Thermal,mechanical, and barrier properties of polyethylene terephthalate‐platelet nanocomposites prepared by in situ polymerization

This study used in situ polymerization to prepare polyethylene terephthalate (PET) nanocomposites incorporating Ethoquad‐modified montmorillonite (eMMT), unmodified hectorite (HCT), or phenyl hectorite (phHCT) particles to study the impact of platelet surface chemistry and loading on thermal, mechanical, and gas barrier properties. eMMT platelets reduced the PET crystallization rate without altering the ultimate degree of crystallinity. In contrast, HCT and phHCT platelets accelerated the polymer's crystallization rate and increased its crystallinity. DMA results for thermally‐quenched samples showed that as T increased past glass transition temperature (T_g), HCT and phHCT nanocomposites (and control PET) manifested precipitous drops in G′ followed by increasing G′ due to cold crystallization; in contrast, eMMT nanocomposites had much higher G′ values around T_g. This provides direct evidence of eMMT reinforcement in thermally‐quenched eMMT nanocomposites. These results suggest that eMMT has a strong, favorable interaction with PET, possibly through Ethoquad‐PET entanglement. HCT and phHCT have a fundamentally different interaction with PET that increases crystallization rate and T_g by 11 to 17°C. Water barrier improvement in eMMT nanocomposites agrees with previously published oxygen barrier results and can be rationalized in terms of a tortuous path gas barrier model. POLYM. ENG. SCI., 52:1888–1902, 2012. © 2012 Society of Plastics Engineers     

Morphology,thermal and mechanical properties of nylon 12/organoclay nanocomposites prepared by melt compounding

Nylon 12 (PA12) nanocomposites with different organoclay loadings were successfully prepared by melt compounding. X‐ray diffraction indicated the dominance of the exfoliated clay morphology throughout the matrix after mixing in a Brabender twin‐screw extruder, in accordance with transmission electron microscopy observations. Thermogravimetric analysis showed that the thermal stability of the PA12 matrix was improved by about 20 °C on incorporation of only 5 wt% clay. Tensile and nanoindentation tests indicated that the elastic modulus and the hardness steadily increased by about 52 % and 67 %, respectively, with a clay concentration up to 5 wt%, while improvements in tensile strength were limited. Impact strength decreased linearly by about 25 % as the clay loading increased (up to 5 wt%), indicating an embrittlement due to clay addition, as evidenced by SEM observation on the fracture surfaces. The embrittling effect may be due to the weak interfacial adhesion between the clay platelets and the polymer matrix. Copyright © 2004 Society of Chemical Industry     

Morphology and mechanical properties of polypropylene/organoclay nanocomposites

Polypropylene (PP) nanocomposites were prepared by melt intercalation in an intermeshing corotating twin‐screw extruder. The effect of molecular weight of PP‐MA (maleic anhydride‐ modified polypropylene) on clay dispersion and mechanical properties of nanocomposites was investigated. After injection molding, the tensile properties and impact strength were measured. The best overall mechanical properties were found for composites containing PP‐MA having the highest molecular weight. The basal spacing of clay in the composites was measured by X‐ray diffraction (XRD). Nanoscale morphology of the samples was observed by transmission electron microscopy (TEM). The crystallization kinetics was measured by differential scanning calorimetry (DSC) and optical microscopy at a fixed crystallization temperature. Increasing the clay content in PP‐ MA330k/clay, a well‐dispersed two‐component system, caused the impact strength to decrease while the crystallization kinetics and the spherulite size remained almost the same. On the other hand, PP/PP‐MA330k/clay, an intercalated three‐component system containing some dispersed clay as well as the clay tactoids, showed a much smaller size of spherulites and a slight increase in impact strength with increasing the clay content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1562–1570, 2002     

Effect of clay on mechanical and gas barrier properties of blown film LDPE/clay nanocomposites

Low density polyethylene (LDPE)/clay nanocomposites, which can be used in packaging industries, were prepared by melt‐mix organoclay with polymer matrix (LDPE) and compatibilizer, polyethylene grafted maleic anhydride (PEMA). The pristine clay was first modified with alkylammonium salt surfactant, before melt‐mixed in twin screw extruder attached to blown‐film set. D‐spacing of clay and thermal behavior of nanocomposites were characterized by Wide‐Angle X‐ray Diffraction (WAXD) and differential scanning calorimetry (DSC), respectively. WAXD pattern confirmed the increase in PEMA contents exhibited better dispersion of clay in nanocomposites. Moreover, DSC was reported the increased PEMA contents caused the decrease in degree of crystallinity. Mechanical properties of blown film specimens were tested in two directions of tensile tests: in transverse tests (TD tests) and in machine direction tests (MD tests). Tensile modulus and tensile strength at yield were improved when clay contents increased because of the reinforcing behavior of clay on both TD and MD tests. Tensile modulus of 7 wt % of clay in nanocomposite was 100% increasing from neat LDPE in TD tests and 17% increasing in MD tests. However, elongation at yield decreased when increased in clay loading. Oxygen permeability tests of LDPE/clay nanocomposites also decreased by 24% as the clay content increased to 7 wt %. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Morphological considerations on the mechanical properties of blown high-density polyethylene films

