Mesua ferrea L. seed oil based amido‐amine modified nanoclay/epoxy nanocomposites

Hydrophilic bentonite and organo‐montmorillonite (OMMT) have been modified by using a vegetable oil based amido‐amine compound. The modified nanoclays were characterized by using X‐ray diffraction (XRD) and FTIR techniques. Increase in the basal spacing after the modification was observed in both the cases. Further, Mesua ferrea L. seed oil based sulfonated epoxy resin nanocomposites have been prepared by using these modified nanoclays [3 (w/w) of clay in each case]. The XRD, TEM, SEM, FTIR, and rheological studies confirmed the formation of partially exfoliated nanocomposites. The study also confirmed that hydrophilic bentonite is not suitable nanofiller for the system, though modified bentonite slightly improves the performance characteristics of the pristine polymer. Modified OMMT based nanocomposite shows significant improvement in tensile strength (～ 1.7 times), scratch hardness (～ 2 times), gloss (14 units), and thermal stability (18°C) compared to the pristine system. This nanocomposite also exhibit better performance than OMMT based analogous nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Ethylene–octene copolymer (engage)–clay nanocomposites: Preparation and characterization

In this work, preparation and properties of nanoclay modified by organic amine (octadecyl amine, a primary amine) and Engage (ethylene–octene copolymer)–clay nanocomposites are reported. The clay and rubber nanocomposites have been characterized with the help of Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). The X‐ray results suggest that the intergallery spacing of pristine clay increases with the incorporation of the amine. The XRD peak observed in the range of 3–10° for the modified clay also disappears in the rubber nanocomposites at low loading. TEM photographs show exfoliation of the clays in the range of 10–30 nm in Engage. In the FTIR spectra of the nanocomposite, there are common peaks for the virgin rubber as well as those for the clay. Excellent improvement in mechanical properties, like tensile strength, elongation at break, and modulus, is observed on incorporation of the nanoclay in Engage. The storage modulus increases, tan δ peak decreases, and the glass transition temperature is shifted to higher temperature. The results could be explained with the help of morphology, dispersion of the nanofiller, and its interaction with the rubber. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 603–610, 2006     

Effect of carbon black on properties of rubber nanocomposites

Polymer based nanocomposites were prepared using brominated poly(isobutylene‐co‐paramethylstyrene) (BIMS) rubber and octadecyl amine modified montmorillonite nanoclay. The effect of nature and loading of carbon black on these nanocomposites and the control BIMS was investigated thoroughly using X‐ray diffraction technique (XRD), Fourier transform infrared spectroscopy (FTIR), and mechanical properties. The addition of 4 parts of the modified nanoclay to 20 phr N550 carbon black filled samples increased the tensile strength by 53%. Out of the three different grades of carbon black (N330, N550, and N660), N550 showed the best effect of nanoclay. Optimum results were obtained with the 20 phr filler loading. For comparison, china clay and silica at the same loading were used. Fifty‐six and 46% improvements in tensile strength were achieved with 4 parts of nanoclay added to the silica and the china clay filled samples, respectively. N330 carbon black (20 parts) filled styrene butadiene rubber (SBR) based nanocomposite registered 20% higher tensile strength with 4 parts of the modified nanoclay. In all the above carbon black filled nanocomposites, the modulus was improved in the range of 30 to 125%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 443–451, 2005     

Preparation and properties of styrene–butadiene rubber based nanocomposites: The influence of the structural and processing parameters

