Preparation and characterization of poly(butylene terephthalate) nanocomposites from thermally stable organic-modified montmorillonite

In this paper, cetyl pyridium chloride (CPC) was employed to modify the montmorillonite. TGA analysis shows that the organic modified clay has higher thermal stability than hexadecyl trimethyl ammonium chloride modified montmorillonite and is suitable to be used for preparing poly(butylene terephthalate) (PBT)/clay nanocomposites at the high temperature. And then PBT/clay nanocomposites were prepared by direct melt intercalation. The results of XRD, TEM and HREM experiments show the formation of exfoliated-intercalated structure. The thermal stability of the nanocomposites does not evidently decrease, but the char residue at 600 °C remarkably increase compared with pure PBT. DSC results indicate that clay improves the melting temperature, the crystallization rate and crystallinity of the PBT molecules in the nanocomposites.     

ABS/clay nanocomposites obtained by a solution technique: Influence of clay organic modifiers

Acrylonitrile-butadiene-styrene (ABS) polymer/clay nanocomposites were produced using an intercalation-adsorption technique from polymer in solution: polymer/clay suspensions were subjected to ultrasonic processing to increase the effectiveness of mixing. Several kinds of organically modified layered silicates (OMLS) were used to understand the influence of the surfactant nature on the intercalation-exfoliation mechanism. We show that only imidazolium-treated montmorillonite (DMHDIM-MMT) is stable at the processing temperature of 200 °C, used for hot-pressing, whereas alkyl-ammonium modified clays show significant degradation.The morphology of ABS based polymer nanocomposites prepared in this work was characterized by means of wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). Dynamic-mechanical analysis (DMA) was used to determine the storage modulus and damping coefficient as a function of temperature, and to investigate the correlations between mechanical properties and morphology of the nanocomposites. The thermal stability was assessed by means of thermogravimetric analysis (TGA). DMA and TGA show that the nanocomposites based on imidazolium-modified clay out-perform the nanocomposites based on quaternary-ammonium-modified clays in terms of mechanical properties and thermal stability.     

Preparation of Novel Coumarin Cyclic Polymer/Montmorillonite Based Nanocomposites

In present study, the synthesis, characterization, and thermal properties of novel coumarin cyclic polymer poly(3-benzoyl coumarin-7-yl-methacrylate) polymer/montmorillonite based nanocomposites were performed. At the characterizations of nanomaterials FTIR, XRD, DSC and TGA techniques were used. It was determined from XRD measurements that the morphologies of nanocomposites were shifted from exfoliated type to intercalated type when the clay ratio in the coumarin polymer matrix was increased from 1 to 5% level. From DSC analysis, a partial increasing at the glass transition temperatures of nanocomposites was observed related to clay ratios. On the other hand, a positive correlation was observed between the clay ratio and thermal stability of nanomaterials from TGA analysis. Also, the increasing of decomposition temperatures of nanocomposites according to homopolymer was recorded to be 9–17°C.     

Polystyrene nanocomposites based on quinolinium and pyridinium surfactants

In this paper pyridine and quinoline-containing salts were employed to modify montmorillonite. TGA analysis shows that the quinolinium modified clay has a higher thermal stability than the pyridinium modified clay. Polystyrene nanocomposites were prepared by in situ bulk polymerisation and direct melt blending using both clays. The X-ray diffraction and transmission electron microscopy results show the formation of intercalated structures. The 50% degradation temperature of the nanocomposites is increased and so is the amount of char from TGA analysis compared to the virgin polymer. Cone calorimetric results indicate that clay reduces the peak heat release rate and average mass loss rate and thus lowers the flammability of the polymer.     

Influence of Fe‐MMT on crosslinking and thermal degradation in silicone rubber/clay nanocomposites

In this article, silicone rubber (SR)/clay nanocomposites were synthesized by a melt‐intercalation process using synthetic Fe‐montmorillonite (Fe‐MMT) and natural Na‐MMT which were modified by cetyltrimethyl ammonium bromide (CTAB). This study has been designed to determine if the presence of structural iron in the matrix can result in radical trapping and then enhance thermal stability, affect the crosslinking degree and elongation. The SR/clay nanocomposites were characterized by X‐ray diffraction (XRD) patterns and transmission electron microscopy (TEM). Exfoliated and intercalated nanocomposites were obtained. Thermo gravimetric analysis (TGA) and mechanical performance were applied to test the properties of the SR/clay nanocomposites. The presence of iron significantly increased the onset temperature of thermal degradation in SR/Fe‐MMT nanocomposites. The thermal stability, gel fraction and mechanical property of SR/Fe‐MMT were different from the SR/Na‐MMT nanocomposites. So the iron not only in thermal degradation but in the vulcanization process acted as an antioxidant and radicals trap. Copyright © 2006 John Wiley & Sons, Ltd.     

