Effect of polymerically‐modified clay structure on the morphology and properties of UV‐cured polyurethane acrylate/clay nanocomposites

Polyurethane acrylate (PUA)/clay nanocomposites were prepared by UV‐curing from a series of styrene‐based polymerically‐modified clays and PUA resin. Effect of the chemical structure of the polymeric surfactants on the morphology and tensile properties of nanocomposites has been explored. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) experimental results indicated that surfactants having hydroxyl or amino groups show better dispersion and some of the clay platelets were fully exfoliated. However, the composites formed from pristine clay and other polymerically‐modified clays without hydroxyl or amino groups typically contained both tactoids and intercalated structure. The mechanical properties of PUA composites were greatly improved where the organoclays dispersed well. Thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) were carried out to examine the thermal properties of the composites. The results showed that the loading of polymerically‐modified clays do not effect the thermal stability, but increased the Tgs of PUA/clay composites. Copyright © 2010 John Wiley & Sons, Ltd.     

Nanotailoring of sepiolite clay with poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene]: structure–property correlation

Poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS)/sepiolite clay nanocomposites are prepared by solvent casting method. Two types of schemes have been adopted to establish the compatibility between nonpolar polymer (SEBS) and needle‐like inorganic filler (sepiolite), either by polar modification of the nonpolar polymer or organic modification of the inorganic filler. Structure–property correlation of nanocomposites derived from two different approaches is compared. Structural and morphological analysis of nanocomposites has been investigated by Fourier transform infrared spectroscopy, X‐ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. Fourier transform infrared result shows better compatibility between SEBS and modified sepiolite clay compared to maleic anhydride grafted SEBS and pristine sepiolite in their nanocomposites. Tensile strength and % elongation are found to increase by 32 and 105%, respectively, with the addition of just 3 parts per hundred parts of resin (phr) modified sepiolite clay to pristine SEBS matrix. Moreover, thermal stability has also improved by 96°C with similar loading. This work provides a new insight into the structure and thermo‐mechanical properties of novel SEBS–sepiolite clay nanocomposites. Copyright © 2017 John Wiley & Sons, Ltd.     

Co‐continuous Polyamide 6 (PA6)/Acrylonitrile‐Butadiene‐Styrene (ABS) Nanocomposites

Summary: Polyamide 6 (PA6)/acrylonitrile‐butadiene‐styrene (ABS) (40/60 w/w) nanocomposites with a novel morphology were prepared by the melt mixing of PA6, ABS and organoclay. The blend nanocomposites had a co‐continuous structure, in which both PA6 and styrene‐acrylonitrile (SAN) were continuous phases. It was found that the toughening rubber particles were only located in the SAN phase and the strengthening clay platelets were selectively dispersed in the PA6 phase. The co‐continuous nanocomposites showed greatly improved mechanical properties over the whole temperature range when compared with the same blend sample without clay.

Schematic diagram for the co‐continuous ABS/PA6 blend nanocomposite.     

Preparation and properties of nanocomposites based on acrylonitrile–butadiene rubber,styrene–butadiene rubber,and polybutadiene rubber

Nanocomposites were prepared with different grades of nitrile rubber with acrylonitrile contents of 19, 34, and 50%, with styrene–butadiene rubber (23% styrene content), and with polybutadiene rubber with Na‐montmorillonite clay. The clay was modified with stearyl amine and was characterized by X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and transmission electron microscopy (TEM). The XRD studies showed an increase in the gallery gap upon the modification of the filler by stearyl amine. The intercalation of the amine chains into the clay gallery gap was confirmed by the presence of some extra peaks (2928, 2846, and 1553 cm^?1) in the FTIR spectra. The clay–rubber nanocomposites were characterized by TEM and XRD. The mechanical properties were studied for all the compositions. An improvement in the mechanical properties with the degree of filler loading up to a certain level was observed. The changes in the mechanical properties, with changes in the nature and polarity of the rubbers, were explained with the help of XRD and TEM results. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1573–1585, 2004     

Brominated poly(isobutylene‐co‐para‐methylstyrene) (BIMS)‐clay nanocomposites: Synthesis and characterization