Rubber‐based nanocomposites were prepared with octadecyl amine modified sodium montmorillonite clay and styrene–butadiene rubber with different styrene contents (15, 23, and 40%). The solvent used to prepare the nanocomposites, the cure conditions, and the cure system were also varied to determine their effect on the properties of the nanocomposites. All the composites were characterized with X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and transmission electron microscopy (TEM). The XRD studies revealed exfoliation for the modified clay–rubber composites. The TEM photomicrographs showed a uniform distribution of the modified clay in the rubber matrix. The thickness of the particles in the exfoliated composites was around 10–15 nm. Although the FTIR study of the unmodified and modified clays showed extra peaks due to the intercalation of the amine chains into the gallery, the spectra for the rubber–clay nanocomposites were almost the same because of the presence of a very small amount of clay in the rubber matrix. All the modified clay–rubber nanocomposites displayed improved mechanical strength. The styrene content of the rubber had a pronounced effect on the properties of the nanocomposites. With increasing styrene content, the improvement in the properties was greater. Dicumyl peroxide and sulfur cure systems displayed similar strength, but higher elongation and slightly lower modulus values were obtained with the sulfur cure system. The curing of the samples at four different durations at 160°C showed that the cure time affected the properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 698–709, 2004     

Poly(ester‐amine) hyperbranched polymer as toughening and co‐curing agent for epoxy/clay nanocomposites

The marriage between hardness and flexibility of epoxy resins (improved toughness) is a desired feature, which broads their application in various industrial fields, especially for high impact resistance purposes. Accordingly, this work aims to improve toughness properties of epoxy resin (Epon‐828)/Ancamine (curing agent) system using amino‐terminated hyperbranched poly(ester‐amine) [Poly(PEODA‐NPA)] (HP) as toughening and/or co‐curing agent, in presence of organo‐modified Montmorillonite clay (OMMT) as a reinforcing filler. HP was synthesized via Michael addition reaction of poly(ethylene glycol) diacrylate (PEODA) to N‐methyl‐1,3‐propanediamine (NPA). Chemical structure and molecular weight of HP were elucidated using infrared (FTIR) spectroscopy and gel permeation chromatography (GPC) techniques, respectively. Epoxy/OMMT nanocomposites toughened with HP (at different concentrations) showed remarkable improvement in their toughness without any adverse effect on the other physico‐mechanical properties. The optimum concentration of HP and OMMT was found to be 20 wt % and 1–3 wt% of the epoxy resin, respectively. The extent of exfoliation and dispersion of OMMT platelets within the epoxy cured films was assessed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM) measurements. In addition, thermal gravimetric analyses (TGA‐DTA) of epoxy/OMMT nanocomposites toughened with HP showed a slight increase in their decomposition temperature, particularly at low OMMT loading. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Effect of Organomodified Ni-Al Layered Double Hydroxide (OLDH) on the Properties of Polypropylene (PP)/LDH Nanocomposites

This work addresses the effect of organomodified layer double hydroxide (OLDH) on the properties of PP/LDH nanocomposites prepared by melt intercalation method using a single screw extruder with maleic anhydride grafted polypropylene (PP-g-MA) as a compatibilizer. For this, Ni-Al LDH was first prepared by the co-precipitation method at constant pH using their nitrate salts. The above synthesized pristine LDH was organically modified using sodium dodecyl sulphate (SDS) by the regeneration method. The structural and thermal properties of LDH and PP nanocomposites were performed by X-ray diffraction (XRD), FTIR spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The influence of LDH loading on the mechanical and thermal properties of the nanocomposite was also investigated. The XRD results confirmed the formation of exfoliated PP/LDH nanocomposites. PP/LDH nanocomposites exhibited enhanced thermal stability relative to the pure PP. When 10% weight loss was selected as a point of comparison, the decomposition temperature of PP/LDH (5 wt%) nanocomposite was 15.3°C higher than that of pure PP. The DSC result indicated an increase in crystallization and melting temperature of the PP/LDH nanocomposites compared to pure PP. Overall, the mechanical properties of the PP/LDH nanocomposites increased with an increase in the LDH content. The maximum improvement of tensile strength, Young's modulus, flexural strength, and flexural modulus for the PP/LDH nanocomposite was found to be 11, 22.5, 28, and 22%, respectively, over neat PP. For comparison purposes, a nanocomposite with 5 wt% modified bentonite (PP/B5) was also prepared under the same operating condition and there was no significant improvement in mechanical properties (tensile strength and modulus).     

