Homopolymerization effects in polymer layered silicate nanocomposites based upon epoxy resin: Implications for exfoliation

Exfoliation of polymer layered silicate nanocomposites based upon epoxy resin has previously been reported to be enhanced by allowing some homopolymerization of the resin to occur, catalyzed by the onium ion of the organically modified clay, before the addition of the cross‐linking agent and the curing of the nanocomposite. In this work we examine the effects of homopolymerization induced by pre‐conditioning the resin/clay mixtures by storing them at various temperatures, from room temperature to 100°C, prior to curing. It is found that pre‐conditioning results in similar increases in both the epoxy equivalent (EE) and the glass transition temperature (T_g) of the resin as a consequence of homopolymerization, with a linear relationship between EE and T_g that depends on the pre‐conditioning temperature. This is attributed to two different homopolymerization reaction mechanisms, activated monomer (AM) and activated chain end (ACE), the former dominating at high temperature and the latter at low temperature. The effects of these homopolymerization reactions on the network and nanostructure of the nanocomposite are discussed, the important aspect emerging being that the ACE mechanism is the one that most significantly enhances the exfoliation process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Eco-friendly flame retardant epoxy nanocomposites based on polyphosphonate and halloysite nanotubes

The preparation of a novel polyphosphonate (PSFR) is described here, starting from phenylphosphonic dichloride and an equimolecular mixture containing equal amounts of two bisphenols, namely 4,4′-dihydroxydiphenyl sulfone and 2-(6-oxido-6H-dibenzo<c,e><1,2>oxaphosphorin-6-yl)-1,4-benzenediol, following the polycondensation reaction in solution. Then, new environmental-friendly nanocomposites having improved flame retardancy have been prepared by incorporating PSFR and halloysite nanotubes (HNTs) into epoxy resin. The effect of PSFR and HNTs contents on the chemical and physical characteristics of epoxy nanocomposites was investigated. The success of the reactions was monitored by infrared spectroscopy (FTIR) while microscopic related techniques (SEM) gave information on the morphology of the products. The thermosets exhibit glass transition temperatures in the range of 62.4–97.1°C and thermal decomposition temperatures in the interval of 296–359°C. The appearance of the char residues obtained by pyrolysis was studied by SEM measurements. The flammability behavior has been studied by microscale combustion calorimetry (MCC) tests. A considerable improvement in the flame retardancy of the thermosets was obtained by simultaneous incorporation of HNTs (10 wt%) and PSFR (equivalent of 1 wt% P) into epoxy resin.     

Investigations on clay dispersion in polypropylene/clay nanocomposites using rheological and microscopic analysis

Morphology assessment plays an important role as the ultimate properties of the processed nanocomposites mainly depend upon the morphology. This study focuses on the evaluation of polypropylene/clay nanocomposite structure using rheological and transmission electron microscopic investigation. Melt processing of nanocomposite was carried out on a co‐rotating twin screw extruder. Maleic anhydride grafted polypropylene (PP‐g‐MA) was used as a compatibilizer to facilitate better mixing of clay in polypropylene. The effect of compatibilizer to clay ratio on dispersion was analyzed through rheological data. An increase in complex viscosity and storage modulus with increase in compatibilizer content is observed at lower frequency region. Shifting of crossover frequencies to a lower value also indicate better exfoliation. Improved exfoliated morphology was also corroborated by Cole–Cole and inverse loss tangent plots. Transmission electron microscopy (TEM) micrograph based unique statistical image analysis was carried out using ImageJ software. A compatibilizer to clay content of 2 : 1 was found to be the optimum composition which was further supported by dielectric and mechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4464–4473, 2013     

