0000000000240201
AUTHOR
N. Tz. Dintcheva
Selective localization of organoclay and effects on the morphology and mechanical properties of LDPE/PA11 blends with distributed and co-continuous morphology
A study was made on the effect of small amounts of organically modified clay on the morphology and mechanical properties of blends of low-density polyethylene and polyamide 11 at different compositions. The influence of the filler on the blend morphology was investigated using wide angle X-ray diffractometry, scanning and transmission electron microscopy and selective extraction experiments. The filler was found to locate predominantly in the more hydrophilic polyamide phase. Although such uneven distribution does not have a significant effect on the onset of phase co-continuity of the polymer components, it brings about a drastic refinement of the microstructure for the blends both with dr…
α-Tocopherol-induced radical scavenging activity in carbon nanotubes for thermo-oxidation resistant ultra-high molecular weight polyethylene-based nanocomposites
?-Tocopherol, a natural antioxidant molecule, was physically immobilized on the outer surface of multi-walled carbon nanotubes (CNTs), and the resulting functionalised particles (f-CNTs) were dispersed in ultra-high molecular weight polyethylene aiming at improving its thermo-oxidation resistance. The success of the functionalization was assessed through spectroscopic and thermal analysis, and the influence of the filler on the thermo-oxidative stability of the nanocomposites was investigated through rheological analyses and infrared spectroscopy. We found that the addition of only 1 wt.% of f-CNTs brings about a surprisingly high oxidation resistance, with a five/ten-fold increase of the i…
Multi-functional polyhedral oligomeric silsesquioxane-functionalized carbon nanotubes for photo-oxidative stable Ultra-High Molecular Weight Polyethylene-based nanocomposites
Abstract Nanohybrid (phPOSS- f -CNTs) based on Carbon Nanotubes (CNTs) and Phenyl Polyhedral Olygomenric Silsesquioxane (phPOSS) have been synthesized to be used as multifunctional filler for polymer nanocomposites. The success of the functionalization procedure has been demonstrated via accurate spectroscopic, spectrometric and thermo-gravimetric analyses. The results reveal that a large portion of phPOSS is covalently linked to CNTs, while a small amount of phPOSS remains physically adsorbed due to the strong interactions coming from π electron coupling between the CNTs and phenyl rings in phPOSS. Small amounts (1 wt.%) of phPOSS- f -CNTs have been dispersed in Ultra High Molecular Weight…
Competition between chain scission and branching formation in the processing of high-density polyethylene: effect of processing parameters and of stabilizers
Two samples of high-density polyethylene with different molecular weight were processed in a batch mixer and the rheological and structural properties were investigated. In particular, the effect of different processing parameters and the eventual presence of different stabilizers were evaluated. Actually, two reactions may occur during processing: branching/crosslinking or chain scission. The results indicate that when the processing conditions promote a scarce mobility of the macromolecular chains (lower temperatures, lower mixing speed, and higher molecular weight), branching is more favored than chain scission. On increasing the mobility of the chain (higher temperature, higher mixing s…
Multi-functional hindered amine light stabilizers-functionalized carbon nanotubes for advanced ultra-high molecular weight Polyethylene-based nanocomposites
Hindered Amine Light Stabilizer (HAS) molecules have been covalently linked on the outer surface of multi-walled carbon nanotubes (CNTs), and the so-obtained multi-functional fillers (HAS-f-CNTs) have been compounded with Ultra High Molecular Weight Polyethylene (UHMWPE) to get composite films. The success of the grafting reaction of the HAS molecules has been confirmed through spectroscopic and thermo-gravimetric analyses. Morphological analyses reveal a segregated microstructure, in which CNT-rich channels surround the polymer domains. This morphology results in improved mechanical properties and appreciable electrical conductive features. More importantly, the addition of only 1 wt.% of …
Processing and Properties of Biopolymer/Polyhydroxyalkanoates Blends
In this paper, the processability and the performance of a biodegradable polymer, Mater-Bi, and of its blends with either a sample of poly (hydroxy alkanoates) (PHA) or with bacterial biomass containing PHAs were compared. Adding PHA or directly the biomass containing it allows improving the processability of the matrix. Moreover, the mechanical behaviour of the systems was compared considering two different preparation methods, namely compression and injection moulding. The injection moulded samples show poorer mechanical performances than those of the compression moulded systems. The impact strength significantly improves when PHA is added while it reduces when bacterial biomass is used i…