Thermomechanical and electrical characterization of epoxy‐organoclay nanocomposites

The effect of amount of clay content on the thermomechanical and electrical properties of epoxy/organoclay nanocomposites is investigated in the present research. An organoclay, cloisite 30B (C30B), was dispersed in the epoxy resin and was cured with an amine curing agent. The morphology of the nanocomposite examined by X‐ray diffraction shows exfoliation for nanocomposites with lesser clay content and intercalation for nanocomposites with higher clay content. The storage modulus (E′) of the nanocomposites increases monotonously with the increase in the amount of clay. The short time alternating current breakdown strength of the nanocomposites increases by the addition of C30B up to a certain clay content and then show a decrease. The space charge measured by pulsed electroacoustic method shows that the nanocomposite accumulate a very less amount of space charge and the charge decay in the nanocomposites are quicker than in the pure polymer. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

New method for the synthesis of clay/epoxy nanocomposites

A new liquid–liquid method for the synthesis of epoxy nanocomposites was developed. This new method improved the dispersion and exfoliation of the organoclay in the polymer matrix, thus improving the end‐use properties. The microstructure and physical properties of the clay/epoxy nanocomposite synthesized by the new method were studied. Rheological tests of the uncured epoxy–organoclay system demonstrated that this method resulted in a great increase in viscosity, much more than the most commonly used direct‐mixing method. The Krieger–Dougherty model successfully described the dispersion of the clay layers in the uncured epoxy. In the 5 wt % organoclay nanocomposite, compressive tests on the cured samples showed that there was a 45% increase in the maximum strength, a 10% increase in the yield strength, and a 26% increase in the modulus over the pure epoxy–amine cured system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4286–4296, 2006     

Synthesis and characterization of epoxy based nanocomposites

Epoxy‐clay nanocomposites were synthesized to examine the effects of the content and type of different clays on the structure and mechanical properties of the nanocomposites. Diglycidyl ether of bisphenol‐A (epoxy) was reinforced by 0.5–11 wt % natural (Cloisite Na⁺) and organically modified (Cloisite 30B) types of montmorillonite. SEM results showed that as the clay content increased, larger agglomerates of clay were present. Nanocomposites with Cloisite 30B exhibited better dispersion and a lower degree of agglomeration than nanocomposites with Cloisite Na⁺. X‐ray results indicated that in nanocomposites with 3 wt % Cloisite 30B, d‐spacing expanded from 18.4 Å (the initial value of the pure clay) to 38.2 Å. The glass transition temperature increased from 73°C, in the unfilled epoxy resin, to 83.5°C in the nanocomposite with 9 wt % Cloisite 30B. The tensile strength exhibited a maximum at 1 wt % modified clay loading. Addition of 0.5 wt % organically modified clay improved the impact strength of the epoxy resin by 137%; in contrast, addition of 0.5 wt % unmodified clay improved the impact strength by 72%. Tensile modulus increased with increasing clay loading in both types of nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1081–1086, 2005     

Molecular interactions in intercalated organically modified clay and clay-polycaprolactam nanocomposites: Experiments and modeling

In this work we have evaluated molecular interactions in organically modified clay and polymer clay nanocomposite using a combination of experimental (photoacoustic FTIR, XRD) and computational (molecular dynamics (MD)) techniques. The FTIR data reveals hydrogen bond and ionic bond interaction between functional end groups of organic modifier and surface oxygen of interlayer clay sheet lying in the organically modified clay; and, the hydrogen bond formation between intercalated polymer and organic modifier and surface oxygen of clay sheet lying in the interlayer clay gallery in the polymer clay nanocomposite. In this work we report the nature of interactions between clay and polymer, clay and organic modifier in polymer-clay nanocomposites through experiments and molecular dynamics simulations.     

