The flame retardancy mechanisms of aluminium diethylphosphinate (AlPi) and its combination with melamine cyanurate (MC) in glass‐fibre‐reinforced poly(butylene terephthalate) (PBT/GF) were analysed using TGA including evolved gas analysis (TGA‐FTIR), cone calorimeter measurements using various irradiations, flammability tests (limited oxygen index, LOI, UL 94) and chemical analyses of residues (FTIR, SEM/EDX). AlPi decomposed mainly through the formation of diethylphosphinic acid and aluminium phosphate and influenced the decomposition of the PBT only slightly. AlPi acted mainly through flame inhibition. A halogen‐free V‐0 PBT/GF material was achieved with a LOI of 44%. Additional charring influenced the flammability. MC decomposed independently of the polymer and showed some fuel dilution effects.
Poultry feather fiber is transformed into biothermoplastics using a twin screw extruder, and the plasticizing effect of four different plasticizers on the material properties is investigated. Conformational changes, viscoelastic behavior, thermal degradation, and phase transitions are assessed by means of FTIR spectroscopy, DMA, TGA, and DSC, respectively. The mechanical properties of the plasticized resins are assessed by tensile measurements, while optical transmittance is recorded using UV‐Vis spectrophotometry. The water uptake behavior of the fiber keratin and plasticized resins is also investigated.
A new completely biodegradable shape‐memory elastomer consisting of PLLCA reinforced by in situ PGA fibrillation is described. The manufacturing processes and shape‐memory effects of the composites are discussed. DMA results reveal a strong interface interaction between in situ PGA fibrillation and PLLCA. Compared with the SMP‐based composites that are commonly used, the shape‐memory test shows that in situ PGA fibrillation can improve the recovery properties of PLLCA; in fact, the shape‐recovery rate increases from 80.5 to 93.2%.
A range of bio‐based rubbery thermosets have been synthesized by the cationic copolymerization of conjugated soybean oil, styrene, and 1,5‐hexadiene or isoprene as flexible crosslinkers. The thermal, and mechanical properties, as well as the wear behavior, of these new bio‐rubbers are reported. The amount of styrene and the type of diene incorporated have the greatest influence on the properties of the final materials. The largest variations are found in glass transition temperature, storage modulus, tan δ values, crosslink density, and abrasive wear depth, while thermal degradation and extraction analyses showed minimal variations with changes in composition.
Bio‐stereo nanocomposite polylactides are prepared by polymerization followed by stereocomplexation in scCO2/dichloromethane through in situ polymerization and master batch processes. The bio‐stereo nanocomposite polylactides show intercalated‐exfoliated and fully exfoliated nanoscale clay distribution in a perfect stereocomplex polylactide matrix. In situ polymerization proves better strategy to produce well‐exfoliated silicate layers in the stereocomplex matrix compared to the MB route that increases the melting temperature by up to ≈64 °C. The thermal properties of these materials maintain both stereocomplex and nanocomposite features simultaneously. The results open a new and versatile way to develop polylactide‐based materials.
A series of hydrogels based on poly(ethylenglycol) methyl ether methacrylate (PEGMEMA) is synthesized using macromonomers of three different molecular weights, in combination with varied degrees of chemical crosslinking. The effects of PEGMEMA, initiator, and crosslinker concentrations on gel yield and swelling properties are studied. In addition, the chemical structure of the gels is characterized by FTIR and solid‐state NMR spectra. The swelling and rheological behaviors of hydrogels as well as protein partitioning into the gels are discussed in terms of the network mesh size. Low protein sorption and bacteria deposition tendencies indicate that PEGMEMA‐based hydrogels could be highly beneficial for uses as fouling‐resistant materials, for instance, as protective coatings for desalination membranes.
A fabrication setup was specially designed so that one stream of sol of polyvinyl pyrrolidone (PVP), electrospun to form a bundle of fibers, acted as an axis between two rotating needles, and a second stream of PVP sol containing copper nitrate was electrospun around the fiber bundle axis to form a coil. This was turned into a coiled ribbon upon treatment in moisture. After calcination and reduction, a helical microcoil of nanocopper ribbon was produced, with controlled diameter and pitch. The width and thickness of the ribbon could be varied by manipulating the diameter of the coiled fiber and its treatment time in moisture.
