Isothermal crystallization of intercalated and exfoliated polyethylene/montmorillonite nanocomposites prepared by in situ polymerization

Polyethylene/montmorillonite (PE/MMT) nanocomposites with different dispersion states of MMT were prepared by in situ polymerization. Isothermal crystallization of the intercalated nanocomposite, in which the PE chains were confined in the MMT layers, was studied and was compared with that of the exfoliated nanocomposite. It is observed that the intercalated sample has longer induction period, longer crystallization half time and larger crystallization activation energy than the exfoliated sample, showing that crystallization of PE is retarded due to confinement of the MMT layers. Analysis of crystallization kinetics shows that Avrami exponent (n) increases gradually with crystallization temperature. However, the maximal value of n is 2.0 for the intercalated sample, but it can reach 3.0 for the exfoliated sample. It is inferred that the stems of the PE crystals confined in the MMT layers are parallel to the MMT layers. The Hoffman-Weeks extrapolation method cannot be applied in the intercalated sample because of the small lateral surface of the PE crystals. Based on the depression of the melting temperature, the specific free energy of the PE/MMT interface was estimated, which is about 1.0 mJ/cm², much smaller than the free energy of the lateral surface of PE crystals. This is attributed to the origin of the strong nucleation effect of MMT.     

Synthesis and properties of polybenzoxazole-clay nanocomposites

A novel polybenzoxazole (PBO)/clay nanocomposite has been prepared from a PBO precursor, polyhydroxyamide (PHA) and an organoclay. The PBO precursor was made by the low temperature polycondensation reaction between isophthaloyl chloride (IC) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane with an inherent viscosity of 0.5 dl/g. The organoclay was formed by a cation exchange reaction between a Na⁺-montorillonite (Na⁺-Mont) clay and an ammonium salt of dodecylamine. The PHA/clay was subsequently thermal cured to PBO/clay. Both X-ray diffraction and transmission electron microscope analyzes showed that the organoclay was dispersed in the PBO matrix in a nanometer scale. The in-plane coefficient of thermal expansion (CTE) of PBO/clay film decreased with increasing amounts of organoclay. The CTE of PBO/clay film containing 7 wt% clay was decreased by 21% compared to the pure PBO film. Both of the glass transition temperature (T_g) and the thermal decomposition temperature of PBO/clay increased with increasing amounts of organoclay. The thermal decomposition temperature and the T_g of PBO/clay containing 7 wt% clay increased to 12 and 16 °C, respectively.     

Polyimide nanocomposites prepared from high-temperature, reduced charge organoclays

Montmorillonite clays modified with the dihydrochloride salt of 1,3-bis(3-aminophenoxy)benzene (APB) were used in the preparation of polyimide/organoclay hybrid films. Organoclays with varying surface charge based upon APB were prepared and examined for their dispersion behavior in the polymer matrix. High molecular weight poly(amide acid) solutions were prepared in the presence of the organoclays. Films were cast and subsequently heated to 300 °C to cause imidization. The resulting nanocomposite films, containing 3 wt% of organoclay, were characterized by transmission electron microscopy and X-ray diffraction. The clay's cation exchange capacity (CEC) played a key role in determining the extent of dispersion in the polyimide matrix. Considerable dispersion was observed in some of the nanocomposite films. The most effective organoclay was found to have a CEC of 0.70 meq/g. Nanocomposite films prepared with 3-8 wt% of this organoclay were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and thin-film tensile testing. High levels of clay dispersion could be achieved even at the higher clay loadings. Results from mechanical testing revealed that while the moduli of the nanocomposites increased with increasing clay loadings, both strength and elongation decreased.     

