Thermal Stability Of Polymers Research Articles

Thermal Stability of Polymers Confined in Graphite Oxide

In this study, polymer–graphite oxide (GO) interactions are demonstrated to induce thermal instability in both the polymer and GO phase in conditions of maximum polymer uptake, in which the polymer chains are either intercalated into the GO interlayer or adsorbed on the GO sheets. We investigate the thermal stability of poly(ethylene oxide) (PEO) intercalated in GO (PEO/GO) in detail, using a combination of techniques including X-ray diffraction (XRD), thermogravimetry (TGA) and TGA–mass spectroscopy (TGA–MS) in dynamic (nonisothermal) and static (isothermal) modes. Our results show that intercalated PEO decomposes at 160 °C lower than neat PEO, and that GO decomposes at 50 °C lower than pristine GO, due to a synergistic instability between GO and intercalated PEO upon heating. Other hydrophilic polymers—such as poly(vinyl methyl ether) (PVME), poly(vinyl alcohol) (PAA), poly(vinylpyrrolidone) (PVP) and poly(acrylic acid) (PAA)—forming polymer-adsorbed GO structures are also observed to decompose at noticeably lower temperatures than either pristine GO or their own corresponding neat polymers. Unlike PEO/GO intercalation compounds, the excess of PEO phase in PEO–GO composites decomposes at temperatures close to that of neat PEO, which demonstrates that those polymer chains far from the adsorbing GO surface are not significantly affected by the presence of GO sheets. Furthermore, isothermal TGA data for PEO/GO intercalation compounds with PEO chains from 5 to 2135 monomeric units are well described by an autocatalytic model similar to that we found for pristine GO in a previous study, which suggests that the overall decomposition of PEO/GO is dominated by the reduction and exfoliation of GO. However, when PEO is adsorbed on graphene substrate, which is thermally stable at the studied temperatures, the kinetic mechanisms follow a first-order reaction similar to neat PEO, but the decomposition occurs with a considerably lower activation energy.

Synthesis, characterization, thermal and optical properties of styrene derivatives having pendant p-substituted benzylic ether groups

The derivatives of styrene monomer, 4-chlorophenyl-4-vinylbenzyl ether (M1), 4-methoxyphenyl-4-vinylbenzyl ether (M2), 4-ethylphenyl-4-vinylbenzyl ether (M3) and 1-naphtylphenyl-4-vinylbenzyl ether (M4) were synthesized. The normal free radical polymerization of monomers in 1,4-dioxane were performed by using 2,2′-azobisisobutyronitrile as an initiator at 65 °C. The monomers and their homopolymers were characterized by FT-IR, NMR and elemental analyses measurements. The thermal stability of polymers was investigated by thermogravimetric and differential scanning calorimetric analysis. Thermal degradation activation energies of the polymers were calculated by the Ozawa and Kissinger methods. In addition, photo-stability tests of the polymers under near-UV irradiation were performed.

Preparation and Characterization of PMMA/MMT Organic-Inorganic Hybrid Materials via RAFT Polymerization

In this article, the poly(methyl methacrylate)/montmorillonite (PMMA/MMT) organic-inorganic hybrid materials were prepared by conventional free radical polymerization and reversible addition-fragmentation chain transfer (RAFT) polymerization, respectively. The kinetics comparison of these two polymerizations was studied. The PMMA/MMT hybrid materials were characterized by gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). According to these results, we knew that the polymerization behavior of MMA showed controlled/living radical polymerization (CLRP) characteristics under the control of RAFT agent. The incorporation of RAFT agent and MMT nanoparticles improved the thermal properties of polymers, and the thermal stability of polymers increased with increasing content of MMT nanoparticles. The structures and morphologies of PMMA/MMT hybrid materials were characterized by FT-IR, XRD and TEM. These results showed that the MMA monomer can be initiated and propagated in the clay layers of MMT via the control of RAFT agent, and then the exfoliated structure was obtained for the hybrid materials.

