An Innovative Approach to the Synthesis of PMMA/PEG/Nanobifiller Filled Nanocomposites with Enhanced Mechanical and Thermal Properties

A facile route was adopted to blend the matrix. The PMMA/PEG blend was reinforced with three types of nanofillers, i.e., pristine MWCNT (P-CNT), amine functionalized MWCNT (PDA-EA-CNT) and nanobifiller i.e. nanodiamond functional MWCNT (PDA-EA-CNT-ND) to yield three different types of nanocomposites i.e. PMMA/PEG/P-CNT, PMMA/PEG/PDA-EA-CNT and PMMA/PEG/PDA-EA-CNT-ND. These nanocomposites were reinforced with nanofiller loading (1 wt. %, 3 wt. %, 5 wt. %, 10 wt. %, 30 wt. % and 50 wt. %) by solution casting method. Structure of composite and nanofillers was confirmed by FTIR. FESEM imaging revealed that nanocomposites have micro porous morphology. At high magnification, distribution of functionalized CNT/ND appears to be protruding out of the polymeric matrix. The TGA result suggests that the thermal stability of the nanocomposites was enhanced in comparison to PMMA due to grafting of filler molecules with PMMA/PEG macromolecules. The DTG results showed that the bifiller nanocomposites (PMMA/PEG/PDA-EA-CNT-ND) exhibited improved thermal stability with T_max (431^°C) as compared to P-CNT and amine functionalized CNT (PMMA/PEG/PDA-EA-CNT) with T_max of 395^°C and 418^°C respectively. XRD results showed fine interaction between filler and the polymeric matrix. As the filler loading was increased the composites showed pronounced XRD peak at 25.9^°, corresponding to (002) reflection of nanotubes. Significant improvement in the mechanical properties of composites was recorded with the reinforcement of fillers as compared to the neat matrix. The most significant improvement in tensile strength and elastic modulus was observed for the bifiller nanocomposites with 5 wt. % PDA-EA-CNT-ND. They showed a tensile strength and elastic modulus of 29.9 MPa and 1474.31 MPa respectively as compared to amine functionalized CNT with tensile strength (25.7) and elastic modulus (1466.99 MPa)and P-CNT with tensile strength(25 MPa) and elastic modulus (1155.75 MPa).     

Synthesis of cellulose/reduced graphene oxide/polyaniline nanocomposite and its properties

A series of conductive nanocomposites cellulose/reduced graphene oxide/polyaniline (cellulose/RGO/PANi) were synthesized via in situ oxidative polymerization of aniline on cellulose/RGO with different RGO loading to study the effect of RGO on the properties of nanocomposites. The results showed that when RGO is inserted into cellulose/PANi structure, its thermal stability and conductivity are increased. So that adding of only 0.3 wt% RGO into the cellulose/PANi structure, its conductivity is increased from 1.1 × 1 10^?1 to 5.2 × 110^?1 S/cm. Scanning electron microscopy results showed that the PANi nanoparticles are formed a continuous spherical shape over the cellulose/RGO template; this increases the thermal stability of nanocomposite.     

Influence of surfactants on properties of electrochemically synthesized pyrrole/1-dimethylaminopyrrole copolymer

The electrochemical copolymerization of pyrrole (Py) and 1-dimethylaminopyrrole (DMAPy) was successfully carried out in the presence of three different types of surfactant (anionic, cationic and non-ionic) by cyclic voltammetric method. The influence of anionic (sodium dodecylbenzenesulfonate) (NaDBS), cationic (tetradecyltrimethylammonium bromide) and non-ionic poly(ethylene oxide)(10) iso-octylphenyl ether (Tween 20) surfactants on the properties of copolymer was investigated. The copolymer has been characterized by the cyclic voltammetry, fourier transform infrared spectroscopy, UV–Vis spectroscopy, scanning electron microscopy, thermogravimetric analysis and conductivity measurements. The results confirmed that the electrochemical reaction of Py and DMAPy in the presence of surfactants generated copolymers. The type of surfactant had an effect on the structural, morphological, thermal and conductivity properties of the copolymers in different ways. According to the initial decomposition temperatures, the thermal stability of the copolymers improved in the presence of surfactants. Py/DMAPy copolymer synthesized in the presence of anionic surfactant NaDBS had the highest initial decomposition temperature (320 °C). The copolymer prepared using various surfactants exhibited different morphologies. The electrical conductivity of pyrrole/1-dimethylaminopyrrole copolymer (8.39 × 10^?3 Scm^?1) was improved using surfactants, especially with anionic surfactant (3.75 × 10^?2 Scm^?1) due to the incorporation of NaDBS into the PPy polymer chain that resulted in a more compact morphology and reduced size of PPy globules.     

