Thermal properties of silica/poly(2,6-dimethyl-1,4-phenylene oxide) films prepared by emulsion polymerization

Thermal properties of the silica/poly(2,6-dimethyl-1,4-phenylene oxide) films prepared via emulsion polymerized mixed matrix (EPMM) method are investigated, and the impact of the synthesis protocol on the silica content, compatibility between the organic and inorganic phases, and the thermal stability of these nanocomposites is studied. Two series of films, namely EPMM-1S and EPMM-2S, synthesized in one- and two-step process, respectively, with different combinations of surfactant and compatibilizer were prepared. The polymerization of the silica precursor in the films was confirmed by ²⁹Si nuclear magnetic resonance, and its content was investigated by inductively coupled plasma mass spectroscopy analysis. Thermal properties of the EPMM films were investigated by differential scanning calorimetry and thermogravimetric analysis. The glass transition temperature (T _g) of EPMM films was greater compared to the neat PPO film. However, an increase in T _g was not related to the concentration of silica in the film, but rather to the quality of dispersion of synthesized nanoparticles. Despite a lower inorganic loading, EPMM-1S films had a greater T _g than EPMM-2S films. On the other hand, both the decomposition temperature and the activation energy for the decomposition were directly related to the silica content in the EPMM films. In general, regardless of the synthesis protocol, the presence of compatibilizer (ethanol) leads to greater inorganic content and improved thermal properties of the EPMM films.     

Morphology and thermal properties of polyhedral oligomeric silsesquioxane/polybutadiene nanocomposites prepared by anionic polymerization

The morphology and thermal properties of Allylisobutyl Polyhedral Oligomeric Silsesquioxane (POSS)/Polybutadiene (PB) nanocomposites prepared through anionic polymerization technique were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results of XRD, SEM and TEM showed that the aggregation of POSS in PB matrix occurred obviously, forming crystalline domains and the size of POSS particles increased with increasing POSS content. The DSC and TGA results indicated that the glass transition temperature (T _g) of the nanocomposites was significantly increased and the maximum degradation temperature (T _dmax) of nanocomposites was slightly increased compared with pure PB, implying an increase in thermal stability.     

Preparation and properties of enhanced nanocomposites based on PLA/PC blends reinforced with silica nanoparticles

In order to lower brittleness of biobased polylactic acid (PLA), its blending with polycarbonate and nanosilica is aimed. In this line, to increase compatibility of the ingredients, dicumyl peroxide (DCP) and Cobalt (II) acetylacetonate (Co) were used as grafting and transesterification catalysts, respectively. The X‐ray diffraction (XRD) spectra demonstrated high compatibility of the ingredients by broadening of the PLA characteristic peaks and, also, good dispersion of nanosilica particles, especially in PLA/PC/Silica/Co sample. The EDX maps confirmed good nanosilica dispersion, too. The silica nanoparticle size was ranged from 20 to 100 nm in transmission electron microscopy (TEM) pictures. All nanocomposites showed improved thermal stability in thermogravimetric analysis (TGA). Differential scanning calorimetry (DSC) results demonstrated lower T_g, T_m, and crystallinity values for the fabricated nanocomposites. Notably, the dynamic mechanical thermal analysis (DMTA) curves confirmed the T_g, T_m, and T_cc trend obtained in DSC; moreover, much higher surface under tan δ peak for PLA/PC/Silica/Co sample was obtained, which implies its higher toughness. The precise tensile study of the samples confirmed significantly higher elongation at break of the nanocomposites, more considerably in PLA/PC/Silica/Co sample, with nearly negligible defect on tensile strength and modulus. In a concise, the obtained results confirmed the higher efficiency of Co catalyst, which leads to the sample with improved characteristics compared with DCP.     