Polymer–clay nanocomposites thermal stability: experimental evidence of the radical trapping effect

The radical trapping flame retardant mechanism of polymer–clay nanocomposites is frequently claimed to be responsible for improving the thermal stability of polymers. However it had never been demonstrated. Herein using in situ time-resolved X-ray Absorption Spectroscopy (XAS) we present experimental evidence that Fe3+ embedded in the clay can act as electron acceptors during polymer thermal decomposition. Therefore it contributes to improve the polymer thermal stability.

Single-component polyfluorene electrolytes bearing different counterions for white light-emitting electrochemical cells

A series of polyfluorene (PF) electrolytes bearing Br−, BF4-, or PF6- counterions were synthesized and characterized. 2,1,3-Benzoselenadiazole moieties were incorporated into polymer main chains to produce single-component white light-emitting polymers. The thermal stability of Br-containing ionic PF was decreased because of the Hofmann elimination occurred at higher temperature. By replacing Br− with BF4- or PF6- counterions, the thermal stability of polymers was significantly improved. UV–vis absorption and photoluminescence spectra revealed that Br-containing ionic PF generates blue shift in methanol, while BF4 and PF6-containing ionic PFs show blue shift in acetonitrile. Electrochemical analysis revealed that oxidation potentials of BF4 and PF6-containing ionic PFs were decreased, resulting in increase in HOMO and LUMO levels. The optimized spin-coated light-emitting electrochemical cell (LEC) with the configuration of ITO/PEDOT/polymer/Ag showed a maximum luminescence efficiency of 1.56lm/W at a low operation bias of 3V. The single-component LEC device exhibited pure white light emission with CIE’1931 coordinates approaching (0.33, 0.33) and high color rendering index (CRI>85), referring to its potential use in solid-state-lighting application.

Synthesis of room temperature ionic liquids based random copolyimides for gas separation applications

Random copolyimides were synthesized using diamino functional room temperature ionic liquid (RTIL) and were characterized. Specifically, a diamino functional RTIL, 1,12-di[3-(3-aminopropyl) imidazolium] dodecane bis[(trifluoromethyl)sulfonyl] imide ([C12(DAPIM)2][Tf2N]2), was reacted with 2,2-bis(3,4-carboxylyphenyl) hexafluoropropane dianhydride (6FDA) and m-phenylenediamine (MDA) to form random cooplyimides with a [C12(DAPIM)2][NTf2]2 concentration varying from 10 to 30mol%. Incorporation of [C12(DAPIM)2][NTf2]2 within the 6FDA–MDA backbone resulted in decreases in the polymer thermal stability, glass transition temperature, d-spacing, fractional free volume and increments in density. The gas permeability, solubility and diffusivity of the random copolyimides decreased and the permeability selectivities increased compared with the pure 6FDA–MDA polyimide.

Photo and electrically switchable behavior of azobenzene containing pendant bent‐core liquid crystalline polymers

AbstractNew class of photo and electrically switchable azobenzene containing pendant bent‐core liquid crystalline monomers (AZBM 1, 2, and 3) and their polymers (AZBP 1, 2, and 3) are reported. The synthesized precursors, monomers, and polymers were characterized by FT‐IR, 1H, and 13C NMR spectroscopy. Thermal stability of polymers was examined by thermogravimetric analysis and revealed stable up to 260 °C. The mesophase transition of monomers and polymers are observed through polarized optical microscopy (POM) and further confirmed by differential scanning calorimetry (DSC). The electrically switching property of monomers and their polymers were studied by electro‐optical method. Among the three monomers AZBM 1, 2, and 3, AZBM 1 and 2 exhibit antiferroelectric (AF) switching and AZBM 3 exhibits ferroelectric (F) switching behavior. On the other hand, low molecular weight polymers (AZMP 1, 2, and 3) show weak AF and F switching behavior. The photo‐switching properties of bent‐core azo polymers are investigated using UV‐vis spectroscopy, trans to cis isomerization occurs around 25 s for AZBP‐1 and 30 s for AZBP‐2 and 3 in chloroform, whereas reverse processes take place around 80 and 90 s. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

Synthesis and characterization of new polyamides derived from alanine and valine derivatives