Blown films having a broad range of morphologies were prepared from high-density polyethylenes (HDPE) with unimodal and bimodal molecular weight distribution under several processing conditions, and the effect of their morphological features on the dart drop impact resistance, Elmendorf tear strength, and tensile properties of the films has been studied. The organization of lamellar stacks seems to play a critical role on the mechanical properties of the blown HDPE films. The dart drop impact resistance of the blown HDPE films is highly dependent on the presence of the network structure of lamellar stacks and the level of the intraconnectivity and interconnectivity of lamellar stacks. The coherent orientation of lamellar stacks leads to significant anisotropy of tear and tensile properties. © 1997 John Wiley & Sons, Inc.     

Physical properties of polyethylene/silicate nanocomposite blown films

Maleated polyethylene/silicate nanocomposite and maleated polyethylene/SiO₂ blown films were prepared by melt extrusion. The silicate and SiO₂ significantly affected the physical properties of the films. The former films showed higher tensile strength than the latter films. This high reinforcement effect seemed to be attributable to the strong interaction between the matrix and silicate as well as the uniform dispersion of silicate layers in the polymer matrix. The addition of silicate beyond a certain content gave a worse Elmendorf tear strength than SiO₂. The silicate did not increase the falling dart impact strength at all. The worst Elmendorf strength apparently originated from the orientation of anisotropic silicate rather than the orientation of lamellae of the polymer matrix, and the silicate made the films more brittle. The well‐dispersed silicate layers in the polymer matrix gave almost the same optical properties as the pure polymer despite the increase in the silicate content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2131–2136, 2003     

Interactions between PLA,organo-montmorillonite and plasticizer: Synergistic effect on the barrier and mechanical properties of PLA nanocomposites blown films

In this study, the impact of incorporating a plasticizer on the compatibility between organo-montmorillonite (OMMt) and polylactic acid (PLA) is investigated, and the resulting barrier and mechanical properties are reported. Four polymers were chosen as plasticizers to prepare the PLA nanocomposite blown films: poly(ethylene glycol), poly(ethylene oxide), polycaprolactone (PCL), and random ethylene-methyl acrylate-glycidyl methacrylate terpolymer. Firstly, 5 wt% of each plasticizer and 3 wt% of OMMt (Dellite® D43B) were mixed simultaneously with PLA in a twin-screw extruder and then introduced into the hopper of a single screw extruder to produce D43B-PLA/plasticizer nanocomposite films. The compatibilization effect was examined based on microstructure observations and thermodynamic predictions. Crystallinity was evaluated using DSC and XRD measurements. The results obtained for permeability and mechanical testing showed that the improvement of barrier and mechanical properties depends directly on the degree of compatibility between plasticizer, OMMt, and PLA. Indeed, the interfacial properties, XRD diffraction, and TEM images showed that a synergistic effect can result from high interfacial interactions between different compounds.     

Rheological,mechanical, optical,and transport properties of blown films of polyamide 6/residual monomer/montmorillonite nanocomposites

Exfoliated nanocomposites of polyamide 6 (PA6) with residual monomer and an organically treated montmorillonite (3 and 5 wt %) were produced by twin‐screw extrusion. The composites had their steady state, dynamic, and transient rheological properties measured by parallel‐plates rheometry; their exfoliation level was characterized by wide angle X‐rays diffraction (WAXD) and transmission electron microscopy (TEM). The characterization showed as follows: (i) the nanoclay's lamellas were well dispersed and distributed thru the PA6, (ii) the postpolymerization of the residual monomer produced more branched chains than linear ones in the pure PA6, (iii) the nanoclay's lamellas acted as entanglement points in the nanocomposites, and (iv) the molecular weight of the PA6 in the nanocomposites decreased. Blown films of the nanocomposites were produced by single screw extrusion; the die pressure during the film blowing of the nanocomposites strongly decreased. The tensile mechanical properties of the blown films were also measured. Along the machine direction (MD), the best mechanical properties were obtained with the 5 wt % nanocomposite, whereas along the transverse direction (TD), the 3 wt % nanocomposite had the best behavior. The glass transition temperature (T_g) of the blown films was measured by dynamic mechanical thermal analyses (DMTA). The 5 wt % nanocomposite had the highest T_g of all the films. The optical properties were measured by spectrophotometry; the nanoclay decreased the films' haze, but the level of transmittance was not affected. The water vapor and oxygen permeability rates of the nanocomposites films were found to be lower than in the pure PA6 blown film as a result of a tortuosity effect. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of clay content and clay/surfactant on the mechanical, thermal and barrier properties of polystyrene/organoclay nanocomposites

