adversely the polymerization reaction and the resulting polymer quality. For this reason, the effects caused by varying water vapor content of the carrier gas on the course of the PET SSP are analyzed, with emphasis on the intrinsic viscosity. The presence of small amounts of water in the carrier gas is found to exert a pronounced effect on the course of polymerization, leading to significant reduction of the molar masses of the final product.
A processing method based on stretching of molten polymer nanocomposites was applied to prepare dichroic films. First, dodecanethiol‐capped gold particles were embedded in low density polyethylene. The resulting isotropic films were stretched in the melt under uniaxial loading using an elongational rheometer. The melt elongation technique resulted in reproducible characteristics of the optical properties and can be directly transferred to an industrial scale. The organic coating of the metal particles plays an important role in the generation of the dichroism. A reactive surface (adsorbed perfluorophenyl azide) led to strongly agglomerated particles which obviously did not lead to dichroic films.
A facile and easily industrialized approach for preparing highly dispersed MMT/polymer nanocomposites is developed by combining the latex compounding method and a spray‐drying process. Clay particles are successfully delaminated into layers, and layer re‐stacking is effectively prevented. HR‐TEM and XRD results confirm that MMT layers achieve exfoliated or nearly exfoliated dispersion in both MMT/styrene‐butadiene rubber and MMT/PS nanocomposites. Compared with melt‐blended MMT/SBR composites, MMT/SBR nanocomposites prepared by this new strategy exhibit extremely high dynamic modulus.
A novel zirconia polyester nanocomposite is prepared using an in situ approach. Surface‐functionalized zirconia nanoparticles are obtained by attaching 3‐phosphonopropionic acid to the metal oxide. Neat and surface‐covered metal oxide particles are incorporated at the beginning of the polyesterification reaction of isophthalic acid and neopentyl glycol resulting in zirconia/poly(neopentyl isophthalate) (PNI) nanocomposites. TEM shows that the dispersibility of the inorganic filler is improved by covering the zirconia surface with carboxylic acid groups. These results are verified by SAXS. Rheological measurements reveal that the viscosities are increasing compared to pristine PNI at particle loads of 10 wt% (neat zirconia) and 5 wt% (phosphonic‐acid‐capped zirconia), respectively.
An in situ lubrication dispersion method is developed to achieve electrical conductivity in PP containing a small amount of MWCNTs. Good dispersion of the MWCNTs in PP is observed even after a short mixing time because the interactions between the entangled nanotubes are reduced. By in situ lubrication dispersion, the electrical percolation threshold of the PP nanocomposite can be as low as 0.5–0.7 wt% MWCNT. Rheological data also support percolation at 0.5 wt% MWCNT. With 0.5 wt% MWCNT, the slope of G′ at low frequency approaches unity and shows non‐terminal behavior. The proposed dispersion method enhances the wetting of MWCNTs and improves MWCNT dispersion compared to both direct mixing of MWCNT powder with a polymer melt and conventional master batch dilution.
A special mold with mechanically driven mold surface motions (rotation and axial) was developed allowing the imposition of different molding sequences, thus enlarging the possibilities of controlling the thermomechanical environment, and consequently the manipulation of the developed morphology. In this work, centre gated discs were injection molded with distinct rotation velocities of the mold surface. The moldings were characterized by several structure sensitive techniques. The imposition of a mold surface rotation has a marked effect on the morphology of the moldings, with novel molding morphologies being developed: a laminated skin–core structure featuring a dual shish‐kebab structure differently oriented relatively to the flow direction, one in each of the skin layer.
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.
Proton exchange membrane fuel cells (PEMFCs) have attracted tremendous attention because of their high efficiency compared to other types of fuel cells. Nafion is the most commonly used polymer for membranes used in PEMFCs. A large variety of nanoparticles of different natures and sizes can be blended with a Nafion matrix, generating a new class of nanostructured electrolyte membrane with interesting physical properties. In this paper, we discuss the recent progress in the field of Nafion‐based nanocomposite membranes. They exhibit a significant improvement in thermo‐mechanical and thermal stability as well as proton conductivity at very low filler contents. The preparation, characterization, and properties of various types of Nafion‐based nanocomposite membranes are critically reviewed, and detailed examples are summarized.
Cyano‐OPV moieties were covalently incorporated into a PETG backbone to create ductile amorphous polymers which change their PL and absorption color as a function of deformation. The cyano‐OPV concentration was systematically varied, and the composition was related to the material's optical response. This approach afforded PETG/dye copolymers which upon annealing display characteristics of aggregated dye molecules. The materials exhibit a significant color change upon compression, consistent with disassembly of the dye aggregates. This mechanochromic response is irreversible and can be detected by the unassisted eye.