Effect of functionalization on dispersion of POSS‐silicone rubber nanocomposites

The nanocomposite of PDMS using functionalized fumed silica and nonreactive POSS as fillers were prepared by blend method in a planetary mixer. Fumed silica was functionalized by aliphatic and aromatic groups to study the filler–filler interactions with the aliphatic and aromatic POSS fillers and consequently their influence on the properties in the PDMS matrix. Transmission electron microscope (TEM) showed a good dispersion in the systems having the silica and POSS fillers with similar modifications. However, aliphatic and aromatic filler combinations showed more aggregated structures. Moreover, aliphatic POSS despite of good dispersion at higher loadings, act as lubricant, which is attributed to the disturbance in the PDMS‐ silica filler interaction and also the filler–filler interaction within fumed silica. There is a decrease in complex viscosity with the functionalization of fumed silica and with the aromatic/aliphatic POSS fillers. The thermal stability of aromatic functionalized fillers improves owing to the thermally stable phenyl groups. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Flame retardancy and mechanical properties of ferrum ammonium phosphate–halloysite/epoxy polymer nanocomposites

To recycle the nitrogen (N) and phosphorus (P) from wastewater, ferrum ammonium phosphate (FAP)–halloysite nanotubes (HNTs) were synthesized with simulated wastewater containing N, P, and Fe pollutants as raw materials. The adsorption–chemical precipitation in situ method was used to synthesize the target products, and the optimal conditions for the synthesis of the FAP–HNTs were obtained. Fourier transform Infrared (FTIR) spectroscopy, energy‐dispersive spectroscopy (EDS), scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis were conducted to characterize the samples. The FAP particle size was 20–30 nm in the FAP–HNTs. The FTIR spectra demonstrated that a small amount of water in the FAP–HNTs promoted the curing reaction. The FAP–HNTs and Exolit OP 1230 (OP) were introduced into epoxy (EP) to prepare the polymer nanocomposites. The heat release rate (HRR) and flammability of the EP composites were tested by microscale combustion calorimetry and UL‐94 instruments. The mechanical properties of the EP composites also were tested by a tension testing system. The results indicate that the flame retardancy and mechanical properties of the EP composites were improved by FAP–HNT. The addition of FAP–HNT and OP gave rise to an evident reduction of HRR and a prolonged burning time for the EP. EP/FAP–HNT/OP (20) (where 20 is the loading weight percentage) passed the UL 94 V‐0 rating. The analysis of the char revealed the synergy of the FAP–HNTs and OP in reducing the flammability of the polymers. We concluded that these polymers show potential for applications in wastewater treatment and N/P recycling. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41681.     

Compatibilized polyimide (R-BAPS)/BAPS-modified clay nanocomposites with improved dispersion and properties

There is a need for clay modifiers that will not thermally degrade at elevated temperatures commonly used in polymer processing operations such as extrusion and injection molding. In this context, natural montmorillonite clay (Na-MMT) was organically modified by varying concentrations of 4,4′-bis(4″-aminophenoxy)diphenylsulfone (BAPS) using different chemical dispersion methods to yield new chemically modified clays that are relatively thermally stable at elevated temperatures compared with current commercial modified clays. This paper shows that the Na-MMT chemical modification (BAPS-MMT) was confirmed by XRD that showed a shift of diffraction peak at 2Θ = 7.3° for Na-MMT towards lower 2Θ = 5.8°. Thermogravimetric analysis of the samples showed a weight loss of organically modified clay that started at a temperature of 350 °C, corresponding to the degradation temperature of the BAPS monomer. Rheological measurements in combination with XRD data showed clearly that the quality of dispersion of BAPS-MMT type particles in R-BAPS type polyimide and oligoimides strongly depends on the clay surface modification, the specific chemical modification method used, and on the polymer molecular weight. Note that the oligoimides were specifically used as model systems to confirm our expectation of improved chemical compatibility between the BAPS-MMT and the polyimide system. This study may stimulate a better understanding of the effects of rational chemical modification methods on the quality of clay dispersion in polyimide matrices, enhancing our ability to prepare useful polyimide/clay nanocomposites with improved properties for targeted high-temperature applications where current polymer nanocomposite systems are not useable.     