In the present paper, three ammonium salts namely, tetraethylammonium bromide (TEAB), tetrabutylammonium bromide (TBAB), and cetyltrimethylammonium bromide (CTAB) were employed to prepare organoclay by cation exchange process. Polystyrene (PS) /clay nanocomposites were prepared by melt blending using commercial nanoclay and organoclays prepared using above mentioned salts. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis indicated that the modified clays were intercalated and/or exfoliated into the polystyrene matrix to a higher extent than the commercial nanoclay. Further, amongst the modified organoclays, TBAB modified clay showed maximum intercalation of clay layers and also exfoliation to some extent into the polystyrene matrix. TEM micrograph exhibited that TBAB modified clay had the best nanoscale dispersion with clay platelet thickness of ∼6–7 nm only. The mechanical properties of the nanocomposites such as tensile, flexural and izod impact strength were measured and analyzed in relation to their morphology. We observed a significant improvement in the mechanical properties of polystyrene/clay nanocomposites prepared with modified clays as compared to commercial organoclay, which followed the order as; PS/TBAB system > PS/CTAB system > PS/TEAB system. Thermogravimetric analysis (TGA) demonstrated that T₁₀, T₅₀ and Tmax were more in case of polystyrene nanocomposites prepared using modified organoclays than nanoclay [nanolin DK4] and maximum being in the case of PS/CTAB system. The results of Differential Scanning Calorimetry (DSC) confirmed that the glass transition temperature of all the nanocomposites was higher as compared to neat polystyrene. The nanocomposites having 2% of TBAB modified clay showed better oxygen barrier performance as compared to polystyrene.     

混炼法制备的NBR/HMMT纳米复合材料的结构与性能研究

通过混炼法实现了NBR在本体状态下对有机改性蒙脱土的插层复合。XRD分析表明该复合材料中蒙脱土层间距从1.2nm扩大到4.8nm，TEM研究表明HMMT以1－10nm薄片分散在橡胶基体中。该体系表现出优良物理机械性能。     

Effects of organoclay Soxhlet extraction on mechanical properties, flammability properties and organoclay dispersion of polypropylene nanocomposites

The organic treatment on a layered silicate used in nanocomposite synthesis is the interface between the hydrophilic layered silicate (clay) and hydrophobic polymer in the case of polypropylene. However, the typical synthesis of an organoclay can result in excess organic treatment which can hinder mechanical and flammability benefits. This excess organic treatment may result in plasticization of the polymer matrix, possibly removing some of the mechanical and flammability property benefits provided by the nanocomposite. In this paper, the effects of using Soxhlet Extraction on the Organoclays after synthesis was investigated. Soxhlet extraction times on organoclays were found to have an effect on the mechanical and flammability properties of the resulting polypropylene nanocomposite. The removal of excess organic treatment by Soxhlet extraction resulted in improvements in flex modulus, improved clay dispersion, delayed time to ignition, and lowered heat release rate during burning.     

Vulcanization behavior and mechanical properties of organoclay fluoroelastomer nanocomposites

The vulcanization behavior and mechanical properties of clay/fluoroelastomer nanocomposites produced by melt‐mixing of Dyneon FPO 3741 (a terpolymer of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene) with 10 phr of unmodified montmorillonite (CloisiteNA) or di(hydrogenated tallow‐alkyl) dimethyl ammonium‐modified montmorillonites (Cloisite15A and Cloisite20A) were studied. The properties of clay/FKM nanocomposites were compared with composites prepared using 10 and 30 phr of carbon black. The effects of clay surfactant and surfactant concentration on the vulcanization behavior, mechanical, and dynamical properties of peroxide cured composites were studied. XRD results of cured composites showed a decrease in d‐spacing and indicated deintercalation of the clays after the vulcanization process. It was also found that organoclays retard the FKM peroxide vulcanization process. Significantly, higher maximum torque on vulcanization was obtained with organoclays versus unmodified clay and carbon black. Although the morphologies of organoclay/FKM nanocomposites studied by XRD and TEM suggest similar intercalated/exfoliated structures, the organoclay with the lowest concentration of surfactant (95 meq/100 g clay) resulted in the highest increase in torque, modulus, hardness, and tear strength in the clay/FKM nanocomposites. It was also found that organoclays can increase both the hydrodynamic reinforcement and hysteresis loss of FKM nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphology development,melt linear viscoelastic properties and crystallinity of polylactide/polyethylene/organoclay blend nanocomposites

