Short electrospun fibers were obtained by using UV cutting method. Either polymers with double bonds with a photocross‐linker (CL) and photoinitiator (PI) or known photochemistry of coumarin ([2 + 2] cycloaddition reaction) without the addition of CL and PI is utilized for making short electrospun fibers. The electrospun fibers were irradiated by UV light in the presence of a mask with a defined width of slits. The uncovered parts of fibers were cross‐linked and therefore became insoluble. The non‐cross‐linked parts were removed by immersion of the fibers into an appropriate solvent. The length of obtained short fibers can be controlled by changing the width of the slits of the employed mask.
Living radical polymerization (LRP) techniques and their ability to improve the morphology of crosslinked polymer networks by controlling polymer chain growth are reviewed. Recent successes in the creation of improved molecularly imprinted polymer networks are also discussed. LRP offers the ability to control molecular weight, polydispersity, and tacticity while reducing microgel formation in polymers created via free‐radical polymerization (FRP). The improved network architecture of polymers created via LRP has great potential, especially when considering imprinted networks which have traditionally been plagued by heterogeneity in network morphology and binding affinities. Using LRP can considerably improve template recognition and further delay template transport in imprinted polymers.
Cellulose microfibers were modified with two different bi‐functional monomers. Composites of EVA copolymer with modified and unmodified cellulose were prepared by melt mixing. The samples were analyzed by SEM, XRD, FT‐IR, DSC, TGA, DMTA and tensile mechanical tests. SEM showed that the presence of reactive groups on cellulose surface enhanced the compatibility, improving the fiber/matrix interfacial adhesion. FT‐IR disclosed the occurrence of chemical reactions between the functionalized cellulose and polymer chains. The incorporation of fibers affected the crystallization behaviour and crystallinity of the polymer matrix. Composites with GMA modified cellulose displayed better compatibility, higher thermal and mechanical properties.
The utilization of silk fibroin protein (SFP) in the field of biomaterials and tissue engineering plays an important role due to its promising mechanical, biological, and processing properties. In the present study, SFP solutions were exposed to ultrasound sonication to assess impact on molecular weight (Mw), sol–gel transition behavior, and physico‐chemical properties. The Mw of SFP was significantly reduced with sonication, determined by sodium dodecyl sulfate polyacrylamide gels (SDS–PAGE) gel electrophoresis. Sol–gel transitions were observed as SFP assembled to form a reversible SFP gel network at different concentrations and sonication time with the formation of a β‐sheet‐rich conformation in the gel state. The conformational changes and morphological properties were correlated over a range of SFP concentrations by circular dichroism (CD), UV spectroscopy, swelling and attenuated total reflectance fourier transformed infrared spectroscopy (ATR‐FTIR).
Cellulose‐based fibers were prepared by electrospinning from cellulose dissolved in NaOH/urea in the presence of a small amount of polyol binders. The as‐spun products were examined with SEM. Pure cellulose solution did not produce fibrous materials, because it often formed spherical nanoparticles with diameters ranging from 100 to 300 nm. However, bicomponent fibrous materials were obtained successfully from mixtures of cellulose and HMPEG or PVA by electrospinning. The cellulose/HMPEG electrospun fibers had average diameters of 400 nm. The content of NaOH and urea as well as the stiffness of cellulose chains were found to have significant effect on the electrospinning process.
Acrylic‐epoxy interpenetrating polymer networks were prepared by means of UV curing. The photopolymerization process was investigated via real‐time FTIR spectroscopy. The hybrid, cured films showed a broad tan δ peak in DMTA demonstrating the high damping properties of the hybrid, cured formulations. A decrease on shrinkage was achieved by increasing the epoxy‐resin content in the photocurable formulation, with a consequent increase in adhesion properties.
cis‐1,4‐Polyisoprene, a significant industrial elastomer, is electrospun into different nanostrucutures. Cis‐1,4‐polyisoprene electrospun fibers are prepared from cis‐1,4‐polyisoprene solutions in dichloromethane or chloroform and characterized by environmental scanning electron microscope and Fourier‐transform infrared spectroscopy. ESEM observation reveals that the cis‐1,4‐polyisoprene fibers show a bamboo‐like morphology with a nearly constant node distance, a diameter of 20–60 µm and a length of about 300 µm. In addition, within the individual nodes parallel grooves are clearly seen, which is very promising for their use in microprinting in the field of microelectronics. Smooth cis‐1,4‐polyisoprene fibers with a diameter of 5–8 µm can be obtained via electrospinning its chloroform solutions. In contrast to most polymers, the jet of cis‐1,4‐polyisoprene does not split during the electrospinning processes, which facilitates the collection of highly aligned fibers by using a rotating mandrel as a ground target.