Synthesis and Characterization of Conductive Blends of Polyaniline with Poly(azomethine ester)s

Polyaniline (PANI) doped with HCl was blended with different poly(azomethine ester)s (10% by weight of PANI) and compressed into pellets. The blends were studied by Fourier Transform Infra-Red (FT-IR) and thermo gravimetric analysis (TGA). Electrical conductivities of the blends determined by four-point probe method, in the temperature range 32°C to 80°C, vary from 24.4 × 10^?3 to 3.15 × 10^?3 Scm^?1. The TGA measurements show that weight loss occurred below 80°C is only about 2%.     

Preparation and Characterization of Conductive Polypyrrole/Organophilic Montorillonite Nanocomposite

Polyvinylpyrrolidone (PVP) was used as organic intercalative modifier to prepare organophilic montorillonite OMMT-P. PPy/OMMT nanocomposites were prepared by the oxidative polymerization of pyrrole (Py) intercalated into the interlayer of OMMT. The effect of Py, OMMT, oxidant, and dopant content on nanocomposites' conductivity were studied, and the conductivity of PPy/OMMT-P was achieved as high as 15.0 S·cm^?1 when the molar ratio of FeCl₃ and Py is 2.50, the mass ratio of Py and OMMT-P is 0.25, and the TSANa concentration is 0.025 g·ml^?1. The structure and properties of the nanocomposites are characterized with FT-IR, TG, and XRD.     

A facile route for the synthesis of mechanically strong MWCNTs/NDs nanobifiller filled polyacrylate composites

ABSTRACT

We present here the synthesis of novel Nano-Bifiller filled composites with extremely promising material properties. To achieve this goal, initially, poly (methyl methacrylate) (PMMA) and poly (ethylene glycol) (PEG) blend were formed. Later, the matrix was reinforced with purified carbon (P-CNT), amino modified carbon nanotube (PDA-CNT) and amino modified carbon nanotube nanodiamond (PDA-CNT-ND). In this way, three series of nanocomposites, i.e. PMMA/PEG/P-CNT, PMMA/PEG/PDA-CNT, and PMMA/PEG/PDA-CNT-ND were synthesized with varying P-CNT, PDA-CNT and PDA-CNT-ND loading (i.e., 1 wt.%, 3 wt.%, 5 wt.%, 10 wt.%, 30 wt.% and 50 wt.%) by a solution blending route. The reinforcement and loading effect of these three types of nanofillers on the matrix was studied. Studies were performed using Fourier transform infrared spectroscopy (FTIR), mechanical testing, thermogravimetric analysis (TGA), field emission scanning electron microscopy (FE-SEM) and X-ray powder diffraction (XRD) to explore the structural, morphological, mechanical and thermal properties of nanocomposites prepared. The inter-association of poly (methyl methacrylate) and poly (ethylene glycol) (PMMA/PEG) due to hydrogen bonding and covalent attachment of matrix to the sidewalls of nanotubes was confirmed by FTIR spectra. The experimental results showed that a loading of 5 wt. % filler in matrix produced a tensile strength and modulus of 26.4 (MPa) and 1255.75 (MPa) in PMMA/PEG/P-CNT nanocomposites, while 28.8 (MPa) and 1411.04 (MPa) in PMMA/PEG/PDA-CNT nanocomposites and 29.4 (MPa) and 1419.41 (MPa) in PMMA/PEG/PDA-CNT-ND nanocomposites as compared to neat PMMA which has tensile strength and modulus of 21.79 (MPa) and 1083.84 (MPa) respectively. These results depict that bifiller nanocomposites showed better mechanical properties as compared to pristine and amine functionalized MWCNT. Scanning electron microscopy revealed granular morphology with few protruding out carbon nanotubes. Thermal stability of PMMA/PEG/PDA-CNT-ND nanocomposites was found higher than PMMA/PEG/PDA-CNT and PMMA/PEG/P-CNT nanocomposites. The T_o (369^°C) and T₁₀ (515^°C) values for PMMA/PEG/PDA-CNT-ND composites was higher than PMMA/PEG/PDA-CNT [T_o (354^°C) and T₁₀ (420^°C)] and PMMA/PEG/P-CNT composites [T_o (312^°C) and T₁₀ (390^°C)]. These results suggest that the bifiller nanocomposites were thermally more stable. The XRD spectra showed a pronounced XRD peak at 25.9^°, corresponding to (002) reflection of the nanotubes indicating that MWCNT structure was not destroyed during composite formation. The peak appeared at 75.3^° were indexed to (220) reflections due to nanodiamond structure.     