Tribological performance and thermal behavior of epoxy resin nanocomposites containing polyurethane and organoclay

A series of epoxy resin nanocomposites modified by polyurethane and organically modified montmorillonite was prepared by effectively dispersing the organically modified montmorillonite in interpenetrating polymer networks (IPNs) of epoxy and polyurethane via the sequential polymeric technique and in situ polymerization. The tribological performance of the resultant EP/PU nanocomposites was investigated by a pin‐on‐disc tester, and the results showed that adding polyurethane and organically modified clay to the EP matrix had a synergistic effect on improving tribological performance of EP/PU nanocomposites. The morphologies of the worn surface were studied by scanning electron microscopy (SEM) observations, and the results indicated that the mechanism of improving tribological performance of EP/PU nanocomposites was different from that of pure EP or pure EP/PU IPNs. The thermal behavior of these nanocomposites was also investigated by thermogravimeric analysis (TGA), and the results indicated that adding organically modified clay to the matrix remedied the deterioration of the thermal degradation temperature of the interpenetrating networks. Copyright © 2008 John Wiley & Sons, Ltd.     

Polystyrene/MMT nanocomposites prepared by soap-free emulsion polymerization with high solids content

Polystyrene/montmorillonite (PSt/MMT) nanocomposite latexes have been synthesized by soap-free emulsion polymerization using MMT clay platelets as stabilizer. Small amounts of methacrylic acid were used as auxiliary monomer to promote clay adhesion to the surface of the particles. Overall solids content of the composite latexes in complete absence of coagulation of up to 30.7?wt% are reported under batch conditions. The 3?wt% MMT clay platelets were sufficient to maintain the colloidal stability and increasing MMT clay content resulted in the increase of particle diameter due to the improved viscosity of reaction medium. Transmission electron microscopy results demonstrate the existence of MMT platelets on the particle surface. X-ray diffraction spectroscopy (XRD) results show that an exfoliated structure of PSt/MMT nanocomposites was obtained in this study with the absence of d₀₀₁ diffraction peak of MMT in the XRD region.     

Thermal Degradation Kinetics of Polyurethane/Organically Modified Montmorillonite Clay Nanocomposites by TGA

Polyurethane (PU) has been prepared by using polyether polyol (jagropol oil) and 1,6- hexamethylene diisocyanate (HMDI) as a cross-linker. The organically modified montmorillonite clay (MMT) is well-dispersed into urethane matrix by an in situ polymerization method. A series of PU/MMT nanocomposites have been prepared by incorporating varying amounts of nanoclay viz., 1, 3, 5 and 6 wt %. Thermogravimetric analysis (TGA) of the PU/MMT nanocomposites has been performed in order to establish the thermal stability and their mode of thermal degradation. The TGA thermograms exhibited the fact that nanocomposites have a higher decomposition temperature in comparison with the pristine PU. It was found that the thermal degradation of all PU nanocomposites takes place in three steps. All the nanocomposites were stable up to 205°C. Degradation kinetic parameters of the composites have been calculated for each step of the thermal degradation processes using three mathematical models namely, Horowitz–Metzger, Coats–Redfern and Broido's methods.     

Radiation-induced synthesis of vinyl copolymer based nanocomposites filled with reactive organic montmorillonite clay

Vinyl copolymer–clay nanocomposites were prepared by γ-irradiation-initiated radical polymerization using a mixture of styrene (St) and divinyl benzene (DVB) in the presence of reactive organic montmorillonite clay (OMMT) in methanol at room temperature. Reactive OMMT was synthesized by a cation exchange reaction of Na⁺-MMT and 1-[(4-ethylphenyl)methyl]-3-butyl-imidazolium chloride as a reactive organic modifier in an aqueous solution. The microstructures of the nanocomposites were confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The thermal stability was examined by thermo gravimetric analysis (TGA). As a result, the reactive OMMT was a good additive material for preparing vinyl copolymer–clay nanocomposites.     

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.     