BackgroundMany efforts have been recently devoted to design, investigate and synthesize biocompatible, biodegradable polymers for applications in medicine for either the fabrication of biodegradable devices or as drug delivery systems. Many of them consist of condensation of polymers having incorporated peptide linkages susceptible to enzymatic cleavage. Polyamides (PAs) containing α-amino acid residues such as L-leucine, L-alanine and L-phenylalanine have been reported as biodegradable materials. Furthermore, polyamides (PAs) derived from C10 and C14 dicarboxylic acids and amide-diamines derived from 1,6-hexanediamine or 1,12-dodecanediamine and L-phenylalanine, L-valyl-L-phenylalanine or L-phenylalanyl-L-valine residues have been reported as biocompatible polymers. We have previously described the synthesis and thermal properties of a new type of polyamides-containing amino acids based on eight new symmetric meta-oriented protected diamines derived from coupling of amino acids namely; Fomc-glycine, Fmoc-alanine, Fomc-valine and Fomc-leucine with m-phenylene diamine or 2,6-diaminopyridine. Results revealed that incorporation of pyridine onto the polymeric backbone of all series decreases the thermal stability.Here we describe another family of polyamides based on benzene dicarboxylic acid, pyridine dicarboxylic acid, and α-amino acid linked to benzidine and 4,4′-oxydianiline to study the effect of the dicarboxylic acid as well as the amino acids on the nature and thermal stability of the polymers.ResultsWe report here the preparation of a new type of polyamides based on benzene dicarboxylic acid, pyridine dicarboxylic acid, and α-amino acid linked to benzidine and 4,4′-oxydianiline to study the effect of the dicarboxylic acid as well as the amino acids on the nature and thermal stability of polymers. The thermal properties of the polymers were evaluated by different techniques. Results revealed that structure-thermal property correlation based on changing the dicarboxylic acid monomer or the diamine monomer demonstrated an interesting connection between a single change (changing the dicarboxylic acids in each series while the diamine is fixed) and thermal properties. The newly prepared polymers may possess biodegradability and thus may find some applications as novel biomaterials.ConclusionsThe thermal properties of the new type of polyamides based on benzene dicarboxylic acid, pyridine dicarboxylic acid, and α-amino acid (alanine and valine) linked to benzidine and 4,4′-oxydianiline were evaluated by thermal gravimetric (TG), differential thermal gravimetric (DTG) and differential thermal analysis (DTA) techniques. Results revealed that the structure-thermal property correlation based on changing the dicarboxylic acid monomer or the diamine monomer demonstrated an interesting connection between a single change (changing the dicarboxylic acids in each series while the diamine is fixed) and thermal properties. In addition, pyridine-containing polymers exhibited semicrystalline characteristic with melting temperature, Tm. where none of the valine-containing polymers showed a melting and crystallization peak indicating that the polymers were amorphous. This is expected since L-valine side chain can inhibit close packing and eliminate crystallization. The newly prepared polymers may possess biodegradability and thus may find some applications as novel biomaterials.

Silsesquiazane/organic polymer blends as organic-inorganic hybrid materials

Silsesquiazane (SSQZ), one of the branched forms of polysilazane, was blended with polystyrene (PS), poly(methyl methacrylate) (PMMA), poly(iso-butyl methacrylate) (PBMA), and poly(vinyl acetate) (PVAc) to produce organic-inorganic hybrid materials. The polymers were selected to provide specific interaction, such as π-π interaction or hydrogen bonding, with SSQZ. AFM studies revealed that carbonyl containing polymers, PMMA, PBMA, and PVAc were miscible with SSQZ while PS was immiscible. DSC analysis of the hybrids also supported the miscibility behaviours of the system. The glass transition behaviour of SSQZ/PS showed individual transition temperature corresponding to the each component while SSQZ/carbonyl-containing polymers displayed one transition temperature that matched with the theoretically calculated values following the Kwei equation. Among the miscible hybrid system, the interaction with SSQZ increased in the order of PMMA> PBMA> PVAc, as determined by the q value in the Kwei equation. This result was confirmed by determining the degree of hydrogen bonding in FT-IR spectra. Thermal stability of organic polymers was improved by incorporating SSQZ regardless of the miscibility.

