Fracture toughness and impact strength of anhydride‐cured biobased epoxy

Biobased neat epoxy materials containing functionalized vegetable oils (FVO), such as epoxidized linseed oil (ELO) and epoxidized soybean oil (ESO), were processed with an anhydride curing agent. A percentage of diglycidyl ether of bisphenol F (DGEBF) was replaced by ELO or ESO. The selection of the DGEBF, FVO, and an anhydride‐curing agent resulted in an excellent combination to produce a new biobased epoxy material having a high elastic modulus and high glass transition temperature. Izod impact strength and fracture toughness were significantly improved dependent on FVO content, which produced a phase‐separated morphology. POLYM. ENG. SCI., 45:487–495, 2005. © 2005 Society of Plastics Engineers     

Mechanical properties and failure surface morphology of amine‐cured epoxy/clay nanocomposites

The tensile and impact properties of amine‐cured diglycidyl ether of bisphenol A based nanocomposites reinforced by organomontmorillonite clay nanoplatelets are reported. The sonication processing scheme involved the sonication of the constituent materials in a solvent followed by solvent extraction to generate nanocomposites with homogeneous dispersions of the organoclay nanoplatelets. The microstructure of the clay nanoplatelets in the nanocomposites was observed with transmission electron microscopy, and the clay nanoplatelets were well dispersed and were intercalated and exfoliated. The tensile modulus of epoxy at room temperature, which was above the glass‐transition temperature of the nanocomposites, increased approximately 50% with the addition of 10 wt % (6.0 vol %) clay nanoplatelets. The reinforcing effect of the organoclay nanoplatelets was examined with respect to the Tandon–Weng and Halpin–Tsai models. The tensile strength was improved only when 2.5 wt % clay nanoplatelets were added. The Izod impact strength decreased with increasing clay content. The failure surfaces of the nanocomposites were observed with environmental scanning electron microscopy and confocal laser scanning microscopy. The roughness of the failure surface was correlated with the tensile strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 281–287, 2005     

Effect of water and crude oil on mechanical and thermal properties of epoxy‐clay nanocomposites

Epoxy‐clay nanocomposites were synthesized by high shear mixing (HSM) technique using diglycidyl ether of bisphenol A (DGEBA) epoxy reinforced by Nanomer I.30E nanoclay. Disordered intercalated with some exfoliated structure were found in the resultant nanocomposites. The fabricated samples were exposed to water and crude oil to investigate the effect of nanoclay addition on diffusivity and amount of liquid uptake. The results showed good improvement in the barrier properties of epoxy as a result of clay addition. The average reduction in diffusivity and maximum water uptake for nanocomposites containing 1% nanoclay were 51% and 8%, respectively. The maximum water uptake was about double the maximum oil ingress for both neat epoxy and nanocomposites. Obvious degradations in thermal and mechanical properties of neat epoxy and nanocomposites were observed as a result of liquid uptake; with less severe impact on nanocomposites. The reduction in glass transition temperature was about 8% for each 1% of water uptake for nanocomposites as compared to 15% for neat epoxy. The tensile strength and the elastic modulus of neat epoxy and nanocomposites were adversely affected by water and oil uptake while the fracture strain was slightly improved; a behavior found to be proportional to the amount of liquid uptake. The diffusion mechanism of water in neat epoxy was well predicted by Fickian model, while that of the nanocomposites was better fitted with Langmuir model. POLYM. COMPOS., 35:318–326, 2014. © 2013 Society of Plastics Engineers     

Synthesis and characterization of exfoliated poly(styrene-co-methyl methacrylate)/clay nanocomposites via emulsion polymerization with AMPS

