Inner surface modification of halloysite nanotubes and its influence on morphology and thermal properties of polystyrene/polyamide‐11 blends

The asymmetry of halloysite surface chemistry was used to perform a selective modification of its inner surface via grafting of a synthesized styrene/(methacryloyloxy)methyl phosphonic acid copolymer. Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA) and pyrolysis gas chromatography/mass spectrometry were used to evidence and quantify the grafting. Then, raw and hybrid nanoparticles were incorporated in polystyrene (PS)/polyamide‐11 (PA11) blends (80/20 and 60/40 wt%). Scanning electron micrographs showed differences in localization of the halloysite nanotubes (HNTs), since raw halloysite is concentrated in the PA11 phase while modified halloysite is also located at the PS/PA11 interface, leading to a better interfacial adhesion between PS and PA11. An inhibiting effect of modified halloysite on PA11 coalescence was evidenced by measuring the particle size distribution of the extracted nodules. Moreover, the presence of modified halloysite at the interface shows an improvement in terms of thermal stability as observed by TGA, but with no significant effects on PA11 crystallization behaviour as shown by differential scanning calorimetry results. Rheological measurements were carried out to study the influence of the surface modification of halloysite on the blend morphology. A gel‐like behaviour was observed for the (60/40 wt%) HNTs reinforced composition that was enhanced in the case of 10% functionalized halloysite. © 2016 Society of Chemical Industry     

Composite short-side-chain PFSA electrolyte membranes containing selectively modified halloysite nanotubes (HNTs)

Aquivion membrane displays improved properties as compared to Nafion membrane, partly due to shorter side chains. However, some improvements are still necessary for proton exchange membrane fuel cell to operate at low relative humidity. To overcome this drawback, the addition of clay nanoparticle into the Aquivion matrix can be considered. In this study, different composite membranes have been prepared mixing short-side-chain PFSA (perfluorosulfonic acid) Aquivion and selectively modified halloysite nanotubes for PEMFC low relative humidity operation. Halloysites were grafted with fluorinated groups, sulfonated groups, or perfluoro-sulfonated groups on inner or outer surface of the tubes. The obtained composite membranes showed improved properties, especially higher water uptake associated with reduced swelling and better mechanical strength compared to pristine Aquivion membrane and commercially available Nafion HP used as reference. The best performance in this study was obtained with Aquivion loaded with 5 wt% of pretreated perfluoro-sulfonated halloysite. The composite membrane, referred to as Aq/pHNT-SF5, displayed the largest water uptake and proton conductivity among the panel of membranes tested. The chemical stability was not affected by the presence of halloysite in the Aquivion matrix.

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Interface/morphology relationships in polymer blends with thermoplastic starch

In this paper, the interface/morphology relationship in polyethylene/TPS blends prepared by a one-step extrusion process is examined in detail. Emulsification curves tracking the change in phase size with added quantity of PE-g-MA copolymer are used to identify the critical concentration required for saturation of the interface as well as to estimate the areal density of grafted copolymer chains at the interface. The level of glycerol content in the TPS is shown to lead to different emulsification behaviors. Dynamic mechanical analysis clearly shows a partial miscibility between glycerol and starch in the TPS with glycerol-rich and starch-rich peaks being clearly identified. This phase separation is more evident in the case of high glycerol levels in the TPS (>24% glycerol). Furthermore, the glycerol-rich peak decreases in intensity with added PE-g-MA graft copolymer. At high glycerol contents (>24% glycerol) in the TPS, a 20% thermoplastic starch-based binary blend with polyethylene can reach an elongation at break value as high as 200%. When also modified at the appropriate level with a PE-g-MA copolymer, this elongation at break further increases to 600%. However, at lower glycerol contents, the elongation at break is comparatively low at 20-50% even after the addition of PE-g-MA copolymer. We explain these results through a proposed double mechanism of interfacial modification between the HDPE matrix and the TPS dispersed phase. Under dynamic melt-mixing conditions, it is suggested that a small portion of the low molecular weight glycerol-rich phase tends to migrate to the HDPE-TPS interface as predicted by Harkins spreading theory. Once at the interface, this glycerol-rich outer layer is readily deformed by an applied stress and this stress is then transferred to the starch-rich phase due to their mutual partial miscibility. Added PE-g-MA copolymer initially reacts with the glycerol-rich outer layer but if the level of copolymer is high enough, it then reacts with the starch-rich phase via a classic interfacial modification protocol. Also, both the elongation at break and impact properties dramatically increase at a copolymer level associated with interfacial saturation. The above mechanism effectively explains all the emulsification and mechanical property observations.     