An efficient strategy of managing irrigation water based on formulating highly absorbent polymer–inorganic clay composites

Summary The management of irrigation water presents a great challenge for the agriculture field. In view of increasing soil water-holding capacity and increasing water-use efficiency, an efficient strategy of managing irrigation water based on formulating highly absorbent polymer–inorganic clay composite (polyacrylic acid–layered double hydroxide; PAA–LDH) was offered. The PAA–LDH composite was synthesized by an incorporation/in situ polymerization technique. Scanning electron microscopy, X-ray analysis and infrared spectroscopy were used to confirm the composite structure. The thermal gravimetric analysis was applied to investigate the polymer thermal stability after the composite formation. The irrigation experiments were conducted in a wooden soil box with a transparent plexiglas side by using a subsurface drip irrigation system. The X-ray patterns and infrared spectra confirmed the incorporation of acrylic acid monomer (AA) into the gallery of LDH. The SEM images emphasized the composite structure of PAA–LDH and indicated its ability to absorb and keep water. The stability of PAA was promoted against the thermal decomposition after the composite formation. The composite structure of PAA–LDH worked as water barrier and secondary water source during the irrigation process. The soil moisture distribution patterns were enhanced after the application of PAA–LDH composites as a soil conditioner.

Experimental and theoretical studies on electrochemical synthesis of poly(3-amino-1,2,4-triazole)

The electrochemical synthesis of poly(3-amino-1,2,4-triazole) (PATA) on the platinum (Pt) electrode was achieved in ammonium oxalate solution by cyclic voltammetry technique. The conductivity of film was measured with four probe technique, the surface morphology was monitored with atomic force microscopy (AFM) and characterization was achieved by Fourier transform infrared spectroscopy (FT-IR) and UV–vis spectroscopy techniques. The thermal stability of polymer has also been investigated by the means of thermogravimetric analysis (TGA). The electrochemical stability of Pt/PATA was investigated in different buffer solutions. The quantum theoretical calculations employed and some parameters (dipole moment, EHOMO, ELUMO) were determined.

Thermal studies on polycaprolactam

Initial granules and thin folia of polycaprolactam formed by pressing under various conditions were studied. Using an apparatus for simultaneous thermal analyses STA 449 F3 Jupiter (NETZSCH—Germany), the thermal behavior of the objects were studied in the temperature interval from 20 to 600 °C. From the DSC curves obtained, a number of thermal and thermo physical properties were determined, including the heats of melting and degrees of crystallinity of the crystalline phases formed. For comparison, the effective kinetic parameters and the most probable rate-determining mechanisms of thermal degradation of certain samples in air and inert media were determined from the TG data curves. The crystalline structure perfectness was proved to exert stabilizing effect while the moisture contained had negative effect on polymer thermal stability, especially in oxidative medium.

Synthesis and characterization of copper ferrite nanoparticles doped polyaniline

In situ chemical oxidation polymerization was carried out to synthesize copper ferrite nanoparticles doped polyaniline (PANI/CuFe2O4). The copper ferrite nanoparticles were prepared by the co-precipitation method using metal nitrates as precursors. The materials were characterized by XRD, FTIR, SEM, TEM and TGA in order to determine the average crystallite size, arrangement of nanoparticles in the polymer matrix and thermal stability of the complex. The nanoparticles doped organic polymer showed good electrical conductivity with an activation energy value of 2.768eV. The materials possess superior thermal stability than pure PANI. Furthermore, the adsorption properties of the materials were investigated by monitoring the adsorption of a textile azo-dye (Direct Yellow-27) in aqueous media using UV–Visible spectrophotometer. Adsorption was found to be a dose dependent performance i.e. as the amount of adsorbent increases, removal rate increases. The adsorption efficiency of the material to remove azo-dye was also tested at four different pH (3.0, 5.0, 8.0 and 11.0) and it was found that the PANI/CuFe2O4 exhibit excellent adsorption at pH 3.4. The results of the present study suggested that desired properties can be attained by mixing different proportions of PANI and nano CuFe2O4.