A method was described for synthesis of exfoliated poly(styrene-co-methyl methacrylate)/clay nanocomposites through an emulsion polymerization with reactive surfactant, 2-acrylamido-2-methyl-1-propane sulfonic (AMPS) which made the polymer end-tethered on pristine Na-MMT.AMPS widened the gap between clay layers and facilitates comonomers penetrate into clay. Silicate layers affect the composition of comonomers, for example A0.3M10S10T5 showed the elevated composition of MMA end tethered on silicate when compared to the feed ratio and polar methyl methacrylate (MMA) was considered to have the stronger interaction with clay layers than styrene.The exfoliated structure of extracted nanocomposite was confirmed by XRD and transmission electron microscopy. The onset of thermal decomposition for nanocomposites shifted to a higher temperature than that for neat copolymer. The dynamic moduli of nanocomposites increase with clay content. Dynamic storage modulus and complex viscosity increased as the clay content increased. In low frequency region all prepared nanocomposites exhibited apparent low-frequency plateaus in the linear storage modulus. Complex viscosity showed shear-thinning behavior as the clay content increases.     

The effect of chemical modification on the fracture toughness of montmorillonite clay/epoxy nanocomposites

The change in fracture toughness and its dependence on the content of clay nanoplatelets and adhesion at the interface between clay nanoplatelets and anhydride-cured epoxy matrix are discussed. Three clay nanoplatelets with different chemical modifications were used in this investigation. To fabricate nanocomposites, the clay nanoplatelets were sonicated in acetone for 2 h. The role of the clay nanoplatelets in the mechanical/fracture properties was investigated by transmission electron microscopy (TEM). Bright-field TEM micrographs showed excellent dispersion of clay nanoplatelets in epoxy matrix. Both intercalation and exfoliation of clay nanoplatelets were observed depending on clay modification. Compact tension specimens were used for fracture testing. The fracture toughness increased with increasing clay content. The fracture toughness of clay/epoxy nanocomposites varied with the clay morphology in the epoxy matrix. Different morphologies of the fracture surfaces, highly dependent on the morphology of dispersed clay nanoplatelets, were observed using environmental scanning electron microscopy (ESEM). The fracture toughness was found to be correlated with the fracture surface roughness measured by confocal laser scanning microscopy (CLSM).     

Morphology,thermal, and mechanical properties of polyamide 66/clay nanocomposites with epoxy‐modified organoclay

A new kind of organophilic clay, cotreated by methyl tallow bis‐2‐hydroxyethyl quaternary ammonium and epoxy resin into sodium montmorillonite (to form a strong interaction with polyamide 66 matrix), was prepared and used in preparing PA66/clay nanocomposites (PA66CN) via melt‐compounding method. Three different types of organic clays, CL30B–E00, CL30B–E12, and CL30B–E23, were used to study the effect of epoxy resin in PA66CN. The morphological, mechanical, and thermal properties have been studied using X‐ray diffraction, transmission electron microscopy (TEM), mechanical, and thermal analysis, respectively. TEM analysis of the nanocomposites shows that most of the silicate layers were exfoliated to individual layers and to some thin stacks containing a few layers. PA66CX–E00 and PA66CX–E12 had nearly exfoliated structures in agreement with the SAXS results, while PA66CX–E23 shows a coexistence of intercalated and exfoliated structures. The storage modulus of PA66 nanocomposites was higher than that of the neat PA66 in the whole range of tested temperature. On the other hand, the magnitude of the loss tangent peak in α‐ or β‐transition region decreased gradually with the increase in the clay loading. Multiple melting behavior in PA66 was also observed. Thermal stability more or less decreased with an increasing inorganic content. Young's modulus and tensile strength were enhanced by introducing organoclay. Among the three types of nanocomposites prepared, PA66CX–E12 showed the highest improvement in properties, while PA66CX–E23 showed properties inferior to that of PA66CX–E00 without epoxy resin. In conclusion, an optimum amount of epoxy resin is required to form the strong interaction with the amide group of PA66. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1711–1722, 2006     

Effect of clay modifier and matrix molar mass on the structure and properties of poly(ethylene oxide)/Cloisite nanocomposites via melt-compounding