Synthesis and characterization of tetrafluorophenyl phosphonic acid functionalized polyacrylates as potential proton conducting materials in fuel cells

Novel acrylate polymers functionalized with tetrafluorophenyl phosphonic acid groups were prepared by free radical polymerization of phosphonic ester acrylate monomers. Liberation of the free acid functions was realized by ester cleavage with Me₃SiBr and the subsequent hydrolysis with methanol. The obtained polymers were analyzed by NMR and IR spectroscopy. The ion exchange capacity of the phosphonic acid functionalized methacrylate polymer was determined to 2.8 mmol/g by titration with 0.1 M NaOH. The proton conductivity under anhydrous conditions was determined to 6.84 × 10⁻⁶ Scm⁻¹ at 120°C by electrochemical impedance spectroscopy.     

Sulfonate based ionic liquid incorporated polymer electrolytes for Magnesium secondary battery

The polymer electrolytes comprising of PVdF-HFP/PVAc/Mg(ClO₄)₂ as salt based polymer blend electrolytes derived from the addition of varying amounts of 1-ethyl – 3-methylimidazolium trifluoromethane sulfonate [EMITF], as dopant were synthesized in the form of films by solution-casting method. The XRD and FTIR patterns confirm the formation of an amorphous phase and also that complex formation between the polymers, salt and ionic liquid. The SEM images show that the polymer electrolyte exhibit a enormous pores, remarkably, the maximum ionic conductivity is obtained in the case of the typical polymer system I₃ is found to be 9.122 × 10^?4 Scm^?1at 303 K.     

Polyaniline doped with α, ω‐alkanedisulfonic acids: preparation and characterization

The use of α, ω‐alkanedisulfonic acid, HO₃S(CH₂)_nSO₃H (n = 1, 4, 6 and 12), as a dopant for polyaniline (PANi) was investigated. This series of disulfonic acids with varying chain lengths were synthesized and used in the doping of PANi. The doped polymers showed conductivity in the range 10^?2 to 10^?1 S cm^?1. Thermal studies showed that the doped polymers, depending on the chain length of α,ω‐alkanedisulfonic acid, were stable up to ca 300 °C and the thermal stability decreased with increasing dopant chain length. The thermal stability of α,ω‐alkanedisulfonic acid‐doped PANi was higher than that of alkanesulfonic acid‐doped PANi which typically degrades around 250 °C, suggesting a moderately broader processing window for α,ω‐alkanedisulfonic acid‐doped PANi for blending with other thermoplastics. Copyright © 2012 Society of Chemical Industry     

Preparation and Properties of High Performance Multilayered PANi/PMMA/PPG-b-PEG-b-PPG/FGHMDA Nanocomposites via in Situ Polymerization

In this attempt, novel conjugated polymer/graphite nanocomposites with exposed surface area were fabricated by in situ polymerization using polyaniline, poly(methyl methacrylate) and poly(propylene glycol)-block-poly(ethylene glycol) block- poly(propylene glycol) as matrices and functionalized graphite as a filler. Structural and morphological analysis revealed the modification of graphite as well as oxidative polymerization of numerous matrices over the surface of modified graphite ensuing multilayered nanocomposites. The increased values of T_g (59 and 103°C) obtained from thermal analysis reflect the improved thermal stability of prepared nanocomposites and exhibit better adsorption capacity (35.5cm³/g). Maximum electrical conductivity (7.4 S/cm) was also observed for multilayered nanocomposite.     