Effect of organoclay purity and degradation on nanocomposite performance, Part 2: Morphology and properties of nanocomposites

Part 1 of this series showed that the purification level and surfactant loadings of organoclays significantly affect their thermal stability; the higher rate of degradation of as-received commercial organoclay is primarily a result of excess surfactant that is intentionally or unintentionally part of the commercial organoclay. Polypropylene nanocomposites and nylon 6 nanocomposites were formed through melt processing to assess the practical consequences, in terms of nanocomposite formation and performance, of using a purified version of the organoclay with no excess surfactant and a lower rate of thermal degradation versus using the as-received organoclay. The properties and morphology of polymer-clay nanocomposites based on both as-received and purified organoclays were evaluated by TEM, WAXS, and mechanical testing. The results from the different techniques were generally consistent with each other suggesting that the differences in thermal stability of organoclays do not appear to have a significant effect on the morphology and properties of the nanocomposites formed from them.     

Nanocomposites from Polycaprolactone (PCL)/Soy Protein Isolate (SPI) Blend with Organoclay

New biobased, ecofriendly nanocomposites were prepared from polycaprolactone (PCL)/soy protein isolate (SPI) blend (80/20 wt/wt) with organically modified clay, by melt compounding. X-ray diffraction and transmission electron microscopy analysis revealed that an intercalated nanocomposite was formed and the silicate layers of the clay were uniformly dispersed at a nanometer scale in matrix polymer. There was great enhancement of both tensile and dynamic mechanical properties in the nanocomposite. A rheological study revealed that the nanocomposite exhibits strong shear-thinning behavior in the melted state, and a percolated network of clay particles was formed in the melted state.     

Polymer nanocomposites based on transition metal ion modified organoclays

A unique class of nanocomposites containing organoclays modified with catalytically active transition metal ions (TMI) and ethylene vinyl acetate (EVA) copolymers was prepared. The morphology, thermal and rheological properties of these nanocomposites were studied by thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray scattering/diffraction and oscillatory shear rheometry. TMI-modified organoclays were thought to possess pillaring of multivalent TMI in the interlayer silicate gallery, leading to a notable reduction of the interlayer d-spacing. The resulting nanocomposites exhibited significantly improved thermal stability and fire retardation properties, but similar morphology (i.e., an intercalated-exfoliated structure) and rheological properties comparable with EVA nanocomposites containing unmodified organoclays. It appears that the compressed organic component in the TMI-modified organoclay can still facilitate the intercalation/exfoliation processes of polymer molecules, especially under extensive shearing conditions. The improved fire retardation in nanocomposites with TMI-modified organoclays can be attributed to enhanced carbonaceous char formation during combustion, i.e., charring promoted by the presence of catalytically active TMI.     

Blown films of nanocomposites prepared from low density polyethylene and a sodium ionomer of poly(ethylene-co-methacrylic acid)

A detailed study of the performance of blown films prepared from nanocomposites based on LDPE and a sodium ionomer of poly(ethylene-co-methacrylic acid) is reported. The organoclay content and film blowing conditions were varied to determine the effect of platelet concentration, exfoliation and orientation on film properties. Mechanical properties including stiffness, puncture resistance, and resistance to tear propagation were evaluated and compared to corresponding properties of unfilled polymer films. Permeability of the films to moisture and common atmospheric gases like oxygen, nitrogen, and carbon dioxide was also measured using standard testing methods.In general, films prepared from nanocomposites based on the ionomer exhibited greater improvements in mechanical and barrier properties over unfilled polymer compared to similar films prepared from nanocomposites based on LDPE. This is due to the greater degree of organoclay exfoliation achieved in the ionomer compared to LDPE. The addition of 3 wt% MMT to the ionomer increased the tensile modulus of blown films by an average of 50% without sacrificing much tear strength, puncture resistance or film extensibility. Gas permeability in these films was lowered by 40% and moisture transmission rate was reduced by 60%.     