UV‐cured polysiloxane epoxy coatings containing titanium dioxide were prepared by means of a cationic photopolymerization process. A good distribution of the inorganic filler was achieved within the polymeric network with an average size dimension of around 500 nm. UV‐vis analysis performed on organic dye (methylene blue) stained coatings showed a high efficiency of the titania photocatalytic activity: a complete degradation of the dye on the coating surface is reached after 60 min of UV irradiation without affecting the matrix photo‐degradation.
The effect of nanosilica addition on the morphology and mechanical properties of blends of isotactic PP and an ethylene/octene copolymer (EOC) is studied. TEM reveals that the well‐dispersed nanoparticles are localized exclusively in the PP phase. In the presence of a maleated PP compatibilizer addition of nanosilica leads to more finely dispersed EOC domains and a finer co‐continuous morphology. The nanoparticles reduce the rate of coalescence of the dispersed phase domains. The mechanical properties depend on the EOC and PP‐g‐MA content. Tensile and flexural properties are significantly enhanced in the presence of the silica nanoparticles, whereas impact properties are not affected. These enhancements are attributed to the favorable microstructure of the blends.
This study explored the combined influence of shear flow and nucleating agents on isotactic polypropylene (iPP) crystallisation. The study showed that oriented α‐iPP crystals were not necessary to form β‐iPP crystals, contrary to the accepted view that the surface of oriented α‐iPP crystals provides nucleation sites for an α‐iPP to β‐iPP growth transition. Instead it was proposed that flow‐induced mesomorphic point‐like nuclei preferentially nucleates β‐iPP. The combined effect of shear flow and nucleant was found to promote γ‐iPP crystals. The surprising γ‐iPP nucleation effect was explained by the high density of flow‐induced and heterogeneous nuclei present at the start of crystallisation.
Polymeric waste materials should be considered resources for the manufacture of new products through recycling processes, with a similar status to virgin fossil‐based plastics and biopolymers from renewable resources. Several efforts can be made to achieve this qualitative quantum leap in plastics recycling, and consequently introduce recycled products, with competitive performance, to the market. Scientific knowledge about the degradation processes during the life cycle and the development of fast and reliable analytical methods for the quality assessment of recycled plastics are fundamental to guarantee their performance in new applications. Different strategies—restabilisation, rebuilding, compatibilisation, and addition of elastomers and fillers—can be used to upgrade the structure and properties of polymeric waste streams. This review discusses recent developments in the mechanical recycling of plastics, focusing on how to produce quality materials from waste streams and, thus, contribute to a sustainable management of resources and energy.
Three types of acrylonitrile‐butadiene‐styrene rubbers with different rubber contents were used in the preparation of PC/ABS/MWCNT composites. It was found that localization of MWCNTs changes from PC to ABS phase when rubber content of ABS varies from 5 to 60%. This is discussed by a combination of thermodynamics and kinetics. Melting sequence and high viscosity of ABS are used to explain the localization of MWCNTs in the high viscosity ABS phase. The relationship between the localization of MWCNTs and the electrical resistivity of the composite is also investigated.
This paper presents the first results of a project aimed at investigating the arrangement of polyelectrolyte layers on unalloyed steel. We studied the structure of double and single polymer layers consisting of cellulose phosphate (HP‐PP‐C) and polyethyleneimine (PEI). Layers were characterized by variable angle ellipsometry, AFM and XPS. In particular, XPS indicated the incorporation of iron ions into cellulose phosphate layers, but, in contrast, these ions could not be observed in PEI layers. Results indicated that the homogeneity and qualitative corrosion performance of double layers (HP‐PP‐C/PEI) on unalloyed steel depend on the deposition of cellulose phosphate at the interface with steel.