Time-resolved rheology as a tool to monitor the progress of polymer degradation in the melt state - Part I: Thermal and thermo-oxidative degradation of polyamide 11
Abstract Thermal and thermo-oxidative degradation of polyamide 11 (PA11) in the melt state (T = 215 °C) are studied by resorting to time-resolved mechanical spectroscopy. Such an approach allows to elude the changes in the rheological properties occurring while testing, thus enabling the rigorous study of polymer degradation in the melt state. Different concurrent degradation reactions in oxidative (air) and non-oxidative (N2) environment are promptly guessed by studying the time evolutions of rheological functions. In particular, changes in the zero-frequency complex viscosity reflects changes in the average molecular weight, while the appearance of a yield stress in the complex viscosity …
Using organoclay to promote morphology refinement and co-continuity in high-density polyethylene/polyamide 6 blends – Effect of filler content and polymer matrix composition
We investigate the gradual changes of the microstructure of two blends of high-density polyethylene (HOPE) and polyamide 6 (PA6) at opposite composition filled with increasing amounts of an organo-modified clay. The filler locates preferentially inside the polyamide phase, bringing about radical alterations in the micron-scale arrangement of the polymer phases. When the host polyamide represents the major constituent, a sudden reduction of the average sizes of the polyethylene droplets was observed upon addition of even low amounts of organoclay. A morphology refinement was also noticed at low filler contents when the particles distributes inside the minor phase. In this case, however, keep…
Rheological Percolation Threshold in High-Viscosity Polymer/CNTs Nanocomposites
AbstractPolystyrene (PS)/multi-walled carbon nanotubes (CNT) nanocomposites have been prepared through melt mixing processing aiming at obtaining a uniform and homogeneous dispersion of the used nanoparticles within the polymeric matrix. Optical and scanning electron microscopy has been employed to determine the dispersion and distribution of CNTs at different length scales. Furthermore, the linear viscoelastic behavior of formulated nanocomposites has been deeply investigated. As a result of CNTs added, the nanocomposites experience a transition from liquid-like to solid-like rheological behavior, and a disappearance of relaxation processes at low frequency can be noticed. By plotting G’ v…
UV-stabilisation of polystyrene-based nanocomposites provided by polyhedral oligomeric silsesquioxanes (POSS)
Abstract The photo-ageing behaviour of Polyhedral Oligomeric SilSequioxane (POSS)-polystyrene (PS) nanocomposites has been investigated for the first time. POSS having different inorganic framework and pendant organic groups have been used in the PS nanocomposite preparation and the formulated films were subjected to accelerated weathering. Compared to pristine PS, the POSS-containing PS developed a lower level of carbonyl and hydroxyl groups as a function of the exposure time, indicating a significantly improved resistance of the nanocomposites to photo-degradation. The results suggest that all of the investigated POSS molecules play a protective role and may extend the in-use lifetime of …
Photo-oxidation behaviour of polyethylene/multi-wall carbon nanotube composite films
Abstract The resistance to accelerated photo-oxidation of polyethylene/multi-walled carbon nanotubes (MW-CNTs) composite films was compared with the photo-oxidation behaviour of pristine polyethylene film. The polyethylene/MW-CNTs films containing different CNTs loading were subjected to accelerated UV-B exposure. At short exposure time, i.e. under 200 h, the rates of carbonyl formation are very similar to that observed for pristine polyethylene film but at longer irradiation times the carbonyl formation increases for lower MW-CNTs contents (0.1, 0.2 and 0.5% wt./wt.), and decreases for higher MW-CNTs contents (1 and 2% wt./wt.). By adding a UV-stabilizer to the films their photo-oxidation …
Photo-oxidation behaviour of polyethylene/polyamide 6 blends filled with organomodified clay: Improvement of the photo-resistance through morphology modification
Abstract The impact of small amounts of organomodified clay (OMMT) on the photo-degradation behaviour of two blends obtained by mixing either low-density polyethylene (LDPE) or high density polyethylene (HDPE) with polyamide 6 (PA6) (LDPE/PA6 and HDPE/PA6 75/25 wt-%) was studied. The complex photo-degradation behaviour was followed by monitoring the main physical–mechanical properties of the blends. In particular, mechanical and spectroscopic tests were performed in conditions of accelerated artificial aging. An accurate mechanical and morphological characterization was previously carried out. The presence of the OMMT promotes the unexpected formation of a co-continuous morphology for the H…
The role of organoclay in promoting co-continuous morphology in high-density poly(ethylene)/poly(amide) 6 blends