Conformance Control with Polymer Gels: What it Takes to be Successful

Whenever water production exceeds economic limits of a given oil or gas field, the need arises for a process by which produced water is reduced. Published data indicate that the petroleum industry spends $40 billion every year to process excessive produced water. Water also causes corrosion, scale and requires the construction of larger downstream handling facilities. Polymer gels, due to their versatile nature, are deemed suitable for reducing water production from oil and gas fields. Treatments utilizing these materials are generally referred to as conformance improvement treatments (CITs). Depending on the type of the crosslinker used, polymer gels can be classified as inorganically crosslinked or organically crosslinked. Examples on each type highlighting their capabilities and shortcomings are provided. Polymer thermal stability, compatibility with mixing waters, correct identification of the water production mechanism and gelation time are all key parameters for successful polymer-gel CITs. We will present an overview of the polymer gels technology available up-to-date with practical examples on key parameters for successful CITs. This paper will serve as a guide for scientists and engineers on the use of polymer gels for water control.

Adsorptive removal of As(III) and As(V) from water and wastewaters using an anion exchanger derived from polymer-grafted banana stem

In this study, the adsorption characteristics of As(III) and As(V) from water and wastewater using polyacrylamide-grafted banana stem with quaternary ammonium functionality (PGBS-AE) were investigated. Infrared spectroscopic, and thermogravimetric analyses were performed to affirm the polymer grafting, functionality, morphology, and thermal stability. Batch experiments were carried out to understand the effect of contact time, concentration, pH, adsorbent dose, and temperature of the solution for the adsorption of As(III) and As(V) onto PGBS-AE. Equilibrium was achieved within 1 h and the optimum pH was found to be 9.0 and 3.0 for As(III) and As(V), respectively. Isotherm studies showed that the Langmuir equation fits best. Maximum adsorption capacities of 50 and 5.5 g kg−1 were obtained for As(III) and As(V) at 30°C. The endothermic nature of adsorption was evident as the adsorption efficiency increased with temperature. The thermodynamic parameters were evaluated to explain the feasibility of adsorption and to predict the nature of adsorption. The competence of the adsorbent for practical purposes was also analyzed by treating with a fertilizer industry effluent sample. Studies pertaining to adsorbent regeneration and readsorption of As(III) and As(V) were carried out for four consecutive cycles.

Effects of hydroxyvalerate contents in thermal degradation kinetic of cellulose acetate propionate/poly(3-hydroxyalkanoates) blends

Thermal stability of polymers is an important parameter that determines the application as well as the processing conditions. The green polymers have shown low thermal stability, such as the polyhydroxyalkanoates (PHAs). The PHAs with different comonomers containing hydroxyvalerate (HV) were studied. It was seen that the green polymer showed a fast thermal degradation process. The addition of the HV comonomer modified this profile and the thermal degradation kinetic. The blend prepared between the PHAs and other polymers can modify the thermal degradation process of the green polymers. In the present study, blends of cellulose acetate propionate and PHAs were prepared, and the thermal degradation kinetics of these blends were evaluated. It was observed that the cellulose acetate propionate (CAP) phase in the blends modified the thermal degradation process and kinetic profile of the PHA phase. In the blends, the thermal stability of the PHAs was slightly modified because of CAP reducing the reactivity of the PHAs. On the other hand, the thermal stability of the CAP phase in the blends is not largely modified by the PHA phase. However, the hydroxyvalerate comonomer decreases the reactivity of the CAP phase at the start of thermal degradation of the same. The interaction between the phases promotes the synergetic interaction, which slightly improves the thermal stability of the two polymers blends.