Thermal characterizations of multifunctional epoxy/anhydride systems used for pultruded composite ropes

The viscoelastic characterization and thermal stability property of some multifunctional epoxy/anhydride systems cured at different schedules were investigated by dynamic mechanical thermal analysis (DMTA) in single cantilever mode at fixed frequency, and by non-isothermal thermogravimetric (TG) analysis, respectively. According to the DMTA results, three obviously different glass transition temperatures (T _g), were observed, among which TGDDM/MHHPA system exhibits the largest T _g. While from the TG curves, the results of the mass loss and thermal stability showed that, after cured for a prolonged duration, the TGDDM/MHHPA system possessed the most excellent performance in heat resistance.     

Effect of different nanoparticles on thermal decomposition of poly(propylene sebacate)/nanocomposites: Evaluation of mechanisms using TGA and TG–FTIR–GC/MS

In the present study poly(propylene sebacate) (PPSeb) nanocomposites containing 2 wt% of fumed silica nanoparticles (SiO₂) or multiwalled carbon nanotubes (MWCNTs), or montmorillonite (MMT) were prepared by in situ polymerization. The thermal degradation of nanocomposites was studied using thermogravimetric analysis (TGA). It was found that the addition of MWCNTs and MMT enhances the thermal stability of the polymer, while SiO₂ nanoparticles do not affect it. From the variation of the activation energy (E) with increasing degree of conversion it was found that the decomposition of nanocomposites proceeded with a complex reaction mechanism with the participation of at least two different steps. To evaluate the thermal decomposition mechanisms and mainly the effect of nanoparticles on the thermal decomposition of PPSeb, TGA/FTIR and a combination of TG-gas chromatography–mass spectrometry (TG/GC–MS) were used. From mass ions detection of the formed decomposition compounds it was found that the decomposition of PPSeb and its nanocomposites, takes place mainly through β-hydrogen bond scission and, secondarily, through α-hydrogen bond scission. The main decomposition products were aldehydes, alcohols, allyl, diallyl, and carboxylic acids.     

Thermal degradation behavior of radiation synthesized polydiallyldimethylammonium chloride

Thermogravimetric analysis (TGA) and differential scanning calorimetric (DSC) studies were carried out on gamma radiation synthesized polydiallyldimethylammonium chloride (PDADMAC). The polymer was found to undergo thermal degradation in two stages. The first stage showed a weight loss of 33% and the second stage showed a weight loss of 67%. The DSC thermogram shows two endothermic peaks corresponding to the two stages in the TG thermogram and the experimental enthalpy change associated with the first and second stages were 650 J g⁻¹ and 129.5 J g⁻¹, respectively. The nth-order kinetic parameters (order of the reaction, activation energy and the pre-exponential factor) were determined from a single dynamic DSC or thermogravimetric (TG) thermogram by the method of least square. Theoretical TG/differential thermogravimetric (DTG) and DSC thermograms derived from the calculated kinetic parameters were in good agreement with the experimental ones at the heating rate employed. However, the kinetic parameters determined using TG and DSC were different. This leads to the conclusion that the degradation mechanism could be complicated and may consists of a number of parallel or consecutive reactions. The glass transition temperature (T_g) of the polymer was found to be around 150 °C depending on the test method employed.     

Thermal behaviour of some mixture of collagen hydrolysates with vinylic polymers

The thermal behaviour was studied by DSC and TG methods for some mixtures of poly(ethyl acrylate) and poly(vinyl alcohol) with collagen to examine compatibility, glass transition temperature and thermal degradation. The mixtures of collagen hydrolysates with poly(ethyl acrylate) have a single glass transition temperature. The mixtures with poly(vinyl alcohol) show a glass transition temperature independent of composition and a melting temperature dependent on composition. The DSC and T_g data reveal partial compatibility at low temperature. By heating above 200°, the mixture separates into the two components which behave independently.     