埃洛石纳米管在高分子纳米复合材料中的应用进展

介绍了埃洛石纳米管（HNTs）的结构和性质,着重说明了相比碳纳米管HNTs具有的优势。详述了利用有机试剂对埃洛石进行改性的方法和取得的效果。综述了HNTs在高分子纳米复合材料领域中的研究和应用进展情况,重点阐述了HNTs/聚烯烃、HNTs/聚酰胺、HNTs/天然橡胶等复合材料的制备方法及性能对比效果;探讨了HNTs在泡沫塑料领域应用的可行性。指出了HNTs在改性高分子纳米复合材料领域的发展方向,并对其研究前景进行了展望。     

Preparation of TiO2 epoxy nanocomposites by ultrasonic dispersion and resulting properties

Nanocomposites gained more and more importance in the last few years because of their improved performance over the neat polymer matrix, that is, toughness and stiffness can be enhanced simultaneously by the addition of nanoparticles. However, the dispersion of these particles in the matrix remains a big challenge. In this study, two types of TiO₂ nanoparticles were dispersed in two different epoxy resins by means of ultrasound. The particle size development in dependence on the dispersion time was investigated by dynamic light scattering for the different material systems. Furthermore, the influence of the viscosity on the sonication process' efficiency was analyzed. The resulting nanocomposites were tested for fracture and Charpy toughness. SEM images revealed that the improved fracture toughness properties are correlated to a rougher fracture surface, whose formation dissipates more energy. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of dispersion states of carbon nanotubes on physical properties of epoxy nanocomposites

Effects of different dispersion states of carbon nanotubes (CNTs) on rheological, mechanical, electrical, and thermal properties of the epoxy nanocomposites were studied. The dispersion states were altered depending upon whether a solvent was employed or not. To characterize dispersion of the CNTs, field emission scanning electron microscope (FESEM) and transmission electron microscopy (TEM) were used. It was found that the nanocomposites containing poorly dispersed CNTs exhibited higher storage modulus, loss modulus, and complex viscosity than ones with well dispersed CNTs. It means that the poorly dispersed CNTs/epoxy composites have, from a rheological point of view, a more solid-like behavior. Tensile strength and elongation at break of the nanocomposites with different dispersion of CNTs were measured. Both of the well and the poorly dispersed CNTs composites showed a percolation threshold of electrical conductivity at less than 0.5 wt.% CNTs loading and the former had higher electrical and thermal conductivities than the latter. Effects of the CNTs content on the physical properties were also examined experimentally. As loading of the CNTs increased, improved results were obtained. From the morphological observation by FESEM and TEM, it was found that when the solvent was not used in the CNTs dispersion process, aggregates of pristine CNTs remained in the nanocomposites.     

A liquid‐like multiwalled carbon nanotube derivative and its epoxy nanocomposites

Multiwall carbon nanotubes (MWCNTs) with liquid‐like behavior at room temperature were prepared with sulfonic acid terminated organosilanes as corona and tertiary amine as canopy. The liquid‐like MWCNT derivative had low viscosity at room temperature (3.89 Pa s at 20°C) and exhibited non‐Newtonian shear‐thinning behavior. The weight fraction of MWCNT in the derivative was 16.72%. The MWCNT derivative showed very good dispersion in organic solvents, such as ethanol and acetone. The liquid‐like MWCNT derivative was incorporated into epoxy matrix to investigate the mechanical performance of the nanocomposites and the distribution of MWCNTs in the matrix. When the liquid‐like MWCNT derivative content was up to 1 wt %, the flexural strength and impact toughness of composites were 12.1 and 124% higher than the pure epoxy matrix, respectively. Transmission electron microscope (TEM) confirmed the very good dispersion of the liquid‐like MWCNT derivative in epoxy matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2217–2224, 2013     