Effect of PEgMA/amine silane compatibilizer on clay dispersion of polyethylene-clay nanocomposites

The compatibilization effects provided by an amine silane modified polyethylene (PEgAS) versus those by a maleated polyethylene (PEgMA), for forming PE–clay based nanocomposites, were studied. PEgAS was prepared by condensation reaction between PEgMA and g-(aminopropyl) triethoxy silane (APTS). It had the triethoxy-silane functionality on one end and was solution mixed with an organomodified clay (Cloisite 20A) to promote the reaction of the silane groups with the hydroxyl groups on the surface of the clay. The obtained masterbatches were then compounded with PE to obtain PE–clay nanocomposites by melt blending in a twin screw extruder, using different compatibilizers and clay contents. FTIR, XRD, STEM, and Instron were used to characterize the structural, morphological, and mechanical properties of the nanocomposites. Results showed that the PEgAS formed more exfoliated–intercalated morphology and better mechanical properties, especially in modulus and tensile strength as compared with PEgMA composites and neat PE. The Young modulus was 35% higher, and the tensile strength was 18% higher with PEgAS composites.     

环氧树脂／超细膨润土复合材料的物理力学性能

采用TG-TA法、SEM、XRD、力学性能及电性能测试等方法对有机胺插入超细膨润土有机复合体与环氧树脂固化体系的结构与性能进行了研究,结果表明,膨润土/胺有机复合体与环氧树脂固化复合时,可形成层间固化与层外固化相结合的结构,所得复合材料的力学性能、电性能得到改善。其中有机活化膨润土/环氧树脂复合材料各项性能改善更加显著,在膨润土含量50%时,与未处理膨润土/环氧树脂复合材料相比,其拉伸强度约提高60%,拉伸模量约提高120%,而材料的弯曲强度和模量约分别提高40%和30%,冲击强度约提高30%;材料的体积电阻系数和表面电阻系数约分别提高8倍和12倍。     

Shape‐memory property and characterization of epoxy resin‐modified Mesua ferrea L. seed oil‐based hyperbranched polyurethane

Modification of existing polymers leads to enhancement of many desirable properties. So, a hyperbranched polyurethane (HBPU) of monoglyceride of Mesua ferrea L. seed oil, poly(ε‐caprolactone)diol (M_n = 3000 g mol^?1), 2,4‐toluene diisocyanate, and glycerol with 30% hard segment (NCO/OH = 0.96) has been modified with different amounts of bisphenol‐A based epoxy resin. The system is cured by poly(amido amine) hardener at 120°C for specified period of time. Improvement of thermostability, scratch hardness, and impact strength are observed by this modification of HBPU. The differential scanning calorimetry (DSC) results show improvement of melting temperature of the modified systems. The enhancement of tensile strength is about 2.4 times compared with that of the unmodified one. The morphology and structural changes due to variation of epoxy content was studied by scanning electron microscopy (SEM) analysis and Fourier transform infrared (FTIR) spectroscopy. The rheological properties of the epoxy‐modified HBPU show the dependence on the amount of epoxy resin. Shape memory study of the crosslinked HBPUs shows 90–98% thermoresponsive shape recovery. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Tannic acid-based tough hyperbranched epoxy thermoset as an advanced environmentally sustainable high-performing material

Bio-based resources are progressively replacing those of petroleum-based to address the detrimental impact on environment and health issues. In this regard, hyperbranched epoxy resins with three different compositions were synthesized by simple polycondensation reaction of bio-based branching reactant, diethanolamide of gallic acid with bisphenol-A, and epichlorohydrin. Diethanolamide of gallic acid was obtained from the reaction between tannic acid and diethanol amine in the presence of sodium methoxide catalyst. FTIR, ¹H NMR, and ¹³C NMR spectroscopic analyses were employed to confirm the structure of branching unit and hyperbranched resins. Poly(amido amine)-cured hyperbranched epoxy thermosets exhibited superior properties, such as tensile strength (45–57.2 against 38.5 MPa), elongation-at-break (16.3–24.2 against 5 %), scratch hardness (>10 against 7 kg), toughness (577.8–859.1 against 150.2 MPa), tensile adhesive strength (1647–2086 against 581 MPa), and biodegradability (17.6–31 against 2.2 %), compared with the conventional bisphenol-A-based epoxy, prepared under the same conditions. These results simply indicate the advantageous of the bio-based moiety and hyperbranched architecture on the overall performance of the thermosets. Moreover, good antioxidative response of these thermosets expands their applications as protective coatings and adhesive materials. Thus, diethanolamide of gallic acid-based hyperbranched epoxy thermoset can be used as potent ecofriendly advanced material in multifaceted applications.     