In this work, preparation and properties of different nanoclays modified by organic amines (octadecyl amine, a primary amine, and hexadecyltrimethylammonium bromide, a tertiary amine) and brominated polyisobutylene‐co‐paramethylstyrene (BIMS)‐clay nanocomposites are reported. The clays and the 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 diffraction peaks observed in the range of 3 °–10 ° for the modified clays disappear in the rubber nanocomposites. TEM photographs show predominantly exfoliation of the clays in the range of 12 ± 4 nm in the BIMS. In the FTIR spectra of the nanocomposites, there are common peaks of virgin rubber as well as those of the clays. Excellent improvement in mechanical properties like tensile strength, elongation at break, and modulus is observed on incorporation of the nanoclays in the BIMS. Structure‐property correlation in the above nanocomposites is attempted. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4489–4502, 2004     

Mechanical properties of polymer‐blend nanocomposites with organoclays: Polystyrene/ABS and high impact polystyrene/ABS

Thirty‐three polystyrene (PS)/acrylonitrile‐butadiene‐styrene (ABS) and high impact PS/ABS polymer blends with organoclay and copolymer additives were prepared by melt processing using different mixing sequences in order to test the putative capability of clay to perform a compatibilizing role in polymer blends. In general, the addition of clay increased the tensile modulus and had little effect on tensile strength. For the blends studied in this work, the addition of organoclays caused a catastrophic reduction in impact strength, a critical property for commercial viability. The polymer‐blend nanocomposites adopted a structure similar to that for ABS/clay nanocomposites as determined by X‐ray diffraction and transmission electron microscopy. It is suggested that clay reinforcement inhibits energy absorption by craze formation and shear yielding at high strain rates. Simultaneous mixing of the three components provided nanocomposites with superior elongation and energy to failure compared to sequential mixing. The clay pre‐treated with a benzyl‐containing surfactant gave the best overall properties among the various organoclays tested and of the two clay contents studied 4 wt % was preferred over 8 wt % addition. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Methacrylate modified clays and their polystyrene and poly(methyl methacrylate) nanocomposites

Two methacrylate‐modified clays have been prepared and used to produce nanocomposites of polystyrene and poly(methyl methacrylate) by in situ polymerization. These nanocomposites have been characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), cone calorimetry and the evaluation of mechanical properties. When the clay contains only a single methacrylate unit, the styrene system is exfoliated but methacrylate is intercalated. When two methacrylate units are present on the cation of the clay, both systems are exfoliated. TGA data show that the thermal stability of all the nanocomposites is improved, as expected. The relationships between the fire properties and nanostructure of the nanocomposites are complicated, as shown by cone calorimetry. The conclusions that one may reach using cone calorimetry do not completely agree with those from XRD and TEM. The evaluation of mechanical properties shows an increase in Young's modulus for all nanocomposites along with a decrease in elongation; tensile strength is decreased for methacrylate nanocomposites but increased for styrenics systems. Copyright © 2004 John Wiley & Sons, Ltd.     

Development of core‐shell structure aided by SiC‐coated MWNT in ABS/LCP blend

Agglomeration is an issue of major concern for unmodified multi‐walled carbon nanotubes (MWNTs)‐aided polymeric composites. To overcome the above‐mentioned problem, multi‐walled carbon nanotubes (MWNTs) are modified by polycarbosilane (PCS)‐derived Silicone carbide (SiC). Acrylonitrile Butadiene Styrene (ABS)/Liquid Crystalline polymer (LCP)/MWCNT nanocomposites are prepared through melt blending in a twin screw extruder. X‐Ray Diffraction (XRD) studies authenticate the creation of ß‐SiC particles. Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM) studies reveal the formation of core–shell morphology involving MWNT as the core and SiC‐coated MWNT as the shell. The degree of dispersion of MWNT is far better when it has been coated with SiC. As viewed from Thermo‐gravimetric analysis (TGA), the thermal stability is substantially increased in SiC‐aided nanocomposite in comparison to ABS/LCP/unmodified CNT blend. Glass transition temperature as well as mechanical properties are improved significantly (in the presence of SiC‐coated MWNT) as a result of homogeneous dispersion exhibited by MWNT. Copyright © 2009 John Wiley & Sons, Ltd.     