Titania-doped multi-walled carbon nanotubes epoxy composites: Enhanced dispersion and synergistic effects in multiphase nanocomposites

Multi-walled carbon nanotube-epoxy composites are modified with titania nanoparticles in order to obtain multiphase nanocomposites with an enhanced dispersion of carbon nanotubes. The dispersion is monitored using rheological and electrical conductivity measurements. An increase in dispersion quality can be correlated to an increased storage shear modulus of the uncured suspensions and to a decreased electrical conductivity in the bulk nanocomposite. The newly formed microstructure is revealed using transmission electron and optical microscopies. Due to chemical interactions between both types of nanoparticles an attractive potential is generated leading to a significant rearrangement in the particle network structure. Besides an enhanced dispersion, the hybrid structure leads to synergistic effects in terms of the glass transition of the nanocomposites. Although a decrease of the glass transition temperature (T_g) is observed for the nanocomposites containing only one type of filler, the combination of titania and carbon nanotubes into a hybrid structure reduces the decrease of T_g, thus demonstrating the potential of such hybrid structures as fillers for multi-functional epoxy nanocomposites.     

Structure–properties-performance relationships in complex epoxy nanocomposites: A complete picture applying chemorheological and thermo-mechanical kinetic analyses

Herein the kinetics of network formation (cross-linking) and network degradation (thermal decomposition) in a complex system based on epoxy resin reinforced with hyperbranched amino polymer-functionalized nanoparticles (HAPF) were discussed. Five classes of nanoparticles, that is, nano-SiO₂, halloysite nanotubes (HNTs), HNTs@nano-SiO₂ core/shell, HAPF/nano-SiO₂, HAPF/HNTs@nano-SiO₂ core/shell were loaded at 0.5, 1.0, 2.0 (optimal loading among prepared samples), and 5 wt% were examined. Parameters of the cure kinetics and degradation were correlated, and the mechanical properties were interpreted in terms of microstructure and rheological analyses. The isothermal chemorheological cure kinetics study (60, 70, and 80°C) revealed a low activation energy for epoxy/HAPF/HNTs@nano-SiO₂ core/shell nanocomposite (72.21 kJ/mol), compared with the blank epoxy (79.99 kJ/mol). Correspondingly, gel time of the system decreased from 1040 to 515 to 237 s upon isotherms of 60, 70, and 80°C, respectively. Tensile strength was also increased vividly (ca. 32%), possibly due to the strong interfacial adhesion, which reflected in an induced shear yielding. Nitrogen-mediated thermal decomposition kinetics suggested an average degradation activation energies of ca. 150 and 210 kJ/mol for the assigned nanocomposites and the blank epoxy, respectively. Overall, there was a complete agreement between the kinetics of network formation and network degradation in the studied epoxy nanocomposite. This work enables understanding of structure-properties-performance in complex epoxy nanocomposites.     

环氧树脂基纳米复合材料的研究进展

介绍了环氧树脂基纳米复合材料的制备方法、性能、作用机理及研究进展。     

Rheology and dispersion behavior of high‐impact polystyrene/ethylene–vinyl acetate copolymer/TiO2 nanocomposites

TiO₂ nanoparticles were introduced into high‐impact polystyrene (HIPS) in the form of a master batch in which TiO₂ was predispersed in composites of HIPS and ethylene–vinyl acetate copolymer (EVA) by melt compounding. The resulting materials were analyzed with a Rosand Precision rheometer, transmission electron microscopy, atomic force microscopy, and ultraviolet–visible light spectrophotometry. The results showed that the introduction of TiO₂ nanoparticles into HIPS influenced the apparent viscosity of the composites to a rather small extent. The addition of EVA could regulate the rheological behavior of the HIPS/TiO₂ master batch greatly. EVA helped the dispersions of the agglomerates of TiO₂ nanoparticles in the flow; this was featured by the distinct yielding in the flow after the introduction of EVA, as well as the large change in the non‐Newtonian indices. The dispersions of the HIPS/TiO₂ master batch in the HIPS matrix were improved greatly by the addition of EVA. TiO₂ nanoparticles were dispersed randomly in HIPS/EVA/TiO₂ nanocomposites. The dispersion improvement of the HIPS/EVA/TiO₂ master batch was also proved by atomic force microscopy and ultraviolet–visible spectroscopy investigations. The mechanical properties of HIPS/EVA/TiO₂ nanocomposites with low TiO₂ contents were slightly higher than those of pure HIPS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4434–4438, 2006     