Effect of bentonite on the physical properties and drug‐release behavior of poly(AA‐co‐PEGMEA)/bentonite nanocomposite hydrogels for mucoadhesive

A series of nanocomposite hydrogels for mucoadhesive were prepared from acrylic acid, poly(ethylene glycol) methyl ether acrylate, and intercalated bentonite clay by photopolymerization. The microstructures were identified by X‐ray diffraction (XRD). Results showed that the swelling ratio for the present nanocomposite hydrogels decreased with an increase of bentonite, whereas the gel strength and Young's modulus of the present gels increased with an increase of bentonite. However, the adhesive force of the present gels did not decrease with an increase of bentonite. XRD results indicated that the exfoliation of bentonite was achieved in the xerogels and swollen gels. Finally, the drug‐release behaviors for these gels were also assessed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2934–2941, 2004     

Synthesis and characterization of styrene butadiene rubber—Bentonite clay nanocomposites

In the present study, naturally occurring unfractionated bentonite clay was used to prepare styrene butadiene rubber/bentonite clay nanocomposite by latex stage blending. The bentonite clay was organo‐modified by in situ resol formation by the reaction of resorcinol and formaldehyde. The latex clay mixture was co‐coagulated with acid. The resulting clay masterbatch was compounded and evaluated by Fourier Transform Infrared spectroscopy, X‐ray diffraction (XRD), Transmission Electron Microscopy (TEM), Energy Dispersive X‐ray spectroscopy (EDS), Scanning Electron Microscopy, Thermogravimetric analysis, and Differential Scanning Calorimetry. XRD showed that the interplanar distance of the in situ resol‐modified bentonite clay increased from 1.23 to 1.41 nm for the unmodified bentonite. TEM analysis indicated partial exfoliation and/or intercalation. EDS (Si and Al mapping) of the clay revealed the nature of the dispersion in the nanocomposites vis‐à‐vis the conventional styrene‐butadiene rubber (SBR)/bentonite clay composite. Thermogravimetric analysis was used to compare the decomposition trends of the SBR/clay nanocomposites with the SBR/clay composite. The glass transition temperature of SBR/clay nanocomposites increased as compared with that of neat SBR. Substantial improvement in most of the other mechanical properties was also observed in case of the nanocomposites. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Simultaneously enhanced cryogenic mechanical behaviors of cyanate ester/epoxy resins by poly(ethylene oxide)‐co‐poly(propylene oxide)‐co‐poly(ethylene oxide) (PEO‐PPO‐PEO) block copolymer and clay

Cryogenic mechanical properties are important parameters for thermosetting resins used in cryogenic engineering areas. The hybrid nanocomposites were prepared by modification of a cyanate ester/epoxy/poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide) (PEO‐PPO‐PEO) system with clay. It is demonstrated that the cryogenic tensile strength, Young's modulus, ductility (failure strain), and fracture resistance (impact strength) are simultaneously enhanced by the addition of PEO‐PPO‐PEO and clay. The results show that the tensile strength and Young's modulus at 77 K of the hybrid nanocomposite containing 5 wt% PEO‐PPO‐PEO and 3 wt% clay were enhanced by 31.0% and 14.6%, respectively. The ductility and impact resistance at both room temperature and 77K are all improved for the hybrid composites. The fracture surfaces of the neat BCE/EP and its nanocomposites were examined using scanning electron microscopy (SEM). Finally, the dependence of the coefficients of thermal expansion (CTE) on the clay and PEO‐PPO‐PEO contents was examined by thermal dilatometer. POLYM. COMPOS., 38:2237–2247, 2017. © 2015 Society of Plastics Engineers     

Properties of novel epoxy/clay nanocomposites prepared with a reactive phosphorus-containing organoclay