Azo-Polymer Based Hybrids Reinforced with Carbon Nanotubes and Silver Nanoparticles: Solution and Melt Processing

The research initially involved the decoration of silver nanoparticles on carbon nanotubes using N,N-dimethylformamide. A new heteroaromatic azo-polymer was prepared and employed as a matrix while Ag–CNTs as filler. Two techniques were exploited to prepare nanocomposites (i.e., melt compounding and solution mixing). The solution mixing method resulted in better dispersion leading to higher mechanical strength 55.09–58.22 MPa relative to melt system 40.11–46.28 MPa. Filler content from 1 to 5 wt% increased electrical conductivity from 3.8 to 5.2 Scm^?1. 10% gravimetric loss was found to increase from 532 to 578°C (solution) and 503 to 544°C (melt).     

Graphite-Filled Polyethylene/Epoxy Blend for High-Conductivity Applications: The Immiscibility Edge

ABSTRACT

Polyethylene (PE)/epoxy blends filled with graphite were prepared and studied in this work. The in-plane and through-plane conductivities of the composites increased from 11.68 Scm^?1 to 73.11 Scm^?1 and 0.20 Scm^?1 to 4.12 Scm^?1, respectively, as graphite content increased from 30 to 80 wt%. Phase bonding effect of the compatibilizer and reinforcing effect of the filler enhanced the flexural modulus and strength of the composites up to 70 wt% filler content. The electrical conductivities attained by these composites being significantly higher than comparable composite formulations in literature show the edge of immiscible PE/epoxy blend for achieving high-conductivity polymer composites.     

Synthesis of polypyrrole nanoparticles in natural rubber–polystyrene blend via emulsion polymerization

Nanoparticles of polypyrrole (PPy) in 40/60 wt % natural rubber (NR)–polystyrene (PS) blends were synthesized by emulsion polymerization using ferric sulfate [Fe₂ (SO₄)₃], sodium dodecyl sulfate (SDS), and n‐amyl alcohol as the oxidant, surfactant, and cosurfactant, respectively. The NR/PS/PPy blends were characterized by Fourier transform infrared spectroscopy (FTIR), elemental analysis, thermogravimetric analysis (TGA), and field emission scanning electron microscopy (FESEM). FESEM micrographs showed that NR/PS/PPy blends were homogeneous, and PPy nanoparticles were well distributed throughout the binary matrix of NR/PS. The size of PPy particles in the blends was in the range of 26–80 nm. The electrical conductivities of the pellets prepared from NR/PS/PPy blends increased as the composition of PPy nanoparticles was increased, which were in the range of 8.9 × 10^?8 – 2.89 × 10^?4 S/cm. Thermal stability of the blends increased as the content of PPy was increased, as shown by TGA thermograms. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Removal of toxic nitrate ions from drinking water using conducting polymer/MWCNTs nanocomposites

New application of conducting polymers as stable nanocomposites for nitrate ion exchange materials in water and wastewater treatment and for environmental protection is introduced in this work. The nanocomposites of multi-walled carbon nanotubes (MWCNTs) with different polymers such as: polyaniline (PANI), polypyrrole (PPY), poly(1,8-diaminonaphthalene) [P(1,8-DAN)] and poly(2-vinylpyridine) (P2VP) were synthesized with different dopants as effective and reusable nanocomposites for nitrate removal from drinking water. Nitrate anions at toxic concentrations were removed from water using ion exchange mechanism without any toxic byproducts. The obtained results demonstrate that effective ion exchange occurs between NO₃ ^? and Cl^?. There are some protonated heteroatoms in polymer chains that are bonded with anions of dopants and their counter ions in nanocomposites. These dopant anions on the =NH⁺– groups of polymers can be exchanged with NO₃ ^? in water. Adsorption of NO₃ ^? on polymer/MWCNTs nanocomposites showed dependency to some parameters. Different experimental parameters such as pH and temperature of the sample, polymers dopant, and the ratio of polymer to MWCNTs in nanocomposites affect the amount of nitrate removal. The highest removal efficiency was achieved at 1.20 g L^?1 of PANI/MWCNTs (3:1) nanocomposite, pH = 6.5 and ambient temperature. After five successive cycles of nitrate removal, this parameter was still up to 70 % compared to the first run (up to 80 %).     