The disorderly exfoliated LDHs/PMMA nanocomposites synthesized by in situ bulk polymerization: The effects of LDH-U on thermal and mechanical properties

The disorderly exfoliated layered double hydroxides/poly(methyl methacrylate) (LDHs/PMMA) nanocomposites were obtained in a two-stage process by the in situ bulk polymerization of methyl methacrylate (MMA) in the presence of 10-undecenoate intercalated LDH (LDH-U). The dispersed behavior of the LDH-U in the PMMA matrix was identified by using X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV/visible transmission spectroscopy. All these nanocomposites showed significantly enhancement of glass transition temperature (T_g) and the decomposition temperatures compared to pristine PMMA, as identified in differential scanning calorimetry (DSC) and thermogravimetric (TGA) analysis. The tensile modulus of these nanocomposites was also enhanced by incorporating the LDH-U into the PMMA matrix and increased as the amount of LDH-U increased. According to the analytical method of Ozawa-Flynn, the degradation activation energies of these nanocomposites are higher than that of pristine PMMA.     

Exploitation of introducing of catalytic centers into layer galleries of layered silicates and related epoxy nanocomposites. I. Epoxy nanocomposites derived from montmorillonite modified with catalytic surfactant‐bearing carboxyl groups

Montmorillonite (MMT) was modified with the acidified cocamidopropyl betaine (CAB) and the resulting organo‐montmorillonite (O‐MMT) was dispersed in an epoxy/methyl tetrahydrophthalic anhydride system to form epoxy nanocomposites. The intercalation and exfoliation behavior of the epoxy nanocomposites were examined by X‐ray diffraction and transmission electron microscopy. The curing behavior and thermal property were investigated by in situ Fourier transform infrared spectroscopy and DSC, respectively. The results showed that MMT could be highly intercalated by acidified CAB, and O‐MMT could be easily dispersed in epoxy resin to form intercalated/exfoliated epoxy nanocomposites. When the O‐MMT loading was lower than 8 phr (relative to 100 phr resin), exfoliated nanocomposites were achieved. The glass‐transition temperatures (T_g's) of the exfoliated nanocomposite were 20 °C higher than that of the neat resin. At higher O‐MMT loading, partial exfoliation was achieved, and those samples possessed moderately higher T_g's as compared with the neat resin. O‐MMT showed an obviously catalytic nature toward the curing of epoxy resin. The curing rate of the epoxy compound increased with O‐MMT loading. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1192–1198, 2004     

Use of polyethylene glycol in the process of sol–gel encapsulation of Burkholderia cepacia lipase

Lipases from Burkholderia cepacia were encapsulated using polyethylene glycol (PEG, M _w 1500) at various concentrations (0.5–3.0 %, w/v) as an additive during the sol–gel immobilisation process. Matrixes immobilized in the presence and absences of additives were characterized by thermal analysis [thermogravimetric (TG) and differential scanning calorimetry (DSC)], scanning electron microscopy (SEM), enzymatic activity, and total activity recovery yield (Ya). The addition of PEG increased the activity values, with Ya just above 1.0 % (w/v) in the presence of PEG. The additional of 1.0 % (w/v) PEG increased enzyme activity from 33.98 to 89.91 U g^?1 and the values of recovery yield were 43.0–91.4 %, compared to values of the samples without PEG. PEG enhanced the thermal stability of the matrix structure in the temperature range 50–200 °C, as confirmed by TG and DSC analyses. This was influenced by the presence of water bound to the matrix. The SEM micrographs clearly showed an increase in the number of deposits on the material surface, producing matrices with greater porosity.     

Effect of nanosilica on thermal oxidative degradation of SBR

The effect of silica content on thermal oxidative stability of styrene–butadiene rubber (SBR)/silica composites has been studied. Morphologies of silica in SBR with different contents are investigated by scanning electron microscopy, which indicates that silica can well disperse in SBR matrix below the content of 40 %, otherwise aggregates or agglomerates will generate. Composites with around 40 % silica content show excellent mechanical properties and retention ratios after aging at 85 °C for 6 days. The values of activation energy (E _a) of pure SBR and its composites are calculated by Kissinger and Flynn–Wall–Ozawa methods based on thermogravimetric (TG) results, which suggests that composite with about 20 % silica has minimum E _a, and composite with 30–40 % silica has maximum E _a. According to TG curves, it is found that silica can suppress the formation of char leading to decline in stability to some extent. On the other side, silica also has positive effect on improving thermal stability of the matrix as filler. Thus, the SBR/silica composites with silica content of 30–40 % can possess both excellent resistance to thermal oxidative degradation and superior mechanical properties.     