Polylactide/polyethylene blends (PLA/PE) and their nanocomposites were prepared via the melt blending process. The effects of organoclay, compatibilizer (PE‐g‐MA), and PE content on morphology, linear viscoelastic properties of the melt and cold crystallization of the samples have been studied. The Palierne model is applied to predict the rheological behavior of unfilled blends. It implies that there is a quantitative agreement between model and experimental data for low PE content blend. From WAXD and the rheological behavior, it is shown that organoclay exhibits a higher extent of intercalation and dispersion in PLA/PE/organoclay nanocomposite than in PLA/organoclay nanocomposite. The DSC results present that the addition of compatibilizer into blend nanocomposite increases cold crystallization temperature of PLA by about 3°C. This can be explained by the role of compatibilizer in transfer of a part of organoclay from PLA matrix to droplets resulting in increase of PLA chain mobility and, therefore, slightly greater cold crystallization temperature. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41300.     

Transparent copolyester/organoclay nanocomposites prepared by in situ intercalation polymerization: Synthesis,characterization, and properties

In this study, amorphous poly(ethylene terephthalate‐co‐1,3/1,4‐cyclohexylenedimethylene terephthalate) (PETG)/organoclay nanocomposites was synthesized by the in situ intercalation polymerization of terephthalic acid, ethylene glycol, 1,3/1,4‐cyclohexanedimethanol, and organoclay. The organoclay was obtained by modifying sodium montmorillonite (clay) with hexadecyl triphenylphosphonium bromide. The thermal, mechanical, optical, and gas barrier properties of these PETG nanocomposites with various organoclay contents (0–3 wt%) were discussed. The differential scanning calorimetry and X‐ray analyses revealed that all of the nanocomposites were amorphous. X‐ray diffraction and transmission electron micrographs showed that the organoclay was well dispersed in the polymer matrix, although some parts of the agglomerated layers remained on the scale of several hundreds of nanometers. The thermal stability and the mechanical property of the nanocomposites increased with organoclay content. The optical transmittances of nanocomposites that contained 0.5, 1, and 3 wt% of organoclay were 86.8%, 84.4%, and 77.4%, respectively. The oxygen transmission rate of the nanocomposite that contained 3 wt% of organoclay was about 50% of the PETG base polymer. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Novel preparation and mechanical properties of rigid polyurethane foam/organoclay nanocomposites

A novel method for preparing rigid polyurethane (PU) foam/organoclay nanocomposites was developed through the direct incorporation of an organoclay into PU foam matrices without the addition of any physical or chemical blowing agent. The resultant foams with an appropriate content of the organoclay had a finer cell structure than the pristine PU foams because the organoclay not only acted as a nucleating agent as expected but also acted as a blowing agent of the PU foams; this could be attributed to the bound water between the interlayers of the organoclay. In addition, the incorporation of the organoclay up to 4 phr resulted in improvements in the tensile and compressive strengths, with the maximum values appearing at 2 phr (110 and 152%, respectively). The significant improvement in the mechanical properties could be attributed to the finer cell structure and the increased internal strength of the materials due to the higher degree of hydrogen bonding. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Polystyrene–organoclay nanocomposites prepared by melt intercalation,in situ,and masterbatch methods

In this study, polystyrene (PS)/montmorillonite nanocomposites were prepared by melt intercalation, in situ polymerization, and masterbatch methods. In the masterbatch method, as the first step, a high clay content composite of PS–organoclay (masterbatch) was prepared by in situ polymerization, and then the prepared masterbatch was diluted to desired compositions with commercial PS in a twin‐screw extruder. The structure and mechanical properties of the nanocomposites were examined. X‐ray diffraction (XRD) analysis showed that the d‐spacing of the in situ formed nanocomposites increased from 32.9 Å for the organoclay powder to 36.3 and 36.8 Å respectively in nanocomposites containing 0.73 and 1.6 wt% organoclay, indicating intercalation. However, the d‐spacing of the other prepared materials remained nearly unchanged when compared with pure organoclay powder. Thus, at these low clay contents, in situ formed nanocomposites showed the best improvement in mechanical properties including tensile, impact strength, and Young's modulus. In situ polymerization method did not prove to be efficient at high clay loadings in terms of intercalation and mechanical properties. At high clay loadings, the effects of the three methods in promoting mechanical properties were not significantly different from each other. POLYM. COMPOS., 27:249–255, 2006. © 2006 Society of Plastics Engineers     