The present study is concerned with the preparation and characterisation of PEO/clay nanocomposites via melt-extrusion. Two different matrix molar masses of PEO were investigated as well as various types of the Cloisite clay range. PEO/Cloisite Na⁺ nanocomposites give rise to intercalated structures displaying only a moderate improvement of the mechanical properties at higher clay concentrations, regardless of the matrix molar mass. The chemical nature of the organic modifier was proven to be detrimental for the final nanocomposite structure and resulting mechanical properties. PEO nanocomposites based on the Cloisite 30B clay, incorporating a polar modifier, give rise to exfoliated structures. They display a strongly increased storage modulus, regardless of the matrix molar mass. The structural organisation of the nanocomposites based on Cloisite 20A, containing an apolar modifier, is very dependent on the matrix molar mass. An exfoliated structure can only be achieved upon melt mixing with a high molar mass PEO. In general, the mechanical properties of the nanocomposites based on the high molar mass PEO matrix are slightly superior. The thermal properties are also distinctly influenced by the addition of clay, although the actual structural organisation of the nanocomposite is proven to be less important. The melt temperature, as well as the crystallinity, decreases upon the addition of clay, especially for the low molar mass PEO matrix. The decomposition temperature shows a slight increase upon the addition of clay, especially for the Cloisite 30B nanocomposites.     

Graphene network enabled high speed electrical actuation of shape memory nanocomposite based on poly(vinyl acetate)

Here strong electroactive shape memory nanocomposites were prepared by incorporating graphene nanoplatelets into poly(vinyl acetate) (PVAc ) through the simple solvent mixing method. TEM and XRD revealed that well exfoliated graphene nanoplatelets formed a continuous network throughout the matrix with a large amount of interconnectedness. Dynamic mechanical analysis showed that the inclusion of graphene significantly improves both glassy and rubbery moduli of the matrix. Furthermore, the prepared nanocomposites demonstrated a marked electrical conductivity up to 24.7 S m^?1 and thereby surprisingly rapid electrical actuation behaviour exhibiting a 100% recovery ratio in 2.5 s. Moreover, PVAc and its nanocomposites displayed scratch self‐healing capability. This work demonstrates that the PVAc /graphene nanocomposites with high modulus and excellent electroactive shape memory performance can be a promising material in many applications such as sensors and fast deployable and actuating devices. © 2016 Society of Chemical Industry     

The use of nanoclay in preparation of epoxy anticorrosive coatings

Epoxy/clay nanocomposites (NC) have become a very interesting topic among researchers in the past two decades because nanoclays have a positive effect on the mechanical, thermal and especially barrier and anticorrosive performances of the polymers. In this study epoxy NCs and NC-based epoxy coatings were prepared by the solution intercalation method using Cloisite 30B as nanoclay. WAXD and SEM analyses revealed that a mainly exfoliated structure was obtained in epoxy NC with 1 wt% clay content, while higher clay loadings reduced the number of exfoliated clay nanolayers and produced a mainly intercalated structure. EIS, TGA and DMA analyses showed that epoxy NCs with clay content below 5 wt% exhibited increased corrosion stability, thermal stability, glass transition temperature (T_g) and storage modulus (G′), in both glassy and rubbery states due to the nanoscale dispersion of Cloisite 30B and the barrier effect of individual nanolayers. Enhanced mechanical properties were also noticed at higher clay loadings, but the rate of improvement was lower. The highest extent of exfoliation and the most homogeneous macromolecular network was found for NC with 1 wt% of clay, leading to the highest improvement of thermal and anticorrosive properties. The salt spray test results showed that anticorrosive properties of epoxy coatings in the presence of 3 wt% and especially 1 wt% of Cloisite 30B were significantly better, thus indicating that nanoclay efficiently modifies the commercial epoxy coatings.     