Multi-walled carbon nanotubes functionalized with triethylenetetramine as fillers to enhance epoxy dimensional thermal stability

Multi-walled carbon nanotubes (MWCNT) have been used as fillers to improve thermal properties such as glass transition temperature (T _g) of epoxy materials. In this work, nanocomposites based on diglycidyl ether of bisphenol A resin and triethylenetetramine (TETA) were prepared by a three-roll mill process with TETA-functionalized (MWCNT–COTETA) and neat MWCNT. Thermogravimetric analysis of the nanofillers showed that in the case of MWCNT–COTETA, there is a 15 % mass loss that can be attributed to –COTETA and residual oxygen-containing functional groups. The influence of chemical modification on the behavior of the glass T _g was evaluated by dynamic scanning calorimetry. The MWCNT–COTETA allowed a ~20 °C reproducible increase of T _g in concentrations in the range of 0.5–1.0 mass%. Furthermore, images obtained by scanning electron microscopy were used to investigate the morphology of the polymer matrix and its interfaces. The quality of the dispersion and interaction of the nanotubes in the epoxy matrix was assessed from the images. Both the neat epoxy and the nanocomposite with MWCNT showed low thermal shrinkage upon curing.     

Thermal studies of chitin–chitosan derivatives

New poly(azo) amino-chitosan compounds were obtained from the azo coupling reaction of N-benzyl chitosan and diazonium salts. The thermal behavior of these compounds was studied by thermogravimetric analysis (TG), differential thermogravimetric analysis (DTG), TG coupled with a Fourier-transform infrared, and differential scanning calorimetry (DSC). TG/DTG curves of chitin–chitosan polymer showed two thermal events attributed to water loss and decomposition of the polysaccharide after cross-linking reactions. Thermal analysis of the poly(azo) amino-chitosan compounds showed that the decomposition temperatures decreased when compared to the starting chitin–chitosan and N-benzyl chitosan. DSC results showed an agreement with the TG/DTG analyses. Thermal behavior of poly(azo) amino-chitosans suggest that these compounds could be considered as potential thermal sensors.     

The effect of carbon nanotubes on epoxy matrix nanocomposites

The paper concerns thermal properties of epoxy/nanotubes composites for aircraft application. In this work, influence of carbon nanotubes on thermal stability, thermal conductivity, and crosslinking density of epoxy matrix was determined. Three kinds of nanotubes were used: non-modified with 1- and 1.5-μm length, and 1-μm length modified with amino groups. Scanning electron microscopy observations were done for examining dispersion of nanotubes in the epoxy matrix. Glass transition temperature (T _g) was readout from differential scanning calorimetry. From dynamic mechanical analysis, crosslinking density was calculated for epoxy and its composites. Also, thermogravimetric analysis was done to determine influence of nanotubes addition on thermal stability and decomposition process of composites. Activation energy was calculated from TGA curves by Flynn–Wall–Ozawa method. Thermal diffusivity was also measured. SEM images proved the uniform dispersion of carbon nanotubes without any agglomerates. It was found that nanotubes modified with amino groups lead to the increase of epoxy matrix crosslinking density. The significant increase in T _g was also observed. On the other hand, addition of carbon nanotubes leads to the decrease of thermal stability of polymer due to the increase of thermal diffusivity.     

Effect of organically modified montmorillonite filler on the dynamic cure kinetics, thermal stability, and mechanical properties of brominated epoxy/aniline formaldehyde condensates system