The supramolecular structure in pipe walls of isotactic PP‐R is a function of compound composition and processing parameters, which both influence the mechanical properties of the pipes. µFTIR shows a gradient of the crystallinity across the pipe wall, with a lower‐crystalline outer layer, and a higher‐crystalline core layer. The rate of extrusion has an influence on the thickness of the outer layer. The nucleating effect on the morphological profile throughout the pipe wall can be visualised. µFTIR shows a homogeneous distribution of the primary antioxidant in the pipe wall. Both the spectral crystallinity and the antioxidant concentration distribution are calculated.
An improvement to a previously published suspension polymerization process for the production of spherical core/shell PVAc/PVA particles is described. To increase the settling time of the beads in the suspension, an expansion stage was introduced. The core/shell structure was obtained through the partial hydrolysis of the PVAc. The particle density was manipulated through addition of a solvent during the suspension polymerization stage and posterior expansion of the polymer beads obtained at the end of the process. This technique allows for effective reduction of the density of the final polymer beads. The expansion stage exerts also a beneficial effect on particle drying, avoiding particle aggregation during post‐polymerization processing of the polymer beads.
The influence of the flow history experienced during injection molding on the mechanical properties of amorphous polymers is investigated. It is demonstrated that flow‐induced molecular orientation only causes a small anisotropic effect on the yield stress, which can be regarded as insignificant with respect to its absolute value. Its influence on the post‐yield strain‐hardening response is also shown to be imperceptible, in contrast to a orientation which is applied during deformation below the glas transition.
Copolymers of 3,4‐ethylenedioxythiophene and 3‐methylthiophene have been prepared by recurrent potential pulses using monomer mixtures with various concentration ratios, their properties being compared with those of the corresponding homopolymers. In addition, different technological applications have been tested for the generated copolymers. Results indicate that the properties of the copolymers are closer to those of poly(3,4‐ethylenedioxythiophene) than to those poly(3‐methylthiophene). Furthermore, the ability of the copolymers to store charge and to interact with plasmid DNA suggest that they are very promising materials.
A systematic study of the effects of , flow rate, voltage, and composition on the morphology of electrospun PLGA nanofibers is reported. It is shown that changes of voltage and flow rate do not appreciably affect the morphology. However, the of PLGA predominantly determines the formation of bead structures. Uniform electrospun PLGA nanofibers with controllable diameters can be formed through optimization. Further, multi‐walled carbon nanotubes can be incorporated into the PLGA nanofibers, significantly enhancing their tensile strength and elasticity without compromising the uniform morphology. The variable size, porosity, and composition of the nanofibers are essential for their applications in regenerative medicine.
The influence of coupling agents on the melt rheological properties of natural fiber composites has been investigated in this work using capillary and rotational rheometers. Scanning electron microscopy was also employed to supplement the rheological data. It was found that molecular weight and molecular weight distribution of the polymer matrix and coupling agent characteristics influence the filler wetting and the melt flow properties of the filled composites. Generally, low molecular weight and narrow molecular weight distribution polyethylene matrix provides relatively larger increase of the viscosity of the composites. Coupling agents tend to increase the resistance to shearing, but wall slip effects may interfere with the measured values, especially at very high filler loadings. Entrance pressure loss in capillaries is also influenced by polymer matrix and coupling agent used.
PSU/MMT nanocomposites are prepared by dispersing MMT nanolayers in a PSU matrix via in situ photoinduced crosslinking polymerization. Intercalated methacrylate‐functionalized MMT and polysulfone dimethacrylate macromonomer are synthesized independently by esterification. In situ photoinduced crosslinking of the intercalated monomer and the PSU macromonomer in the silicate layers leads to nanocomposites that are formed by individually dispersing inorganic silica nanolayers in the polymer matrix. The morphology of the nanocomposites is investigated by XRD and TEM, which suggests the random dispersion of silicate layers in the PSU matrix. TGA results confirm that the thermal stability and char yield of PSU/MMT nanocomposites increases with the increase of clay loading.