Improvement of the fire behavior of poly(1,4‐butanediol succinate)/flax biocomposites by fiber surface modification with phosphorus compounds: molecular versus macromolecular strategy

The grafting of phosphorus compounds onto natural fibers has been investigated as a strategy for improving poly(1,4‐butanediol succinate)/flax biocomposite fire behavior. Three phosphorus compounds ? dihydrogen ammonium phosphate, poly(methacryloyloxy)methyl phosphonic acid homopolymer and poly(methacryloyloxy)methyl phosphonic acid methylmethacrylate copolymer ? were selected. The aim of this work was to compare the fire performance conferred by the grafted compounds depending on whether phosphorus is brought by a molecule or a macromolecule. TGA, pyrolysis combustion flow calorimetry and cone calorimetry were used to characterize the thermal stability and fire behavior of the samples. The pyrolysis combustion flow calorimetry results showed that in all cases the presence of phosphorus changes the degradation pathway and thus the flammability properties of flax. The ability of the grafted flame retardant to promote char formation and residue formation was found to be dependent on the nature and quantity of phosphorus covalently bonded to flax. Conversely, cone calorimeter tests revealed similar fire behavior whatever the grafting agent. A significant increase of the char amount and a global enhancement of fire parameters were observed with increasing grafting rate. Moreover, phosphonated polymers promoted a charred sheath around the fibers which acts in addition to their charring, conferring a fire performance close to that of dihydrogen ammonium phosphate for the biocomposite.     

Influence of the morphology on the fire behavior of a polycarbonate/poly(butylene terephthalate) blend

Polycarbonate/Poly(butylene terephthalate) (PC/PBT) blends are used in various industrial sectors, particularly in the cable industry. In this work, the fire behavior of PC/PBT blends was studied for the entire range of blend composition to investigate the relation between fire properties and blend morphology. The morphology of the binary blends used presents a phase inversion point for 25–30 wt % PBT. Various tests have been performed to characterize the fire behavior [limiting oxygen index (LOI), epiradiator test, cone calorimeter, and pyrolysis combustion flow calorimeter (PCFC)]. A change in fire behavior has been observed when the PBT content increases from 20 to 30 wt %, corresponding to the phase inversion, from a continuous rich-PC phase to a continuous rich-PBT phase. Consequently, it can be suggested that the control of the morphology of binary polymer blends is crucial to improve their fire properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structuration,selective dispersion and compatibilizing effect of (nano)fillers in polymer blends

Hybrid ternary blends comprising two polymers and one mineral (nano)filler are increasingly studied because they are starting to be widely used to respond to industrial issues. The objective of this review is to gather information on these particular systems. Concerning first thermodynamic effects of fillers on the phase separation of an immiscible polymer blend, Flory–Huggins theory demonstrate stabilization. This theory was particularly taken up and developed for the case of two polymers and one filler by Lipatov and Nesterov in the 90s. More recently, Ginzburg generalized this theory to the case of unfavorable enthalpic interactions between a particle and the two polymers. They showed that the amount of particles had to attain a certain threshold to stabilize the system and the lower the particle radius, the higher the stable zone area. Generally speaking, all the phenomena regarding the morphology of polymer blends are governed by thermodynamics and/or kinetic effects, as well as the localization of nanoparticles. The main discussed thermodynamically controlling parameter of the localization is the wetting parameter ω_AB. However, because of the viscosity of the system, the equilibrium dictated by ω_AB may never be reached. Hence, concerning the kinetic effects, the final localization of fillers in a polymer pair is guided by the sequence of mixing of the components, the viscosity ratio, the composition, the temperature, the shear rate and the time of mixing. When the particles are placed at the interface between two polymers, coalescence can be suppressed or/and interfacial tension can be reduced. In that case, particles are known to play the role of a compatibilizer. In a ternary system, (i) the shape of the particle (spheres, rods or “onions-shape”), (ii) the particle radius (R_p) versus the radius of gyration of the polymers (R_g) and (iii) the surface chemistry of the particles affect the final localization of the particles (thus, the compatibilizing effect) and the final properties of the material, such as mechanical, conductive, magnetic and thermal properties. This review details recent works for which those four above mentioned properties are improved by incorporating different kind of fillers in polymer blends.     