Surface morphology,thermomechanical and barrier properties of poly(ether sulfone)‐toughened epoxy clay ternary nanocomposites

Poly(ether sulfone) (PES)‐toughened epoxy clay ternary nanocomposites were prepared by melt blending of PES with diglycidyl ether of bisphenol A epoxy resin along with Cloisite 30B followed by curing with 4,4′‐diaminodiphenylsulfone. The effect of organoclay and thermoplastic on the fracture toughness, permeability, viscoelasticity and thermomechanical properties of the epoxy system was investigated. A significant improvement in fracture toughness and modulus with reduced coefficient of thermal expansion (CTE) and gas permeability were observed with the addition of thermoplastic and clay to the epoxy system. Scanning electron microscopy of fracture‐failed specimens revealed crack path deflection and ductile fracture without phase separation. Oxygen gas permeability was reduced by 57% and fracture toughness was increased by 66% with the incorporation of 5 phr clay and 5 phr thermoplastic into the epoxy system. Optical transparency was retained even with high clay content. The addition of thermoplastic and organoclay to the epoxy system had a synergic effect on fracture toughness, modulus, CTE and barrier properties. Planetary ball‐milled samples gave exfoliated morphology with better thermomechanical properties compared to ultrasonicated samples with intercalated morphology. Copyright © 2010 Society of Chemical Industry     

Facile dispersion of exfoliated graphene/PLA nanocomposites via in situ polycondensation with a melt extrusion process and its rheological studies

This work attempted to improve the dispersion of graphene by coating poly(lactic acid) pellets with a masterbatch before melt processing. An in situ polycondensation reaction of lactic acid oligomer was utilized to prepare the masterbatch (MB) of exfoliated graphene (GR). MB dispersed composites of poly(lactic acid) (PLA) were fabricated by melt extrusion of MB‐coated PLA. One normal coated composite without MB coating (PLA‐M‐0.2GR) was fabricated for comparing properties. X‐ray diffraction, Raman spectroscopy, and morphological studies revealed better compatibility, dispersion, and interaction of GR for the diluted‐MB composite compared to the normal coated composite. The thermal stability, crystallization properties, and mechanical properties of the composites were examined, and the effect of short PLA chains in diluted‐MB composites was observed. The melt rheology nature of the composites was examined. Cole–Cole plots and Han plots suggested a uniform distribution of graphene. The sample PLA‐MB‐0.05GR showed improved modulus and elongation at break. It also showed better dispersion of GR, comparable thermal stability, good miscibility, good chain mobility, and high activation energy. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46476.     

Quantification of carbon nanotube dispersion and its correlation with mechanical and thermal properties of epoxy nanocomposites

An experimental study is carried out to quantitatively assess the dispersion quality of carbon nanotubes (CNTs) in epoxy matrix as a function of CNT variant and weight fraction. To this end, two weight fractions (0.05% and 0.25%) of as-grown, oxidized, and functionalized CNTs are used to process CNT/epoxy nanocomposites. Scanning electron microscopy, X-ray diffraction, and Fourier transform infrared analysis of different variants of CNTs are used to establish the efficiency of purification route. While the relative change in mechanical properties is investigated through tensile and micro-hardness testing, thermal conductivity of different nanocomposites is measured to characterize the effect of CNT addition on the average thermal properties of epoxy. Later on, a quantitative analysis is carried out to establish the relationship between the observed improvements in average composite properties with the dispersion quality of CNTs in epoxy. It is shown that carboxylic (-COOH) functionalization reduces the average CNT agglomerate size and thus ensures better dispersion of CNTs in epoxy even at higher CNT weight fraction. The improved dispersion leads to enhanced interfacial interaction at the CNT/epoxy interface and hence provides higher relative improvement in nanocomposite properties compared to the samples prepared using as-grown and oxidized CNTs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48879.     