Effects of organoclay platelets on morphology and mechanical properties in PTT/EPDM-g-MA/organoclay ternary nanocomposites

The addition of up to 6 part per hundred (phr) of an organoclay to a 80/20 (w/w) PTT/EPDM-g-MA blend led to ternary compounds that came together as a means of balancing stiffness/strength versus toughness/ductility. The effect of organoclay platelets on morphologies and mechanical properties of PTT/EPDM-g-MA/organoclay ternary nanocomposites had been studied by SEM, TEM, WAXD, and mechanical testing. For the 80/20 (w/w) blend, the clay platelets are located inside the dispersed domains of EPDM-g-MA phase. The clay platelets do not act effectively as a barrier for the coalescence of the dispersed domains. The complex viscosities (η^∗) of the 80/20 (w/w) PTT/EPDM-g-MA blend increased with the amount of the organoclay increasing, which are proposed as the reason for the dispersed domain size (D) that becomes smaller at higher clay content. Mechanical tests show that the Young's modulus increases, whereas the tensile strength and the impact strength decrease when the content of the clay increases.     

Ternary nanocomposites: Curing,morphology, and mechanical properties of epoxy/thermoplastic/organoclay systems

The influence of two organically modified montmorillonites on the curing, morphology and mechanical properties of epoxy/poly(vinyl acetate)/organoclay ternary nanocomposites was studied. The organoclays and poly(vinyl acetate) (PVAc) provoked contrary effects on the epoxy curing reaction. Ternary nanocomposites developed different morphologies depending on the PVAc content, that were similar to those observed in the epoxy/PVAc binary blends. The organoclays were only located in the epoxy phase independently of the morphology. All nanocomposites showed intercalated structures with similar clay interlayer distances. Both PVAc and organoclays lowered the T_g of the epoxy phase, the presence of clays did not influence the T_g of the PVAc phase. The addition of the organoclays to the epoxy improved stiffness but lowered ductility while the adition of PVAc improved toughness although reduced stiffness of epoxy thermoset. Ternary nanocomposites exhibited optimal properties that combine the favourable effects of the clay and the thermoplastic. POLYM. COMPOS., 37:2184–2195, 2016. © 2015 Society of Plastics Engineers     

Characteristics of polystyrene/polyethylene/clay nanocomposites prepared by ultrasound‐assisted mixing process

In this study, polymer‐clay nanocomposites of various concentrations were prepared by ultrasonically assisted polymerization and melt‐mixing processes. A sonication process using power ultrasonic waves was employed to enhance nano‐scale dispersion during melt‐mixing of polymer blends and organically modified clay. We expected enhanced breakup of layered silicate bundles and further reduction in the size of the dispersed phase, with better homogeneity compared to the different immiscible blend pairs. X‐ray diffraction (XRD) and Transmission Electron Microscopy (TEM) were used to characterize the structures of the nanocomposites. The rheological behaviors of the obtained nanocomposites were measured with parallel plate rheometry. It was found that the ultrasound‐assisted process successfully generated exfoliated nanocomposites and promoted in‐situ compatibilization of the matrix comprising an immiscible pair of polymers in a blend. The resulting nanocomposite exhibited superior thermal stability and elastic modulus compared to the base polymer. Polym. Eng. Sci. 44:1198–1204, 2004. © 2004 Society of Plastics Engineers.     

Effect of the organoclay preparation on the extent of intercalation/exfoliation and barrier properties of polyethylene/PA6/montmorillonite nanocomposites

Nanocomposites of HDPE matrix and 3 wt % organoclay/PA6 discontinuous phase were prepared in a mixer chamber. These nanocomposites of organoclay, PA6, and HDPE were characterized by X‐ray diffraction, scanning electron and transmission electron microscopy (SEM and TEM). Barrier properties were determined by cyclohexane pervaporation and solubility. The results show that the degree of exfoliation and/or intercalation and the barrier properties depend on a combination of the proper chemical treatment and optimized processing in these polyethylene‐organoclays nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010