Epoxy resin/exfoliated clay hybrid materials with high thermal properties

A new type of organophilic clay grafted with the protonated 4, 4′-methylenediamine was prepared. The epoxy was modified using the organophilic clay and was prepared by “acetone-clay slurry” method. The morphology of the clay platelets into epoxy matrix were characterized by wide angle X-ray diffraction and transmission electron microscopy. The results indicated that the epoxy resin/exfoliated clay hybrid materials were successfully prepared and the exfoliation of clay into epoxy matrix occurred in the curing process. The excellent thermal mechanical properties of the hybrid materials with the values of the storage modulus and glass transition temperature (T_g) of the hybrid materials were studied by dynamic mechanical analysis. When 7 wt% of modified clay was added into epoxy, the storage modulus of hybrid materials increased to 1131 MPa at 110°C, and 51 MPa at 220°C in comparison to the pristine cured epoxy (661 MPa at 110°C and 6 MPa at 220°C). The high thermal stabilities of the hybrid materials especially in high temperature were also been researched by thermogravimetric analysis. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Characterization of latex-based isotactic polypropylene/clay nanocomposites

Polypropylene/clay nanocomposite (PCN) containing 1 wt% organo-modified clay was prepared by latex technology, previously successfully applied for preparation of carbon nanotubes (CNTs)/polymer composites. The level of dispersion of organoclay and the microstructure of the resulting PCNs were characterized by means of X-ray diffraction analysis, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The obtained results have demonstrated that the latex technique represents a promising method for preparation of PP/clay nanocomposites with good dispersion of exfoliated nanoclay particles. The influence of clay nanoparticles on nonisothermal crystallization of PCN was investigated by DSC. The crystallization onset temperature of the matrix rises for about 5 °C when crystallizing from the quiescent melt. Improved thermal stability of PP/nanoclay was observed as evaluated by TGA. The dynamic mechanical analysis reveals an increase in storage modulus of PP matrix in the nanocomposites for 30% over a temperature range, indicating an increase in the stiffness of the material with the addition of organically modified clay.     

Characterization of polyisoprene-clay nanocomposites prepared by solution blending

The effects of clay dispersion and the interactions between clays and polymer chains on the viscoelastic properties of polymer/clay nanocomposites are investigated using oscillatory shear rheology, X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). Four different montmorillonite silicates of natural clays, plasma-treated clays, and organically modified clays (OCs) have been used in this study. For the polyisoprene (PI)/clay nanocomposites, the exfoliation of the OC dispersed in the PI matrix is confirmed with XRD and SAXS although TEM images show both exfoliated and non-exfoliated nanoclay sheets. In contrast aggregation or intercalation is obtained for the other PI/clay composites studied here. Additionally, the effective maximum volume packing fraction of OC for the exfoliated nanocomposites is determined from the overlapping of dynamic viscosity at low frequency regime, in which the effective maximum volume packing fraction is larger than the percolation threshold determined from the storage modulus of the nanocomposites.     

Hydroxyl terminated poly(ether ether ketone) with pendant methyl group‐toughened epoxy clay ternary nanocomposites: Preparation,morphology, and thermomechanical properties

Hydroxyl terminated poly(ether ether ketone) oligomer with pendant methyl group (PEEKMOH) was prepared. Ternary nanocomposites were processed by blending PEEKMOH oligomer with diglycidyl ether of bisphenol‐A (DGEBA) epoxy resin along with organically modified montmorillonite (Cloisite 25A) followed by curing with 4,4'‐diamino diphenyl sulfone. Tensile moduli and flexural moduli were increased, while the tensile strength and Izod impact strength were decreased with increase in clay content. Similarly, storage moduli and loss moduli were increased and glass transition temperature was decreased as the percentage of clay increased. X‐ray diffractograms showed exfoliated morphology even with higher concentration of clay content (8 phr). Scanning electron microscopy of fractured surfaces and tensile failed specimens revealed slow crack propagation and increase in river markings with nanoclay incorporation confirming the improvement in toughness. The domain size of PEEKMOH was decreased with the incorporation of nanoclay into the epoxy matrix, indicating the restriction of growth mechanism by nucleation during phase separation. With increase in clay content, phase separation disappeared indicating gelation occurs before phase separation. Fracture toughness was increased with the addition of PEEKMOH and clay in epoxy resin. Coefficient of thermal expansion of nanocomposites decreases up to 3 phr clay concentrations thereafter it increases. A marginal increase in thermal stability was observed with increase in clay content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of bone ash fillers on mechanical and thermal properties of biobased epoxy nanocomposites