Synthesis of polythiophene/graphene oxide composites by interfacial polymerization and evaluation of their electrical and electrochemical properties

We report a new method for the synthesis of polythiophene (PTh)/graphene oxide (GO) nanocomposites by interfacial polymerization. Polymerization occurred at the interface of two immiscible solvents, i.e. n‐hexane containing thiophene and nitromethane containing GO and an initiator. Characterizations were done using Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, and electrochemical and electrical conductivity measurements. Spectroscopic analyses showed successful incorporation of GO in the PTh matrix. Morphological analysis revealed good dispersion of GO sheets in the polymer matrix. The PTh/GO composites showed marked improvements in thermal stability and electrical conductivity (2.7 × 10^?4 S cm^?1) compared to pure PTh. The composites exhibited excellent electrochemical reversibility compared to pure PTh at a scan rate of 0.1 V s^?1. The composites were stable even up to 100 electrochemical cycles, indicating good cycle performance. The specific capacitance of the composites was calculated using cyclic voltammetry and was found to be 99 F g^?1. © 2014 Society of Chemical Industry     

Study on the Effect of Polypyrrole and Polypyrrole/Graphene Oxide Nanoparticles on the Microstructure,Electrical and Tensile Properties of Polypropylene Nanocomposites

In this article Polypropylene/Polypyrrole (PP/PPy) and Polypropylene/polypyrrole-graphene oxide (PP/PPy-GO) nanocomposites were prepared by melt mixing. PPy nanoparticles and PPy-GO nanocomposite were prepared by chemical polymerization and served as nanofillers. FTIR, XRD and SEM analysis were used for the characterization of PPy and PPy-GO composites. The effects of PPy and PPy-GO loading level on the morphology, tensile and electrical properties of PP-based nanocomposites were examined. It was found that the Young's modulus and tensile strength increased with the increase of nanofiller content. Tensile results also showed that PPy-GO composite significantly affected the mechanical properties of PP based nanocomposites compared to the PPy nanoparticles. It was observed that the addition of 1% wt. PPy-GO into PP, increased the Young's modulus about 30% compared as with pure PP. Electrical conductivity measurements showed that conductivity of PP nanocomposites increased up to 1 × 10^?3 S/cm for PP/PPy-GO nanocomposites. It was also observed that PP-g-MA improved the distribution of PPy and PPy-GO nanocomposites and affected the morphology, electrical and mechanical properties of PP-based nanocomposites.     

Synthesis and proton conductivity studies of methacrylate/methacrylamide‐based azole functional novel polymer electrolytes

Anhydrous polymer electrolytes based on azole functional methacrylates and methacrylamides have been produced for use in proton exchange membrane fuel cells (PEMFCs). Poly(methacryloyl chloride) (PMAC) was prepared first by free‐radical polymerization of methacryloyl chloride, followed by side chain functionalization with 5‐aminotetrazole (ATet), 3‐amino‐1,2,4‐triazole (ATri) and 1H‐1,2,4‐triazole (Tri). Finally, the obtained polymers were doped with triflic acid (TA) at stoichometric ratios of 1.0, 2.0 and 4.0 with respect to azole units, and the anhydrous polymer electrolytes were obtained. The membranes were characterized by FT‐IR, ¹³C‐NMR, and elemental analysis. Thermal behaviour of polymers was explored by TGA and DSC. The samples were thermally stable up to approximately 200 ^oC. Proton conductivity was measured by impedance spectroscopy. Trifilic acid doped poly(methacryloyl aminotetrazole) (PMAATet‐(TA)₄), poly(methacryloyl‐3‐amino‐1,2,4‐triazole) (PMA‐Tri‐(TA)₄), and poly(methacryloyl‐1,2,4‐triazole) (PMA‐ATri‐(TA)₄) showed maximum proton conductivities of 0.01 Scm^?1, 0.02 Scm^?1 and 8.7x10^?4 Scm^?1, respectively, at 150^°C and anhydrous conditions. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39915.     