The effect of organically modified clay on the morphology, rheology and mechanical properties of high-density polyethylene (HDPE) and polyamide 6 (PA6) blends (HDPE/PA6 ¼ 75/25 parts) is studied. Virgin and filled blends were prepared by melt compounding the constituents using a twin-screw extruder. The influence of the organoclay on the morphology of the hybrid was deeply investigated by means of wide-angle X-ray diffractometry, transmission and scanning electron microscopies and quantitative extraction experiments. It has been found that the organoclay exclusively places inside the more hydrophilic polyamide phase during the melt compounding. The extrusion process promotes the formation o…
Using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for the characterization of functionalized carbon nanotubes
RATIONALE Functionalization of carbon nanotubes (CNTs) generates complex systems that require the development of suitable characterization protocols. New techniques have been explored, and existing analytical and spectroscopic methods to characterize functionalized CNTs have been adapted. Presently, chemical characterization of functionalized CNTs (f-CNTs) remains a difficult task. METHODS Matrix-assisted laser desorption/ionization (MALDI) analysis is performed on f-MWCNT samples prepared via grafting or absorption of anti-oxidant (AO) molecules on both MWCNT-COOH and MWCNT-OH. Covalently functionalized MWCNTs were subjected to thermal degradation and/or hydrolysis reaction before analysis…
The role of organoclay and matrix type in photo-oxidation of polyolefin/clay nanocomposite films
Abstract In this paper the photo-oxidation behaviour of polyolefin/clay nanocomposite films was studied; in particular, the effect of the amount of organo-modifier and the matrix polarity on the photo-oxidation was investigated. Two different organo-modified clays and compositions of LDPE/EVA blend films were used and the photo-oxidation was followed by mechanical and spectroscopic analyses. The organoclay and matrix type strongly influence the photo-oxidative behaviour of nanocomposite films. The films filled with CL15A show a faster loss of mechanical performance and higher carbonyl formation with respect to the films filled with the CL20A. Additionally, the LDPE based nanocomposite under…
Time-resolved rheology as a tool to monitor the progress of polymer degradation in the melt state – Part II: Thermal and thermo-oxidative degradation of polyamide 11/organo-clay nanocomposites
Abstract Thermal and thermo-oxidative degradation of nanocomposites based on polyamide 11 (PA11) and organo-modified clay (Cloisite® 30B) are studied in the melt state (T = 215 °C) via time-resolved mechanical spectroscopy (TRMS). The goal is assessing the potentiality of rheological analysis for studying polymer degradation in complex systems such as polymer nanocomposites, whose rheological response stems from the combination of the contributions of polymer and nanoparticles. We prove that a thorough analysis grounded on TRMS allows to isolate the effect of degradation of the polymer matrix, whose progress can be hence profitably monitored. Essentially the same degradation mechanisms as i…
Low-density polyethylene/polyamide/clay blend nanocomposites: Effect of morphology of clay on their photooxidation resistance
The photooxidation behaviour of low-density polyethylene (LDPE)/polyamide (PA) blends, containing polyamide 11 (PA11) or polyamide 6 (PA6), has been investigated in the absence and presence of a small amount of commercial organomodified clay (OMMT). The polymer blends LDPE/PA11 and LDPE/PA6 at 75/25 wt./wt.%, with and without OMMT, have been prepared by a two-step procedure: extrusion and sheet formulation. The formulated complex systems have been subjected to accurate morphological analysis in order to evaluate the effect of the OMMT presence on the refinement of the blend morphology. Furthermore, the produced sheets have been subjected to arterial UVB exposure and the variations of the me…
Effects of phenolic-like intercalated layered double hydroxides on poly(lactic acid) based nanocomposites
Two phenolic-like antioxidants (AOs), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 6-hydroxy-2,5,7,8-tetrametilcromano-2-carboxylate anions, were intercalated by anion exchange in layered double hydroxides (LDHs). The two AO-LDHs were dispersed by ultrasound-assisted solution mixing in poly(lactic acid) (PLA) and the thermal oxidation stability of the composites was evaluated following the variation of the molecular weight by SEC, after a controlled aging process, and determining the oxidation induction time (OIT) by DSC. The results evidenced that the intercalation of both the AO molecules within the LDH galleries prevent their own thermal and thermo-oxidative degradation as well a…
Multi-functional Stabilizers-functionalized Carbon Nanotubes for advanced Ultra-High Molecular Weight Polyethylene-based Nanocomposites