Preparation of fluorinated methacrylate/clay nanocomposite via in‐situ polymerization: Characterization,structure, and properties

Novel fluorinated coating containing well‐dispersed silicate nanolayers is successfully produced via in‐situ free radical polymerization of 2,2,2‐trifluoroethyl methacrylate in the presence of vinylbenzyl‐functionalized montmorillonite with different loading. The organic modification of sodium montmorillonite is achieved through an ion exchange reaction with triphenylvinylbenzylphosphonium chloride as surfactant prepared before use by reaction with vinylbenyl chloride and phosphine. The following in‐situ polymerization in the presence of organomodified clay leads to fluorinated nanocomposites with of partially exfoliated and intercalated morphologies, as determined via XRD and TEM analysis. The nanoscale dispersion of clay layers is also evidenced by thermal analysis; a moderate decrease of the glass transition temperature about 2–8 °C compared to their virgin PMATRIF and an improvement of their thermal stability as evidenced by TGA. The wettability of the nanocomposite films is also studied by contact angle measurements with water. The incorporation of organomodified clays not only increases the hydrophobicity of the fluorinated polymers but also improves the surface properties of obtained nanocomposites. Compared the virgin homopolymer, the mechanical properties of the nanocomposites are reduced by addition of organomodifed clay at temperature from 30 to 60 °C, whereas this trend is gradually decreased at higher temperature. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 411–418     

Effect of the premelting temperature and sample thickness on the polymorphic behavior of syndiotactic polystyrene/clay nanocomposites

X‐ray diffraction methods and differential scanning calorimetry thermal analysis have been used to investigate the structural changes of syndiotactic polystyrene (sPS)/clay nanocomposites. sPS/clay nanocomposites have been prepared by the mixing of sPS polymer solutions with organically modified montmorillonite. X‐ray diffraction data and differential scanning calorimetry results indicate that the dominating crystal forms and their relative fractions in sPS and sPS/clay nanocomposites are different for various premelting temperatures (T_max's). Higher T_max's favor the formation of the thermodynamically more stable β‐crystalline form, and its relative fraction has been obtained from the X‐ray diffraction data in the range of 11.5–13°. The intensity of the X‐ray diffraction data in the range of 11.5–13° decreases as the thickness of sPS/clay nanocomposites decreases from 150 to 20 μm. At the same time, the intensity of the X‐ray data in the range of 6–7° becomes sharper as the thickness of sPS/clay nanocomposites decreases. The calculation ratio based on the peak intensities at 6.2 and 6.8° for sPS/clay nanocomposites of equal thickness and crystallinity in the pure β and α forms has also been determined in this study. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1730–1738, 2003     

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     

Effect of surface modification of montmorillonite on the properties of aromatic polyamide/clay nanocomposites

The surface modification of montmorillonite clay was carried out through ion‐ exchange reaction using p‐phenylenediamine as a modifier. This modified clay was employed to prepare aromatic polyamide/organoclay nanocomposite materials. The dispersion behavior of clay was examined in the polyamide matrix. Polyamide chains were synthesized from 4‐aminophenyl sulfone and isophthaloyl chloride (IPC) in dimethylacetamide. These amide chains were suitably end‐capped with carbonyl chloride end groups to interact chemically with modified montmorillonite clay. The resulting nanocomposite films containing 2–20 wt% of organoclay were characterized by TEM, X‐ray diffraction (XRD), thin‐film tensile testing; thermogravimetric analysis (TGA), differential scanning calorimetric (DSC) and water absorption measurements. Mechanical testing revealed that modulus and strength improved up to 6 wt% organoclay loading while elongation and toughness of nanocomposites decreased with the addition of clay content in the matrix. Thermal decomposition temperatures of the nanocomposites were in the range 225–450 °C. These nanocomposites expressed increase in the glass‐transition temperature values relative to pure polyamide describing interfacial interactions among the phases. The percent water uptake of these composites reduced upon the addition of modified layered silicate depicting improved barrier properties. Copyright © 2008 John Wiley & Sons, Ltd.     