Nanoalloy Based on Clays: Intercalated‐Exfoliated Layered Silicate in High Performance Elastomer

A novel method is described for the preparation of nanocomposites comprising a high performance rubber for tire application and layered silicates clay. In this work nanocomposites of solution‐styrene butadiene rubber (S‐SBR) with montmorillonite layered silicate were prepared with carboxylated nitrile rubber (XNBR), a polar rubber, as a compatibilizer. A sufficient amount of organomodified layered silicate was loaded in carboxylated nitrile rubber (XNBR) and this compound was blended as a master batch in the S‐SBR. Mixed intercalated/exfoliated morphologies in the nanocomposite are evinced by X‐ray diffraction measurements and transmission electron microscopy. Dynamic mechanical analysis also supports the compatibility of the composites. A good dispersion of the layered silicate in the S‐SBR matrix was reflected from the physical properties of the nanocomposites, especially in terms of tensile strength and high elongation properties.     

Influence of gamma irradiation on high density polyethylene/ethylene‐vinyl acetate/clay nanocomposites

The study of high density polyethylene (HDPE)/ethylene‐vinyl acetate (EVA)/and organically‐modified montmorillonite (OMT) nanocomposites prepared by melt intercalation followed by exposure to gamma‐rays have been carried out. The morphology and properties of the nanocomposites were studied using X‐ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and cone calorimetry. The purpose of the study focuses on the influence of gamma irradiation on the morphology, thermal stability and flammability properties of the nanocomposites. XRD studies and TEM images verified that the ordered intercalated nanomorphology of the nanocomposites was not disturbed by gamma irradiation. TGA data showed that the nano‐dispersion of clay throughout the polymer inhibited the irradiation degradation of HDPE/EVA blend, which led to the nanocomposites exhibiting superior irradiation‐resistant properties than that of the pure blend. Cone calorimetry results indicated that the improvement in heat release rate (HRR) for irradiated HDPE/EVA blend was suppressed efficiently when clay was present. Increasing clay loading from 2 to 10% was beneficial by improving the flammability properties of the nanocomposites, but promoted a rapid increase in the sub‐peak HRR at high irradiation dose level. Copyright © 2004 John Wiley & Sons, Ltd.     

Enhanced mechanical properties of MWCNT reinforced ABS nanocomposites fabricated through additive manufacturing process

Multiwall carbon nanotubes (MWCNTs) can be spread out in acrylonitrile butadiene styrene (ABS) using a twin-screw micro-compounding extruder. It can significantly improve the mechanical properties of 3D-printed objects. Dispersed MWCNTs in pure ABS to develop the nanocomposites through a two-time micro compounding extruding process. 3D printed filaments with a diameter of 1.75 mm have been prepared by processing the acquired composite structure through a filament extruder. The mechanical and other properties of 3D printed pure ABS and 1, 2, and 3 wt.% of the fused deposition modeling (FDM) process were studied for MWCNTs/ABS composites. Compared with pure ABS, the tensile and thermal properties were significant for 1, 2, and 3 wt.% of MWCNTs/ABS composites. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) were also analyzed for 0, 1, 2, and 3 wt.% MWCNTs/ABS composites. Additive manufacturing (AM) processes have recently been emphasized for their applications in electronics, aerospace, biomedical, and automobile engineering.     

Investigation of clay modifier effects on the structure and rheology of supercritical carbon dioxide‐processed polymer nanocomposites

Superior property enhancements in polymer–clay nanocomposites can be achieved if one can significantly enhance the nanoclay dispersion and polymer–clay interactions. Recent studies have shown that nanoclays can be dispersed in polymers using supercritical carbon dioxide (scCO₂). However, there is need for a better understanding of how changing the clay modifier affects the clay dispersability by scCO₂ and the resultant nanocomposite rheology. To address this, the polystyrene (PS)/clay nanocomposites with “weak” interaction (Cloisite 93A clay) and “strong” interaction (Cloisite 15A clay) have been prepared using the supercritical CO₂ method in the presence of a co‐solvent. Transmission electron microscopy images and small‐angle X‐ray diffraction illustrate that composites using 15A and 93A clays show similar magnitude of reduction in the average tactoid size, and dispersion upon processing with scCO₂. When PS and the clays are coprocessed in scCO₂, the “dispersion” of clays appears to be independent of modifier or polymer–clay interaction. However, the low‐frequency storage modulus in the scCO₂‐processed 15A nanocomposites is two orders of magnitude higher than that of 93A nanocomposites. It is postulated that below percolation (solution blended composites), the strength of polymer–clay interaction is not a significant contributor to rheological enhancement. In the scCO₂‐processed nanocomposites the enhanced dispersion passes the percolation threshold and the interactions dictate the reinforcement potential of the clay–polymer–clay network. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 823–831, 2010     

Morphological and thermal properties of ABS/montmorillonite nanocomposites using two different ABS polymers and four different montmorillonite clays