Nanocomposites, based on tetrabromo-bisphenol-A epoxy and aniline formaldehyde condensates, containing 5 and 10 % organically modified montmorillonite (O-MMT), were prepared. The morphologies of these nanocomposites were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The influences of O-MMT on the dynamic cure kinetics, thermal stability, and mechanical properties were investigated by differential scanning calorimetry, thermogravimetric analysis, and non-destructive ultrasonic testing techniques. The XRD and SEM results indicated a good dispersion of O-MMT within the epoxy matrix. The relation between the activation energy, E _a, and the degree of cure, α, for the examined systems was obtained by applying model-free isoconversional Kissinger–Akahira–Sunose method. As α increases, E _a increases gradually, almost independent of the amount of O-MMT. The dynamic cure kinetics of the neat epoxy system as well as its nanocomposites were described by ?estàk–Berggren, [SB (m, n)], autocatalytic model. The O-MMT enhances the thermal stability of the examined epoxy system. The results of the mechanical properties indicated that the addition of O-MMT enhances the Young’s and shear elastic modulus and microhardness. The values of these parameters increase with increasing O-MMT loading.     

Thermal properties and flame retardancy of novel epoxy based on phosphorus‐modified Schiff‐base

Through addition reaction of Schiff‐base terephthalylidene‐bis‐(p‐aminophenol) ( DP‐1 ) and diethyl phosphite (DEP), a novel phosphorus‐modified epoxy, 4,4'‐diglycidyl‐(terephthalylidene‐bis‐(p‐aminophenol))diphosphonate ether ( EP‐2 ), was obtained. An modification reaction between EP‐2 and DP‐1 resulted in an epoxy compound, EP‐3 , possessing both phosphonate groups and C?N imine groups. The structure of EP‐2 was characterized by Fourier transform infrared (FTIR), elemental analysis (EA), ¹H, ¹³C, and ³¹P NMR analyses. The thermal properties of phosphorus‐modified epoxies cured with 4,4'‐diaminodiphenylmethane (MDA) and 4,4'‐diaminodiphenyl ether (DDE) were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The activation energies of dynamic thermal degradation (E_d) were calculated using Kissinger and Ozawa's methods. The thermal degradation mechanism was characterized using thermogravimetric analysis/infrared spectrometry (TG‐IR). In addition, the flame retardancy of phosphorus‐modified epoxy thermosets was evaluated using limiting oxygen index (LOI) and UL‐94 vertical test methods. Via an ingenious design, phosphonate groups were successfully introduced into the backbone of the epoxies; the flame retardancy of phosphorus‐modified epoxy thermosets was distinctly improved. Due to incorporation of C?N imine group, the phosphorus‐modified epoxy thermosets exhibited high thermal stabilities; the values of glass‐transition temperatures (T_gs) were about 201–210°C, the values of E_d were about 220–490 kJ/mol and char yields at 700°C were 49–53% in nitrogen and 45–50% in air. These results showed an improvement in the thermal properties of phosphorus‐modified epoxy by the incorporation of C?N imine groups. Copyright © 2010 John Wiley & Sons, Ltd.     

Novel polyester/SiO2 nanocomposite membranes: Synthesis,properties and morphological studies

In this paper, a new type of soluble polyester/silica (PE/SiO₂) hybrid was prepared by the ultrasonic irradiation process. The coupling agent γ-glycidyloxypropyltrimethoxysilane (GOTMS) was chosen to enhance the compatibility between the polyester (PE) and silica (SiO₂). Furthermore, the effects of the coupling agent on the morphologies and properties of the PE/SiO₂ hybrids were investigated using UV-vis and FT-IR spectroscopies and FE-SEM. The densities and solubilities of the PE/SiO₂ hybrids were also measured. The results show that the size of the silica particle was markedly reduced by the introduction of the coupling agent, which made the PE/SiO₂ hybrid films become transparent. Furthermore, thermal stability, residual solvent in the membrane film and structural ruination of membranes were analyzed by thermal gravimetric analysis (TGA). The effects of SiO₂ nanoparticles on the glass transition temperature (T_g) of the prepared nanocomposites were studied by differential scanning calorimetry (DSC). Moreover, their mechanical properties were also characterized. It can be observed that the Young's moduli (E) of the hybrid films increase linearly with the silica content. The results obtained from gas permeation experiments with a constant pressure setup showed that adding SiO₂ nanoparticles to the polymeric membrane structure increased the permeability of the membranes.     