Cross‐linked alginate capsules a few millimeters in diameter have been formed by immersion in a CaCl2 solution. When adding cellulose whiskers or microfibrillated cellulose to the aqueous alginate solution, nanocomposite capsules containing 40 wt.% cellulosic nanoparticles were obtained. The morphology and compression strength of these capsules were investigated by microscopic observations and crushing tests, respectively. The capsules were extruded with a thermoplastic polymer. Visual inspection of the ensuing films shows a nonhomogeneous dispersion of the capsules that kept their integrity after extrusion. It results in preliminary disappointing mechanical properties of the composite films. However, further investigation is in progress to optimize this simple and ecofriendly process.
Ice‐templated aerogels made from water soluble/dispersible raw materials are formed through an environmentally friendly freeze‐drying process. The structures that result from ice templating are capable of absorbing liquids into their large void volume. The effects of polymer chemistry and material loading on the absorption into the dried materials are studied. Low‐density samples were able to absorb liquids rapidly but the liquid‐saturated structures lacked mechanical integrity. The higher‐density samples absorbed liquids more slowly and again retained little structural integrity. The addition of fibers and firing of low‐density clay aerogels into ceramics provide multiple routes to creating structures exhibiting rapid absorption and a rigid, stable structure when saturated.
The potential synergy of melamine polyphosphate and layered silicates for enhancing the flame retardancy and physical properties of polyamide 6 is investigated. Through melt blending, exfoliated nanocomposites were prepared, suffering, however, from polymer degradation. In the presence of the additives, the ability of polyamide 6 to crystallize was restrained and its thermal stability was deteriorated. Nevertheless, the stiffness of the polymer was increased, yet at the expense of ductility. Apart form stiffness, the additives exerted a positive effect on the fire resistance of polyamide 6; melamine polyphosphate and layered silicates cooperated during combustion to provoke the formation of a superficial protective barrier, yielding materials of inferior flammability.
The processes of melting and crystallization of blends based on HDPE and EOC were investigated. DSC thermograms showed that a separate crystallization and co‐crystallization occurred in the blends studied. Avrami approach was used to analyze the kinetics of crystallization in the blends. It is shown that the Avrami exponent depends on the EOC concentration of the samples studied. The difference in the Avrami parameters for HDPE, EOC and the blends indicated that the nucleation mechanism and dimension of the spherulite growth of the blends were different from that of HDPE to some extent. The crystal growth was examined in the context of the Lauritzen‐Hoffman theory. DSC traces obtained at different cooling rates were used for analyzing the non‐isothermal crystallization. It was found that the Ozawa model was rather inapplicable for the materials studied. In contrast, the Avrami equation modified by Jeziorny can be used more efficiently to describe the non‐isothermal crystallization behavior of HDPE‐EOC blends.
In the present work, the functionalisation of oxidised SWCNTs and MWCNTs is studied. The functionalised fillers are characterised by Raman spectroscopy and TGA. The functionalised fillers are dispersed in a PBT‐PTMO thermoplastic elastomer matrix via in situ polymerisation. The functionalisation causes a fine filler dispersion right at beginning of nanocomposite manufacturing. The fillers act as nucleating agents for crystallisation and evidences for a grafting from PBT at the surface of the functionalised nanotubes are found. An outstanding reinforcement effect by the functionalised CNTs is confirmed by tensile tests.
Lysozyme, an enzyme with bactericidal activity over Gram‐positive bacteria cells, is incorporated into PEDOT to prepare films with high biological and electrochemical activity. Two different strategies are used: (1) PEDOT films are coated with a layer of enzyme, which was adsorbed on the surface; and (2) the lysozyme is added to the polymerization medium used for the preparation of the conducting polymer. The enzyme adsorbed at the surface of the polymer produces a biphasic system that retains the electrochemical properties of the conducting polymer but is not able to protect against bacterial growth. In contrast, the addition of lysozyme to the polymerization medium results in a homogeneous composite with high bactericidal and electrochemical activities.