Fire retardancy effect of phosphorus‐modified halloysite on polyamide‐11 nanocomposites

Halloysite nanotubes (HNTs) were successfully incorporated as flame retardants in polyamide‐11 (PA11) after their modification with methyl phosphonic acid. Fourier transform infrared spectroscopy, thermal gravimetric analysis (TGA) and pyrolysis–gas chromatography–mass spectrometry were used to evidence the functionalization of the clay. Raw and modified HNTs were then incorporated by melt mixing in PA11 at 20 wt%. Compositions containing both ammonium polyphosphate (APP) and HNTs were also prepared. TGA and pyrolysis combustion flow calorimeter exhibited enhancement in thermal stability upon incorporation of both raw and modified halloysite nanotubes while APP causes degradation at lower temperature. Cone calorimeter data showed that modified halloysite acts by forming an insulating barrier during the combustion, which limits heat and mass transfers. Moreover, elemental analysis of sample residues after cone test evidenced that a part of the phosphorus of the modified halloysite was transferred to the gaseous phase. These results suggest the full potential of halloysite as fire retardant agent for polyamides. POLYM. ENG. SCI., 59:526–534, 2019. © 2018 Society of Plastics Engineers     

Grafting of 4‐Hydroxybenzenesulfonic Acid onto Commercially Available Poly(VDF‐co‐HFP) Copolymers for the Preparation of Membranes

The grafting of a phenate bearing sulfonate group in solution onto commercially available poly(VDF‐co‐HFP) copolymers, where VDF and HFP stand for vinylidene fluoride and hexafluoropropene, respectively, is presented. This reaction leads to novel fluoropolymers, bearing aryl sulfonic acid side functions, which are fuel cell membrane precursors. A mechanism similar to the grafting of bisphenol onto VDF‐containing copolymers is discussed. First, the sulfonate phenate is modified to give the didecyldimethylammonium bromide sulfonate phenate salt, in order to promote the substitution onto a fluorine atom in VDF unit adjacent to one HFP unit onto a fluorine atom in the copolymer. The substitution of this salt onto the fluorinated copolymer yields low molar percentages of grafted phenate, ranging from 1.8 to 5.1 mol‐%, whereas it reaches values up to 13 mol‐% grafting when the NH₂‐CH₂‐CH₂‐S‐CH₂‐CH₂‐C₆H₄‐SO₃Na amine is used as the grafting agent. NMR characterization is used to monitor the grafting process. The electrochemical properties of the resulting phenate grafted‐poly(VDF‐co‐HFP) copolymer are studied. The theoretical ion exchange capacities are half that of Nafion®. The proton conductivities are also lower than that of Nafion®, although one conductivity measurement reached a value of 5.1 mS cm^–1, showing a non‐negligible conductivity. The water uptake is lower than these noted for a sulfonated amine‐grafted copolymer, and is of the same order as that for Nafion®. Finally, it is shown that these novel materials start to decompose above 200 °C, showing a similar thermostability as that of an amino‐containing aryl sulfonate‐grafted poly(VDF‐co‐HFP) copolymer.     

Thermal degradation of polyesters filled with magnesium dihydroxide and magnesium oxide

Magnesium dihydroxide (MDH) was evaluated as char promoter into different polymers exhibiting various chemical structures. Char promotion was characterized using thermogravimetric analysis and pyrolysis‐combustion flow calorimetry. Gases released during pyrolysis were identified using pyrolysis coupled gas chromatography/mass spectrometry and thermogravimetric analysis coupled Fourier transform infrared spectroscopy. Relationships between the MDH effect (according to the char content and its thermal stability) and the chemical structure of the host polymers were identified. It was shown that MDH can be a good char promoter for aromatic polyesters such as polybutylene terephtalate and polyethylene terephtalate. Char promotion can be considered as one of the main mode‐of‐action of MDH at low or moderate filler content. An optimum was observed at approximately 20wt.% of MDH. Magnesium oxide was also studied as substitute to MDH to avoid hydrolysis phenomena due to the water release. But it was demonstrated that MDH was more efficient as a char promoter for polybutylene terephtalate than magnesium oxide. Copyright © 2015 John Wiley & Sons, Ltd.     

Incorporation of modified Stöber silica nanoparticles in polystyrene/polyamide-6 blends: Coalescence inhibition and modification of the thermal degradation via controlled dispersion at the interface

The controlled dispersion of Stöber silica nanoparticles (SiNPs) at the interface of a PS/PA6 (80/20 wt%) blend was achieved by means of surface modifications using 3-methacryloxypropyltrimethoxysilane (MPS). The final localization of SiNPs in the blend was predicted using wetting parameter calculation and confirmed by scanning electronic microscopy (SEM) observations. Stability of blends during annealing was evaluated qualitatively by laser diffraction particle size analyzer. Morphologies of the blends in the molten state were observed using optical microscopy. Flammability of blends was investigated using pyrolysis-combustion flow calorimeter (PCFC). Results showed that both microstructure stability during annealing and thermal degradation of the blend, were improved when MPS-modified SiNPs are located at the interface. SEM pictures revealed that the MPS-modified SiNPs form a solid barrier between PS and PA6 phases which inhibits coalescence process and modifies the thermal degradation mechanisms.