In situ synthesis of A3‐type star polymer/clay nanocomposites by atom transfer radical polymerization

A series of A₃‐type star poly(methylmethacrylate)/clay nanocomposites is prepared by in situ atom transfer radical polymerization (ATRP) initiated from organomodified montmorillonite containing quaternary trifunctional ATRP initiator. The first order kinetic plot shows a linear behavior, indicating the controlled character of the polymerization. The resulting nanocomposites are characterized by spectroscopic (XRD), thermal (DSC and TGA), and microscopic (TEM) analyses. The exfoliated nanocomposite has been obtained when polymerization was conducted with 1% of organic clay loading. Thermal analyses show that all nanocomposites have higher glass transition values and thermal stabilities compared to neat polymer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5257–5262     

Organo-modified montmorillonite/poly(?-caprolactone) nanocomposites prepared by melt intercalation in a twin-screw extruder

Nanocomposites based on biodegradable poly(?-caprolactone) organo-modified clay have been prepared by melt intercalation using a twin-screw extruder. The screw configuration developed allowed us to obtain an intercalated/exfoliated nanocomposite structure using a modified montmorillonite containing no polar groups, in contrast to previous work using mainly alkyl ammonium containing hydroxyl polar groups in poly(?-caprolactone). Montmorillonite nanocomposites were prepared using a specific extrusion profile from a 30 wt% masterbatch of organo-modified clay, which was then diluted at 1, 3 and 5%. Intercalated and/or exfoliated nanocomposites structures were assessed using rheological procedures and confirmed by transmission electron microscopy analysis. Mechanical and thermal properties were found to be strongly dependent on morphology and clay percentage. Crystallinity was only slightly affected by the clay addition. Effect of exfoliation on Young's modulus and thermal stability was investigated. Young's modulus increased significantly and onset degradation temperature measured by TGA was significantly reduced for an exfoliated nanocomposite composition containing 5 wt% organoclay.     

Preparation of polylactic acid/epoxidized palm oil/fatty nitrogen compounds modified clay nanocomposites by melt blending

In this study, new biopolymer nanocomposites have been prepared. Fatty nitrogen compounds (FNCs); fatty amide (FA), fatty hydroxamic acid (FHA), and carbonyl difatty amide (CDFA), which were synthesized from palm oil, have been used as one of organic compounds to modify natural clay (sodium montmorillonite). The clay modification was carried out by stirring the clay particles in an aqueous solution of FA, FHA, and CDFA by which the clay layer distance increases from 1.23 to 2.71, 2.91 and 3.23 nm, respectively. The modified clay was then used in the preparation of the polylactic acid/epoxidized palm oil (PLA/EPO) blend nanocomposites. The interaction of the modifier in the clay layer was characterized by X-ray diffraction (XRD), and Fourier transform infrared (FTIR). Elemental analysis was used to estimate the presence of FNCs in the clay. The nanocomposites were synthesized by melt blending of the modified clay and PLA/EPO blend at the weight ratio of 80/20. The nanocomposites were then characterized using XRD, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and tensile properties measurements. The XRD and TEM results confirmed the production of nanocomposites. PLA/EPO modified clay nanocomposites show higher thermal stability and significant improvement of mechanical properties in comparison with those of the PLA/EPO blend.     

Preparation of poly(propylene)/clay layered nanocomposites by melt intercalation from pristine montmorillonite (MMT)

Poly(propylene)/clay nanocomposites were prepared by melt intercalation, using pristine montmorillonite (MMT), hexadecyl trimethyl ammonium bromide (C16), poly(propylene) (PP) and maleic acid (MA) modified PP (MAPP), The nanocomposites structure is demonstrated using X‐ray diffraction (XRD) and high resolution electronic microscopy (HREM). Our purpose is to provide a general concept for manufacturing polymer nanocomposites by melt intercalation starting from the pristine MMT. We found different kneaders (twin‐screw extruder or twin‐roll mill) have influence on the morphology of the PP/clay nanocomposites. Thermogravimetric analysis (TGA) shows that the thermal stability of PP/clay nanocomposites has been improved compared with that of pure PP. Copyright © 2003 John Wiley & Sons, Ltd.     

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.     

用可聚合的眯唑型表面活性剂制备聚苯乙烯／粘土纳米复合材料

用本体聚合法制备了聚苯乙烯／粘土纳米复合材料,用傅里叶红外光谱（FTLR）对有机改性的蒙脱土进行了表征,用X-射线衍射（XRD）表征了纳米复合材料的结构,用热重分析（TGA）、微分热分析（DTA）表征了纳米复合材料的热稳定性。结果表明,聚苯乙烯可以插入含双键的咪唑盐表面活性剂改性的粘土中,形成部分剥离的结构;复合材料的热稳定性较高,开始分解的温度达到414．6℃。