ABS/Clay nanocomposites were prepared using two ABS with different Acrylonitrile (AN) contents and four montmorillonite clays; a natural clay (CNa+) and three modified clays, Cloisites 10A, 20A, and 30B. The composites were prepared in a twin‐screw extruder. Results were analyzed considering the effect of clay and ABS type, on the clay dispersion, intercalation and exfoliation, as well as on the storage modulus and thermal stability of the nanocomposites. XRD and TEM confirm that when using an ABS with higher AN content (ABS2), a better dispersion and intercalation–exfoliation can be obtained. Cloisites 20A and 30B, respectively the one with greater initial intergallery spacing, but lower polarity and with smaller inter‐gallery spacing but greater polarity, produce the ABS nanocomposites with the greater intergallery spacing. Both ABS polymers have similar storage modulus and T_g and in both cases, the modulus increases with the 4 wt % clay. This increase is greater with the modified clays and slightly greater with the ABS2. T_g, from tan δ, increases very little with the 4 wt % clay, but again, this is slightly greater with ABS2. TGA and flammability tests show that the dispersed clay enhances the thermal stability and that the ABS with higher AN content produces a greater increase in fire retardancy. Tests also show that the better thermal stability and fire retardancy is obtained with the Cloisites 20A or 30B. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 190–200, 2008     

Studies of ABS-graft-maleic anhydride/clay nanocomposites: Morphologies, thermal stability and flammability properties

ABS-g-MAH (maleic anhydride) with different grafting degree, ABS/OMT (organo montmorillonite) and ABS-g-MAH/OMT nanocomposites were prepared via melt blending. The grafting reaction, phase morphology, clay dispersion, thermal properties, dynamic mechanical properties and flammability properties were investigated. FTIR spectra results indicate that maleic anhydride was successfully grafted onto butadiene chains of the ABS backbone in the molten state using dicumyl peroxide as the initiator and styrene as the comonomer and the relative grafting degree increased with increasing loading of MAH. TEM images show the size of the dispersed rubber domains of ABS-g-MAH increased and the dispersion is more uniform than that of neat ABS resin. XRD and TEM results show that intercalated/exfoliated structure formed in ABS-g-MAH/OMT nanocomposites and the rubber phase intercalated into clay layers distributed in both SAN phase and rubber phase. TGA results reveal the intercalated/exfoliated structure of ABS-g-MAH/OMT nanocomposites has better barrier properties and thermal stability than intercalated ones of ABS/OMT nanocomposites. The T_g of ABS-g-MAH/OMT nanocomposites was also higher than that of neat ABS/OMT nanocomposites. The results of cone measurements show that ABS-g-MAH/OMT nanocomposites exhibit significantly reduced flammability when compared to ABS/OMT nanocomposites even at the same clay content. The chars of ABS-g-MAH/OMT nanocomposites were tighter, denser, more integrated and fewer surface microcracks than ABS/OMT residues.     

Silicon‐methoxide‐modified clays and their polystyrene nanocomposites

Silicon‐methoxide‐containing modified clays were obtained through cationic exchange between the sodium clay and the ammonium cation of [3‐(trimethoxysilyl)propyl]octadecyldimethylammonium chloride (Si18). The nanocomposites were prepared through bulk polymerization of styrene in which the Si18 clay was dispersed. The silicon‐methoxide offers the possibility of reaction between the methoxide and a clay hydroxyl group to link together the cation and the clay. The nanocomposites were characterized by X‐ray diffraction, transmission electron microscopy, and atomic force microscopy. Their thermal stability and flame retardancy were measured by thermogravimetric analysis (TGA) and cone calorimetry. Linkage between the silicon and the clay apparently occurs in the clay but is not likely to occur in the nanocomposite, perhaps because of the presence of the polystyrene spreading the distance between the reactive sites, which makes reaction more difficult. The results from TGA and cone calorimetry were similar to those obtained with other nanocomposites. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1498–1503, 2002     

Polypropylene/montmorillonite nanocomposites toughened with SEBS‐g‐MA: Structure–property relationship