Stabilizing molecules, such as hindered phenols (both synthetic and naturally occurring), polyphenols and hindered amine light stabilizers, were covalently linked or physically absorbed onto outer surface of multi-walled carbon nanotubes (CNTs) and the obtained multi-functional fillers (Stab-f-CNTs) were dispersed in Ultra High Molecular Weight Polyethylene (UHMWPE) aiming at obtaining advanced nanocomposites with enhanced thermo- and/or photo-oxidative stability, electrical and mechanical properties. The chemical grafting or physical absorption of stabilizing molecules is confirmed by spectroscopic, spectrometric and thermo-gravimetric analyses, and the influence of the multi-functional na…
The Role of Elongational Flow in Morphology Modification of Polyethylene/OMMt Nanocomposite System
The formulation of high-performance polymer based nanocomposites depend on many factors, such as polymeric matrix type, nanoparticle type, loading and morphology, affinity between the polymeric matrix and nanoparticles, presence of compatibilizer and processing conditions [1-4]. During the industrial processing the polymer based systems are subjected to two different processing flows, i.e. the shear and elongational flow. The shear flow plays a significant role in polyethylene/OMMt manufacture processing but it is not able to change the system morphology, while, the elongational flow, involved in spinning and film-blowing processing operations, can induce considerably clay morphology variat…
The role of the disposition of the recycled polymer on the properties of films for greenhouses coverage
Multilayer films, by using postconsumer materials in the central layer, i.e., multilayer composition: virgin polyethylene/postconsumer polymer/virgin polyethylene, allows to get a film for greenhouses coverage with good mechanical properties and photo-oxidation resistance, similar to that of the films made from virgin material and certainly better than the photo-oxidation resistance of the film made melt blending the virgin polyethylene and the postconsumer polymer. Moreover, the disposition of the postconsumer polymer containing oxygenated groups only in the central layer determines a significant slowdown of the photo-oxidation process of the multilayer film although faster than of the pri…
Effect of elongational flow on morphology and properties of polymer/CNTs nanocomposite fibers
Carbon nanotubes (CNTs) have been attracting increasing interest for the fabrication of polymer-based nanocomposites because of their excellent properties. Traditional methods for the preparation of polymer/CNTs nanocomposites are in situ polymerization, solution blending, and melt mixing. The achievement of a good CNT dispersion and a percolation network is important in order to obtain better mechanical and electrical properties. However, the rheological behavior of polymer/CNTs systems, in particular regarding the extensional flow, has not been much investigated so far. In this work we present, for the first time, rheological data in non-isothermal extensional flow and an investigation on…
Influence of the e-beam irradiation and photo-oxidation aging on the structure and properties of LDPE-OMMT nanocomposite films
Abstract In this paper two systems, polyethylene (LDPE) and polyethylene/commercial organo-modified montmorillonite (LDPE/OMMT) nanocomposite, were subjected to e-beam irradiation at different doses and both the molecular modifications and mechanical properties have been investigated through solubility, FT-IR, calorimetric and tensile tests. Moreover, in some of the irradiated systems photo-oxidation aging was performed and its effects were studied. The results show an enhancement with irradiation of the positive effect of the nano-filler loading, related to the increase of the mechanical properties, due to the increase of the nano-filler polymer interaction. Nevertheless calorimetric and F…
Grafting of polymer chains on the surface of carbon nanotubes via nitroxide radical coupling reaction
Poly(butylene succinate)/MWCNTs nanocomposites with improved dispersion and with nanotubes embedded/immobilized into the polymer matrix were here prepared by an alternative "grafting to" method based on thenitroxide radical coupling reaction. Poly(butylene succinate) (PBS) was grafted on the surface of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) modified multi-walled carbon nanotubes (MWCNTs) via a nitroxide radical coupling reaction. TEMPO functionalized MWCNTs (MWCNTs-g-TEMPO) were synthesized using the Cu(I)-catalyzed azide/alkyne click chemistry approach and the covalent bond of the nitroxide moieties onto the MWCNTs was confirmed via electron paramagnetic resonance (EPR) spectroscopy.…
Reactive melt blending of functionalized-MW/CNTs with polyolefin
Adding nanotube adding into a polymeric matrix leads to the formulation of nanocomposites with enhanced macroscopical performances, and, moreover, the use of functionalized MW-CNTs leads to the nanocomposite formulation with even better properties. Furthermore, the reactive melt blending can be considered as a powerful processing method, i.e. reasonably simple and ecologically friendly, in order to formulate polymer based nanocomposite with good performance. In this work, the reactive melt blending between an ethylene-acrylic acid co-polymer, bis-oxazoline and functionalized MW-CNTs was performed and the rheological properties of the formulated systems were investigated.