In this study, the fabrication and characterization of bone ash filled biobased epoxy resin (Super SAP 100/1000, contains 37% biobased carbon content) nanocomposites are presented. Biosource bone ash was modified by size reduction and surface modification processes using a combination of ball milling and sonochemical techniques and characterized using X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The modified bone ash particles were incorporated into biobased epoxy with noncontact mixing process. The as-fabricated nanocomposites were characterized using various thermal and mechanical analyses. The nanocomposites showed significant improvement in flexural strength (41.25%) and modulus (34.56%) for 2 wt% filler loading. Dynamic mechanical analysis (DMA) results showed improvement in both storage modulus and loss modulus. Additionally, DMA results showed a slight reduction in glass transition temperature which also complies with differential scanning calorimetry results. Thermomechanical analysis results showed a reduction in the coefficient of thermal expansion. Thermogravimetric analysis results showed improved thermal stability at both onset of degradation and the major degradation. These enhanced thermal and mechanical performances of the epoxy nanocomposites allows them to be suitable for lightweight aerospace, automotive, and biomedical applications.     

Synthesis of poly(arylene disulfide)–vermiculite nanocomposites via in situ ring‐opening polymerization of macrocyclic oligomers

Exfoliated poly(4, 4′‐oxybis(benzene)disulfide)/vermiculite (POBDS/VMT) nanocomposites were successfully synthesized via in situ melt intercalation of cyclo(4, 4′‐oxybis(benzene)disulfide) oligomers (COBDS) into octadecylammonium‐exchanged VMT (organo‐VMT). The POBDS/VMT nanocomposites were melt fabricated in a two‐step process. First, the COBDS/VMT nanocomposite precursor was fabricated by melt delaminating organo‐VMT with COBDS at a temperature slightly higher than its melting point. Subsequently, exfoliated POBDS‐VMT nanocomposites can be prepared in situ via instant melt ring‐opening polymerization of the COBDS‐VMT nanocomposite precursor. The nanoscale dispersion of VMT layers within POBDS polymer was confirmed by X‐ray diffraction, scanning electron microscopy and transmission electron microscopy. High molecular weight POBDS polymer was formed in a few minutes at the same time as the nanocomposite formation. The results of dynamic mechanical analysis showed that the storage modulus and glass transition temperature of the nanocomposites are much higher than those of the POBDS matrix, even with a very small amount of VMT addition. This methodology provides a potential approach to synthesize high‐performance polymer/clay nanocomposites. Copyright © 2004 Society of Chemical Industry     

Thermo-physical and impact properties of epoxy nanocomposites reinforced by single-wall carbon nanotubes

The thermo-physical properties and the impact strength of diglycidyl ether of bisphenol F (DGEBF) epoxy nanocomposites reinforced with fluorinated single-wall carbon nanotubes (FSWCNT) are reported. A sonication technique was used to disperse FSWCNT in the glassy epoxy network resulting in nanocomposites having large improvement in modulus with extremely small amount of FSWCNT. The glass transition temperature decreased approximately 30 °C with an addition of 0.2 wt% (0.14 vol%) FSWCNT, without adjusting the amount of the anhydride curing agent. This was because of non-stoichiometry of the epoxy matrix that was caused by the fluorine on the single-wall carbon nanotubes. The correct amount of the anhydride curing agent needed to achieve stoichiometry was experimentally examined by dynamic mechanical analysis (DMA). The storage modulus of the epoxy at room temperature (which is below the glass transition temperature of the nanocomposites) increased up to 0.63 GPa with the addition of only 0.30 wt% (0.21 vol%) of FSWCNT, representing an up to 20% improvement compared with the neat epoxy. The Izod impact strength slightly decreased when the amount of FSWCNT was increased to 0.3 wt%. The excellent improvement in the storage modulus was achieved without sacrificing impact strength.     