Thermal properties of single walled carbon nanotubes composites of polyamide 6/poly(methyl methacrylate) blend system

The nanocomposites of polyamide 6 (PA6)/poly(methyl methacrylate) (PMMA)/non-functionalized and functionalized [carboxylic acid (COOH) and hydroxyl (OH)] single wall carbon nanotubes (SWCNTs) were prepared in mass ratios of 79.5/19.5/1, 49.5/49.5/1, and 19.5/79.5/1 by melt–mixing method at 230 °C. The PA6/PMMA blends with mass ratios of 80/20, 50/50, and 20/80 served as references. The Fourier transform infrared analyses of nanocomposites showed the formation of hydrogen bond interactions among PA6, PMMA, and OH and COOH functional groups of SWCNTs. The nanocomposites and blends had higher thermal stability with respect to the PMMA. The differential scanning calorimeter (DSC) curves showed that the nanocomposites and blends exhibited two T _g values at around 51 and 126 °C for PA6 and PMMA, respectively. About 20 °C early crystallization was observed in nanocomposites compared to the blends. The dynamic mechanical analysis (DMA) results suggested that among all the compositions of blends and nanocomposites, storage modulus (E′) was higher for PMMA-rich blends and nanocomposites. At 25 °C, the E′ values were higher for blends and nanocomposites compared to the neat PA6. The tan δ curves indicated that the more heterogeneity of the hybrid nature resulted in PA6/PMMA/SWCNTs-OH or SWCNTs-COOH with 79.5/19.5/1 mass ratio nanocomposites compared to the PA6/PMMA with 80/20 mass ratio blend. The higher T _g values of PA6 and PMMA were observed in DMA studies compared to the DSC studies for PA6 and PMMA as neat and in blends and nanocomposites. The significant improvements in crystallization of nanocomposites were considered resulting from achieving better compatibility among the polymer components and carbon nanotubes.     

Preparation of nano poly(phenylsilsesquioxane) spheres and the influence of nano-PPSQ on the thermal stability of poly(methyl methacrylate)

The nano poly(phenylsilsesquioxane) spheres (nano-PPSQ) were prepared by the sol?Cgel method and incorporated into poly(methyl methacrylate) (PMMA) by in situ bulk polymerization of methyl methacrylate. The structure of nano-PPSQ was confirmed by transmission electron microscope and thermogravimetry analysis (TG). The interaction between nano-PPSQ and PMMA was investigated by Fourier transform infrared spectra (FT-IR). The influence of nano-PPSQ on the thermal stability of PMMA was investigated by TG and differential scanning calorimetry (DSC) measurements. The results indicated that nano-PPSQ enhanced the thermal stability and the temperatures of glass transition (T _g) of nanocomposites. The effect of the heating rate in dynamic measurements (5?C30?°C?min^?1) on kinetic parameters such as activation energy by TG both in nitrogen and air was investigated. The Kissinger method was used to determine the apparent activation energy for the degradation of pure PMMA and nanocomposites. The kinetic results showed that the apparent activation energy for degradation of nanocomposites was higher than that of pure PMMA under air.     

Bismaleimide/rice husk silica reinforced composites

Silica derived from the renewable resource rice husk is modified using stearic acid and N-[4-(chlorocarbonyl)phenyl]maleimide. These materials are used as fillers in the bismaleimide, 4,4′-bismaleimidodiphenylmethane (BMIM), and thermally cured. The thermogravimetric (TG) curves for polyBMIM/silica composites showed no pronounced changes compared to the TG curve for the pure polyBMIM. Kissinger–Akahira–Sunose, Flynn–Wall–Ozawa, and Friedman methods are used to compute the activation energy (E _a) for degradation. Silica and surface-modified silica using stearic acid dispersed by ultrasonication increase the activation energy for degradation and show considerable influence on the thermal stability of cured BMIM. The long alkyl chain present in the stearic acid modified silica and the bulky spacer present in the chemically modified silica definitely alter the degradation process of cured BMIM. The SEM studies indicated uniform dispersion of the silica particles in the polyBMIM.