Lithium Ion-conducting Blend Polymer Electrolyte Based on PVA–PAN Doped with Lithium Nitrate

A new blend polymer electrolyte based on poly(vinyl alcohol) and polyacrylonitrile doped with lithium nitrate (LiNO₃) has been prepared and characterized. The complexation of blend polymer (92.5 PVA:7.5 PAN) with LiNO₃ has been studied using X-ray diffraction and Fourier transform infrared spectroscopy. Differential scanning calorimetry thermograms show a decrease in glass transition temperature with the addition of salt. The maximum ionic conductivity of the blend polymer electrolyte is 1.5 × 10^?3 Scm^?1 for 15 wt% LiNO₃ doped–92.5 PVA:7.5 PAN electrolyte. The conductivity values obey Arrhenius equation. Ionic transference number measurement reveals that the conducting species are predominantly ions.     

Chemical Grafting of Crosslinked Polypyrrole and Poly(vinyl Chloride) onto Modified Graphite: Fabrication,Characterization, and Material Properties

ABSTRACT

Conjugated polymer/graphite nanocomposites have been known as high performance materials owing to improve the physicochemical properties relative to conventional once. Multilayered polymer nanocomposites based on polypyrrole (PPy), polyvinylchloride (PVC) as matrices and p-phenylene diamine (PDA) as linker were prepared via chemical in situ polymerization process and subsequently investigated the physical characteristics of fabricated nanocomposites at various loadings. The structural characterization and morphology of prepared nanocomposites were inspected by Fourier transform infrared spectroscopy (FTIR), X-ray photon spectroscopy (XPS), energy dispersive X-ray spectroscope (EDX), field emission scanning electron microscope (FESEM), respectively. The composite III showed higher thermal stability at 10 wt% loading of PPy. According to differential scanning calorimetry (DSC), the glass transition temperature (T_g), melting temperature T_m, and crystallization temperature (T_c) of nanocomposites increases with PPy loading (2–10 wt%) owing to crosslinking and chain rigidity. Moreover, higher surface area was displayed by the multilayered PPy/PVC/PDA@FG nanocomposites. Remarkably, electrical conductivity of ultimate nanocomposites was also found to be a function of PPy loading.     

Field emission of MWCNTs/PANi nanocomposites prepared by ex‐situ and in‐situ polymerization methods

The present work describes the field‐emission properties of multiwalled carbon nanotubes (MWCNTs) coated with conducting polymer polyaniline (PANi). MWCNTs/PANi nanocomposites have been prepared by ex‐ situ polymerization methods and inex‐ situ chemical polymerization and are analyzed by SEM and Raman spectroscopy. It is fairly clear from SEM images that PANi is coated on the surface of MWCNT. SEM image of PANi powder also shows that the powder obtained is PANi nanofibers. It is also observed from SEM images that the shell diameter of MWCNTs depends on PANi content in thenanocomposites. The average outer diameter of MWCNTs increases from 7–15 to 50–80 nm upon PANi coating. Field‐emission study shows that although there is decrease in the value of turnex‐on field E_to and increase in the value field enhancement factor β of the nanocomposites as we go from direct solid‐state mixing method to inex‐ situ chemical polymerization method, the parameters obtained by inex‐ situ polymerization chemical method shows superior field emission. The turn‐on field of the nanocomposites are between 2.5 and 4.5 V/μm and the field enhancement factors are significantly high, between 1.2 × 10³ and 9.2 × 10³ while. PANi nanofibers does not show any field emission. POLYM. COMPOS. 34:1298–1305, 2013. © 2013 Society of Plastics Engineers