Polypropylene (PP)/organo‐montmorillonite (Org‐MMT) nanocomposites toughened with maleated styrene‐ethylene‐butylene‐styrene (SEBS‐g‐MA) were prepared via melt compounding. The structure, mechanical properties, and dynamic mechanical properties of PP/SEBS‐g‐MA blends and their nanocomposites were investigated by X‐ray diffraction (XRD), polarizing optical microscopy (POM), tensile, and impact tests. XRD traces showed that Org‐MMT promoted the formation of β‐phase PP. The degree of crystallinity of PP/SEBS‐g‐MA blends and their nanocomposites were determined from the wide angle X‐ray diffraction via profile fitting method. POM experiments revealed that Org‐MMT particles served as nucleating sites, resulting in a decrease of the spherulite size. The essential work of fracture approach was used to evaluate the tensile fracture toughness of the nanocomposites toughened with elastomer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3112–3126, 2005     

Preparation and properties of polysiloxane grafting multi‐walled carbon nanotubes/polycarbonate nanocomposites

Carboxyl multi‐wall carbon nanotubes (MWNTs‐COOH) were grafted by diaminopropyl terminated dimethylpolysiloxane (DPD) to the modified MWNTs‐COOH (MWNTs‐DPD). The surface structure and thermal stability of MWNTs‐DPD and MWNTs‐COOH were characterized using Fourier‐transform infrared spectroscopy, X‐ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). Then PC/MWNTs‐COOH and PC/MWNTs‐DPD nanocomposites were prepared by the solution method and melt extrusion method. The mechanical properties, transmission electron microscopy (TEM), TGA, limiting oxygen index (LOI), UL‐94 test, and permittivity test were used to evaluate the properties of the composites. The results showed that the MWNTs‐DPD was dispersed well in the PC matrix, and its tensile strength, flexual strength, flexural modulus, and flame retardancy were better than that of PC/MWNTs‐COOH. MWNTs‐DPD can improve the electrical properties of the nanocomposites at the low loading in PC. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of poly(styrene‐maleic anhydride)‐montmorillonite nanocomposite

Poly(styrene‐maleic anhydride)‐montmorillonite nanocomposites were prepared by intercalation of layered montmorillonite with the polymer ions. Synthetic approaches including polymerization and phosphonium salt formation have been used for polymer intercalation and dispersion of the host layers in the polymer matrix. The ratio of the mineral in the composites ranged 30–50%. Wide‐angle X‐ray diffraction (WAXD) disclosed that the d₍₀₀₁₎ spacing between the internal lamellar surface were only expanding to about 13 and 15 Å according to the type of phosphonium salt suggesting packing of polymer molecules between the layers. Examination of these materials by scanning and transmission electron microscopy showed spherical nano size particles of average diameter, 350 nm. Copyright © 2002 John Wiley & Sons, Ltd.     

Preparation and Characterization of PET/LDH or Clay Nanocomposites through the Microcompounding Process

Thermally stable modifier were used to modify clay or lithium aluminum layered double hydroxides (LiAl LDH) nanoparticles for preparation of poly (ethylene terephthalate)/clay or LiAl LDH nanocomposites. The effect of modify agent, studied by microcompouding process. The PET nanocomposites which were made by twin‐screw microcompounder dispersion morphology of inorganic layered materials in nanocomposites could be explained by wide‐angle X‐ray diffraction (WXRD), and transmission electron microscopy (TEM). Nanocomposite also formed the better mechanical, UV resistance, and gas barrier properties. Optical properties and crystallization behaviour of these new types of nanocomposites are investigated in this paper.     

Amine‐cured epoxy/clay nanocomposites. I. Processing and chemical characterization

The processing of nanocomposite materials composed of amine‐cured diglycidyl ether of bisphenol A (DGEBA) reinforced with organomontmorillonite clay is reported. A novel sample preparation scheme was used to process the modified clay in the glassy epoxy network, resulting in nanocomposites where the clay was both exfoliated and intercalated by the epoxy network. The processing scheme involves sonication of the constituent materials in a solvent, followed by solvent extraction to generate a composite with homogeneous dispersions of the nanoclay. Fourier transform infrared spectroscopy (FTIR) and Fourier transform (FT‐)Raman spectroscopy confirmed that the chemical structure of the epoxy network was not affected by the use of solvents in this processing scheme. The glass‐transition temperature, T_g, linearly increased with an increased weight ratio of the nanoclay. The microstructure of clay nanoplatelets in the composites was observed with transmission electron microscopy (TEM), wide‐angle X‐ray scattering (WAXS), and small‐angle X‐ray scattering (SAXS). It was found that the clay nanoplatelets were well‐dispersed, and were intercalated as well as exfoliated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4384–4390, 2004