A simple method to interpret the rheological behaviour of intercalated polymer nanocomposites
Abstract Nanocomposites are a new class of polymer composites that exhibit an interesting combination of chemical, physical, thermal and mechanical properties. Only small amounts of nanofiller are sufficient to generate great variations of many properties. This work focuses on the rheological behaviour of the intercalated polymer nanocomposites in shear flow. The increase of the viscosity and the more pronounced non-Newtonian behaviour is interpreted simply considering the increase of volume of the inert phase caused by the intercalation of the macromolecules. Indeed, the volume of the intercalated tactoids increases with increasing the interlayer distance. On the other hand, the interlayer…
Effect of different dispersing additives on the morphology and the properties of polyethylene-based nanocomposite films
In this work, the use of a polar wax, e.g. amphiphilic Tegomer ® E 525 (TEG) is investigated with the aim of mod- ifying, and possibly improving, the dispersion of an organically modified nanoclay (OMMT), loaded at 5 wt%, in a poly- ethylene matrix (PE) at relatively low loading levels. We have indeed found that the incorporation of low loadings, e.g. 0.5 wt%, of TEG, an amphiphilic block co-polymer, into a PE/OMMT sample results in a substantial improvement of the clay dispersion in the nanocomposite and, consequently, of the mechanical and thermomechanical properties of the films. The achieved results are comparable to those obtained for systems containing traditional dispersing agents su…
Effect of extrusion and photoxidation on polyethylene/clay nanocomposites
Polyethylene (a 1:1 blend of m-LLDPE and z-LLDPE) double layer silicate clay nanocomposites were prepared by melt extrusion using a twin screw extruder. Maleic anhydride grafted polyethylene (PEgMA) was used as a compatibiliser to enhance the dispersion of two organically modified monmorilonite clays (OMMT): Closite 15A (CL15) and nanofill SE 3000 (NF), and natural montmorillonite (NaMMT). The clay dispersion and morphology obtained in the extruded nanocomposite samples were fully characterised both after processing and during photo-oxidation by a number of complementary analytical techniques. The effects of the compatibiliser, the organoclay modifier (quartenary alkyl ammonium surfactant) …
Thermo-oxidative resistant nanocomposites containing novel hybrid-nanoparticles based on natural polyphenol and carbon nanotubes
Abstract Quercetin (Q), a natural antioxidant molecule, is physically immobilized onto multi-walled carbon nanotubes (CNTs) bearing covalently-linked long-chain alkyl functional groups, and the so obtained hybrid-nanoparticles are used to prepare Ultra High Molecular Weight PolyEthylene-based nanocomposite films with enhanced thermo-oxidation resistance. The effective immobilization of the Q molecules is confirmed by spectroscopic (micro-Raman, ATR-FTIR, and FTIR) and thermo-gravimetric analyses, and the influence of the nanoparticles on the rheological behaviour and thermo-oxidative stability of the nanocomposites are investigated. Rheological analyses (linear viscoelasticity and stress re…