Synthesis and characterization of polypropylene/clay nanocomposites

Polypropylene/clay (PP/clay) nanocomposites were synthesized via intercalative polymerization. The nanostructure of the composites was investigated by wide‐angle X‐ray diffractometry (WAXD) and transmission electron microscopy (TEM). The WAXD patterns of the PP/clay nanocomposites indicated that the characteristic diffraction peak of the clay disappeared. The TEM image showed the clay was exfoliated into nanometer size and dispersed uniformly in the PP matrix. The composites exhibited much higher storage modulus compared to that of pure PP. At temperatures higher than T_g, the storage modulus of the PP/clay nanocomposites with 8.1 wt % clay content increased three times that of the pure PP. Additionally, the thermal stability of the nanocomposites significantly increased. The maximum decomposition temperature was increased by 44°C with the introduction of about 10 wt % clay. The heat‐distortion temperatures (HDTs) of the nanocomposites also increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3611–3617, 2001     

Development of high‐performance epoxy/clay nanocomposites by incorporating novel phosphonium modified montmorillonite

Novel organoclays were synthesized by several kinds of phosphonium cations to improve the dispersibility in matrix resin of composites and accelerate the curing of matrix resin. The possibility of the application for epoxy/clay nanocomposites and the thermal, mechanical, and adhesive properties were investigated. Furthermore, the structures and morphologies of the epoxy/clay nanocomposites were evaluated by transmission electron microscopy. Consequently, the corporation of organoclays with different types of phosphonium cations into the epoxy matrix led to different morphologies of the organoclay particles, and then the distribution changes of silicate layers in the epoxy resin influenced the physical properties of the nanocomposites. When high‐reactive phosphonium cations with epoxy groups were adopted, the clay particles were well exfoliated and dispersed. The epoxy/clay nanocomposite realized the high glass‐transition temperature (T_g) and low coefficient of thermal expansion (CTE) in comparison with those of neat epoxy resin. On the other hand, in the case of low‐reactive phoshonium cations, the dispersion states of clay particles were intercalated but not exfoliated. The intercalated clay did not influence the T_g and CTE of the nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polypropylene nanocomposite film: A critical evaluation on the effect of nanoclay on the mechanical,thermal, and morphological behavior

Polypropylene (PP)/clay nanocomposites prepared by melt blending technique using different percentages of clay with and without maleic anhydride grafted PP (MA‐PP) were studied. The intercalated and exfoliated structure of nanocomposites was characterized by X‐Ray Diffraction (XRD) and transmission electron microscopy (TEM). Because of the typical intercalated and exfoliated structure, the tensile modulus of the nanocomposites were improved significantly as compared to virgin PP. The viscoelastic behavior of the nanocomposites was studied by dynamical mechanical analysis (DMA) and the results showed that with the addition of treated clay to PP there was substantial improvement in storage modulus increases. The thermal stability and crystallization of the PP nanocomposites as studied by differential scanning calorimeter (DSC) and thermo gravimetric analysis (TGA) were also improved significantly compared to PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Comprehensive high‐performance epoxy nanocomposites co‐reinforced by organo‐montmorillonite and nano‐SiO2

Comprehensive high‐performance epoxy nanocomposites were successfully prepared by co‐incorporating organo‐montmorillonite (o‐MMT) and nano‐SiO₂ into epoxy matrix. Because of the strong interaction between nanoscale particles, the MMT layers were highly exfoliated, and the exfoliated nanoscale MMT monoplatelets took an interlacing arrangement with the nano‐SiO₂ particles in the epoxy matrix, as evidenced by X‐ray diffraction measurement and transmission electron microscopy inspection. Mechanical tests and thermal analyses showed that the resulting epoxy/o‐MMT/nano‐SiO₂ nanocomposites improved substantially over pure epoxy and epoxy/o‐MMT nanocomposites in tensile modulus, tensile strength, flexural modulus, flexural strength, notch impact strength, glass transition temperature, and thermal decomposition temperature. This study suggests that co‐incorporating two properly selected nanoscale particles into polymer is one pathway to success in preparing comprehensive high‐performance polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012