Highly‐aligned luminescent electrospun nanofibers were successfully prepared from two binary blends of PFO/PMMA and PF+/PMMA. The PFO/PMMA aligned electrospun fibers showed a core/shell structure but the PF+/PMMA fibers exhibited periodic aggregate domains in the fibers. The aligned fibers had polarized steady‐state luminescence with a polarized ratio as high as 4, much higher than the non‐woven electrospun fibers or spin‐coated film. Besides, the PF+/PMMA aligned electrospun fibers showed an enhanced sensitivity to plasmid DNA. Such aligned electrospun fibers could have potential applications in optoelectronic or sensory devices.
The aim of the present contribution is to understand how ionic strength, brought by the addition of salt to laponite/PEO nanocomposite dispersions, influences the texture and adhesion characteristics at nano‐ and microscales in multilayered nanocomposite films prepared from such dispersions. At the nano‐scale, SAXS and XRD measurements indicated that the clay platelets orient parallel to the film plane and that the polymer chains intercalate the clay platelets regardless of salt addition. A gradual transition from an agglomerated structure, containing polymer‐rich and clay‐rich domains, to a fine‐balanced structure with smaller distinct details without excess PEO was observed, via AFM, on the exposed edges of cryo‐microtomed films with increasing ionic strength.
Silane coatings with different thicknesses were synthesized on CNFs for reinforcement of polyethylene composites. The thickness of the silane coating was adjusted by using a basic catalyst to increase the overall reactivity of the silane groups, resulting in a thick coating of ≈46 nm (ca. 90% increase in fiber diameter). DMA performed on the polyethylene composites showed a substantial increase in storage modulus from 1.68 to 2.34 GPa (40%) at low temperatures in the composite with the thick silane coating (≈46 nm) at a low loading of 0.4 wt.‐%. We believe that the silane‐treated nanofillers with thick coatings are very promising for high‐performance nanocomposites with non‐polar polymer matrices.
TMC/LLA copolymers with several TMC/LLA ratios are synthesized and a composite is obtained by reinforcing with short PLGA fibers. In vitro degradation is studied at 37 °C in pH = 7.4 buffer and compared with a PLLA homopolymer. The degradation of the copolymers appears slower than that of PLLA, showing that TMC units are more resistant to hydrolysis than LLA. Compositional changes indicate a preferential degradation of LLA units as compared to TMC ones. Morphological changes with crystallization of degradation by‐products are observed. The composite degrades much faster than the neat copolymer and PLLA because the faster degradation of PLGA fibers speeds up the degradation of the matrix. The composite appears promising for the fabrication of totally bioresorbable stents.
A new flame retardant based on an ammonium phosphonate is studied with respect to its thermal decomposition and its mode of action in wood‐plastic composites (WPCs). The measurements are carried out by means of fire tests (cone calorimeter) and pyrolysis investigations (thermogravimetry, infrared spectroscopy). The flame retardant acts mainly in the condensed phase by increasing the amount of residue formed by the wood part in the WPC. Additional flame dilution is achieved by the release of water, ammonia and carbon dioxide during the decomposition of the flame retardant.
The influence of the functionalization of fully condensed POSS cages on the properties of POM‐based nanocomposites is studied. POSS with different organic substituents [glycidylethyl, aminopropylisobutyl, and poly(ethylene glycol)] are taken into account and melt mixed with POM. Good dispersion was achieved upon the addition of amino functionalized POSS, leading to an increase on the thermal decomposition temperature under nitrogen atmosphere up to 50 °C. However, µm‐size aggregates were observed for other nanocomposites. There is no significant change in other thermal properties of the nanocomposites. The relationships among these effects and the morphological characteristics of the systems were analyzed.
This work reviews principles of Raman and infrared imaging, as well as applications of the art to understand physiochemical phenomena in polymer systems. Image sequences may be assessed in terms of spatial or spectral changes that occur over time, either within a specific region or across the field of view. As such, the methods have enabled the analysis of diffusion and dissolution processes at polymer interfaces, drug release from polymer matrices, and structural transitions among others. Despite analytical limitations imposed by resolution (spectral or spatial) and sample preparation, Raman and infrared imaging are powerful tools for relating performance attributes to molecular‐level characteristics.