In this study, a reactive phosphorus-containing organoclay (RPC) was successfully prepared through the cationic exchange reaction of sodium montomorillonite clay with hexyltriphenylphosphonium bromide and surface modification by grafting it with glycidyloxypropyltrimethoxy silane. It is characterized using X-ray diffraction (XRD) and Fourier transform IR (FTIR) measurements. A series of novel epoxy/clay nanocomposites (ERPC) was then prepared with a selected epoxy resin and varying amounts of RPC. The results of XRD and TEM of the nanocomposites showed that the RPC particles were well dispersed in the epoxy matrix with a highly exfoliated structure due to the presence of the reactive epoxide group of RPC. The as-prepared epoxy/RPC nanocomposites (ERPC) were thermally stable up to 388 °C. Thermal stability was increased by increasing the RPC content as indicated by the corresponding activation energies (E_a) and the integral procedural decomposition temperatures (IPDT). Furthermore, the storage modulus in the glass state of the nanocomposites was dramatically increased with the increase in RPC content. In addition, the large increment of limiting oxygen index (LOI) which was 11 units higher than that of the neat epoxy indicates that an extraordinary enhancement of flame retardancy was obtained from the nanocomposite containing 5 wt% of RPC.     

Epoxidized Mesua ferrea L. seed oil-based reactive diluent for BPA epoxy resin and their green nanocomposites

An epoxidized vegetable oil of Mesua ferrea L. seed was prepared and used as a reactive diluent for commercial BPA-based epoxy resin at different compositions for the first time. The prepared epoxidized oil (ENO100) was characterized by determination of physical properties like epoxy equivalent, viscosity, hydroxyl value, saponification value, iodine value, acid value, etc. and FTIR study. The morphology and rheological characteristics of the ENO100 modified commercial epoxy systems have been studied by SEM and rheometer. The performance of poly(amido amine) cured above resin systems have been investigated by the measurement of drying time, tensile strength, elongation at break, adhesive strength, impact resistance, scratch hardness, gloss and chemical resistance studies. The results indicate that the epoxidized oil not only reduces the viscosity of the BPA-based epoxy resin but it also enhances the performance of the cured resin. The performance of this system (50 wt.% dilution) was further enhanced by formation of nanocomposites using ex-situ technique with organically modified nanoclay at different dose levels (1–5 wt.%).The formation of nanocomposites was confirmed by XRD, SEM and FTIR studies. The studies of above performance indicate the enhancement of properties compared to pristine system. As naturally renewable diluent is used in the above studies, so the resultant nanocomposites are green high performance materials with zero VOC.     

Mechanical and physical properties of polymer‐based nanocomposites containing different types of clay

Epoxy‐clay nanocomposites based on diglycidyl ether of bisphenol A (DGEBA) epoxy reinforced with 2 wt% of four different types of clay were prepared by high shear mixing (HSM) technique. The resultant nanocomposites were investigated to determine the effects of clay addition and clay types on their mechanical, thermal, and physical properties. The XRD and TEM analyses revealed that good dispersions of nanoclay within the epoxy matrix have been achieved especially for the samples prepared with I.30E clay where a combination of disordered intercalated and exfoliated morphology was observed. The structure of samples synthesized with other types of clay was dominated by intercalated morphologies. The tensile results illustrated that the nanocomposite containing I.30E clay has the best mechanical properties as compared to other nanocomposites. This is mainly due to better dispersion of I.30E nanoclay in the epoxy matrix for this nanocomposite. The increase or decrease in the glass transition temperatures of nanocomposites were found to be dependent on the type of clay used. The effect of clay addition on the barrier properties was examined using water exposure test which demonstrated that the addition of 2% of I.30E and C10A clays resulted in 60% reduction in diffusivity. Noticeable reduction in maximum water uptake was also observed for all nanocomposites. The improvement in these physical properties was attributed to the tortuosity effect, where water molecules have to move around clay layers during diffusion in nanocomposites. POLYM. COMPOS., 36:1998–2007, 2015. © 2014 Society of Plastics Engineer