The influence of shaped TiO2 nanofillers on thermal properties of polyvinyl alcohol

PVA-based nanocomposites consisting of shaped TiO2 nanocrystals (nanoparticles, nanotubes or nanorods) were synthesized by direct blending of polymer and titania nanocrystals solution or powder. In order to elucidate the influence of shape of titania nanocrystals on thermal stability of polymer matrix and particles interaction with PVA chain, structural and thermal characterizations of PVA/TiO2 nanocomposites were performed. Faceted nanoparticles increased the thermal stability of PVA matrix. Titania nanotubes and nanorods did not show any stabilizing effect on polymer matrix in argon atmosphere. The thermo-oxidative degradation temperature of PVA increased with addition of faceted TiO2 nanoparticles. The thermo-oxidative stability of the PVA matrix was affected more by the presence of titania nanotubes and nanorods in comparison with its thermal stability in inert atmosphere. The crystallinity degree (Xc=32 %) of PVA matrix slightly decreased in the presence of faceted TiO2 nanoparticles in nanocomposite sample.

Impact of modified alumina oxides on the fire properties of PMMA and PS nanocomposites

AbstractGrafting of ethylene glycol methacrylate phosphate (EGMP) monomer polymerized from alumina nanoparticles has been performed in order to confer a better thermal stability and fire retardancy to PMMA and PS nanocomposites. Grafting and polymerization processes have been investigated using FTIR, TGA, and elemental analyses. Thermal stability and decomposition routes of monomer and polymer grafted alumina have been studied using thermogravimetric analysis and compared with the thermal behavior of the same alumina modified with octylsilane. The thermal stability of EGMP supported by the nanoparticles is higher than that of free EGMP. The incorporation of 5 wt% of both surface treated alumina in PMMA and PS leads to an improvement of thermal stability in comparison with unfilled polymers as well as nanocomposites containing unmodified alumina. Furthermore, the grafting of organic compounds on alumina also allows the peak of heat release rate measured using a cone calorimeter to be significantly reduced for PMMA nanocomposites. Copyright © 2010 John Wiley & Sons, Ltd.

Synthesis, characterization polymerization and antibacterial properties of novel thiophene substituted acrylamide

Ethyl 2-acrylamido-4,5,6,7-tetrahydrobenzo [b] thiophene-3-carboxylate (ETTCA) has been synthesized and its structure has been elucidated by elemental analysis and spectral tools. Free radical polymerization of (ETTCA) has been conducted in several solvents using azobisisobutyronitrile (AIBN) as an initiator. The kinetic parameters of polymerization of the ETTCA were investigated, and it was found that the polymerization reaction follows the conventional free radical scheme. The overall activation energy of polymerization Δ E was determined (Δ E = 45.11 kJ mol −1). The copolymerization of ETTCA with three conventional monomers was carried out in dioxane at 65 °C. The monomer reactivity ratios for the copolymerization of ETTCA with methyl methacrylate (MMA), vinyl acetate (VA) and vinyl ether (VE) were calculated. Thermal stability of the ETTCA polymer and its copolymers were investigated by thermogravimetric analysis. It has been found that the prepared polymer (PETTCA) and its copolymers with VA have moderate biological activity and highly dependent on the copolymer composition.

Thermal behavior of poly(ethylene-co -propylene) containing carbon nanofibers

The effect of carbon nanofiber on the thermal behavior of poly(ethylene-co-propylene) (PEP) as revealed by differential scanning calorimetry and thermogravimetric analysis is reported. Analysis showed faster crystallization of PEP at higher temperature upon cooling with the increase of carbon nanofiber (CNF) content. The crystallization behavior changed to a single narrow crystallization peak as compared with the broad double crystallization peak of the neat polymer. This demonstrates the nucleation ability of CNF to induce crystals with more uniform distribution. The modifiedAvrami approach was used to study the crystallization behavior. We found that the crystallization rate constant increased with addition of CNFs. The dimensionality of crystal growth was found not to depend significantly on the content of CNF. Thermal degradation in air was monitored using thermogravimetric analysis and observed that the incorporation of nanofiber greater than 2.4 vol% improves thermal stability of PEP. All these results indicate that CNFs can significantly help polymer processing and increase thermal stability of polymers. POLYM. ENG. SCI., 52:408–413, 2012. a 2011 Society of Plastics Engineers