Processing–structure–properties relationships of mechanically and thermally enhanced smectite/epoxy nanocomposites

Mechanically reinforced and thermally enhanced smectite/epoxy nanocomposites were synthesized using “direct” (without solvent) and “solvent” processing techniques. The molecular dispersion of smectite clay in the epoxy resin was investigated for its role in the rheology, structure formation, and properties of nanocomposites. The effects of three types of organic modifiers on the dispersion structure were compared. The use of solvent during processing assists in the enhancement of clay exfoliation. Rheology was used as a method to compare the degree of clay delamination in the resin matrix, as well as to estimate the suspension structure. The critical volume fraction (Φ*) and maximal packaging of smectites were determined and used for prediction of the viscosity. The qualitative changes in the nanostructure of suspensions above Φ*, due to flocculation of exfoliated clay layers, were compared with the alteration of the properties of nanocomposites, related to the structure formation and morphology. The curing kinetics were found to depend on both the organic modifier and solvent, but the extent of curing was roughly equivalent for the pure epoxy resin and the nanocomposites. The structure of the nanocomposites, either intercalated or exfoliated, produced by the direct processing technique was controlled by the organic modifier. By using solvent processing, the effect of the solvent dominates that of the organic modifier, presumably leading to exfoliated nanocomposites. The mechanical and thermal properties are strongly enhanced above the Φ* of smectites, and they are significantly dependent on the type of nanocomposite structure and the use of solvent. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2499–2510, 2005     

Cure kinetics and rheology characterization of soy‐based epoxy resin system

A novel soy‐based epoxy resin system was synthesized by the process of transesterification and epoxidation of regular soy bean oil, which has the potential to be widely usable in various composite manufacturing processes. Cure kinetics and rheology are two chemical properties commonly required in process modeling. In this work, the cure kinetics and rheology of the soy‐based resin system were measured by means of differential scanning calorimetry (DSC) and viscometer. DSC was used to measure the heat flow of dynamic and isothermal curing processes. The cure kinetics models of the different formulations were thus developed. A Brookfield viscometer was used to measure the change in viscosity under isothermal conditions. A novel neural network‐based model was developed to improve modeling accuracy. The models developed for cure kinetics and rheology for soy‐based epoxy resin system can be readily applied to composite processing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3168–3180, 2006     

Effect of blending sequence on the morphologies of poly(butylene terephthalate)/epoxy/clay nanocomposites by a rheological approach

Epoxy resin was used as a compatilizer to prepare poly(butylene terephthalate)/clay nanocomposites via melt intercalation. Three different mixing sequences were attempted in the present work: (1) to mix poly(butylene terephthalate) (PBT), epoxy, and organoclay in one step; (2) first to mix epoxy and organoclay, and then mix it with PBT; (3) to prepare PBT/organoclay hybrid first, and then mix it with epoxy to get the final nanocomposites. The results from X‐ray diffraction (XRD) reveal that all these hybrids present an intercalated structure. However, it can be observed that there are distinct differences in the amount and average size of clay tactoids dispersed in those hybrids from the transmission electron microscope (TEM) photographs, which are further confirmed successfully by the rheological measurements. On the basis of the strain overshoot intensity and the low‐frequency solid‐like response level in the small amplitude oscillatory shear (SAOS) measurements, it can be concluded that the blending sequence (2) is the best way to obtain a nice dispersion of clay in the matrix, forming a percolated tactoids network with highest density and intensity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 340–346, 2006