An exfoliation of organoclay in thermotropic liquid crystalline polyester nanocomposites

A thermotropic liquid crystalline polyester (TLCP) with an alkoxy side-group was synthesized from 2-ethoxyhydroquinone and 2-bromoterephthalic acid. Nanocomposites of TLCP with Cloisite 25A (C25A) as an organoclay were prepared by the melting intercalation method above the melt transition temperature (T_m) of the TLCP. Liquid crystallinity, morphology, and thermo-mechanical behaviors were examined with increasing organoclay content from 0 to 6%. Liquid crystallinity of the C25A/TLCP hybrids was observed when organoclay content was up to 6%. Regardless of the clay content in the hybrids, the C25A in TLCP was highly dispersed in a nanometer scale. The hybrids (0-6% C25A/TLCP) were processed for fiber spinning to examine their tensile properties. Ultimate strength and initial modulus of the TLCP hybrids increased with increasing clay content and the maximum values of the mechanical properties were obtained from the hybrid containing 6% of the organoclay. Thermal, morphological and mechanical properties of the nanocomposites were examined by differential scanning calorimetry (DSC), thermogravimetric analyzer (TGA), polarized optical microscope, electron microscopes (SEM and TEM), and capillary rheometer.     

Catalytic degradation of polyethylene over SAPO-37 molecular sieve

The degradation of high-density polyethylene (HDPE) was studied alone and in presence of silicoaluminophosphate type silicoaluminophosphate (SAPO-37) as catalyst. This material was synthesized by the hydrothermal method using tetrapropylammonium hydroxide and tetramethylammonium chloride as organic templates. The characterization by X-ray diffraction, infrared spectroscopy, thermogravimetry and scanning electron microscopy showed that typical faujasite structure for the SAPO-37 was obtained. The total acidity, determined by n-butylamine adsorption, it was equivalent to 0.558 mmol g⁻¹, corresponding to moderate acid strength. For catalytic reaction, a physical mixture of 25%SAPO-37/HDPE was decomposed in a thermobalance at heating rates of 5, 10 and 20 °C min⁻¹, from 380 to 520 °C. At the maximum degradation rate, the products were collected in a cold trap and analyzed by a coupled gas chromatograph/mass spectrometer. The degradation of HDPE without catalyst was carried out at the same conditions for comparison with the obtained data with SAPO-37. The HDPE alone suffers decomposition to a wide range of hydrocarbons (C₅–C₂₅) while in the presence of catalyst, light hydrocarbons (C₂–C₁₂) were obtained. By the application of the Vyazovkin model-free kinetic method, it was observed that the activation energy decreased from 290 kJ mol⁻¹ for HDPE alone, to 220 kJ mol⁻¹ for 25%SAPO-37/HDPE, evidencing that SAPO-37 is an effective catalyst for polyethylene degradation.     

High-performance EPDM/organoclay nanocomposites by melt extrusion

Ethylene-propylene-diene terpolymer (EPDM)/organoclay nanocomposites were prepared by melt extrusion in a twin-screw extruder. The organoclay was characterized by XRD and TGA. As observed by transmission electron microscopy (TEM), the organoclay particles were exfoliated in EPDM. The tensile strength of the nanocomposites increased to 12.3 MPa at the same 3.0 phr amounts of fillers, which was a five-fold increase compared to pure EPDM and 2.8 times compared to the nanocomposite prepared by direction blending; furthermore it was above that of carbon black composites with 15.0 phr. The results of co-reinforcement system exploited a promising application prospect of the organoclay and the nanocomposites. The processability of the terpolymer was improved as a result of the decrease of mooney viscosity; the improvement of the thermal stability of the nanocomposite was determined by TGA.     

Investigation on the polyamide 6/organoclay nanocomposites with or without a maleated polyolefin elastomer as a toughener

Polyamide 6 (PA 6)-based nanocomposites were prepared using a melt-mixing technique in this study. One commercial organoclay (denoted 30B) and one maleated polyolefin elastomer (denoted POEMA) served as the reinforcing filler and toughener, respectively. The X-ray diffraction (XRD), scanning electron microscopy combined with energy dispersive spectroscopy (SEM/EDS) and transmission electron microscopy (TEM) results confirmed the nano-scaled dispersion of 30B in the composites. Different mixing sequences presented similar phase morphology for the same formulated nanocomposites. XRD results also revealed that both 30B and POEMA would induce the formation of γ form PA 6 crystal, with 30B exhibiting a higher efficiency. Differential scanning calorimetry (DSC) results indicated that the addition of 30B altered the crystallization kinetics of PA 6, which was mainly attributed to the prevailing formation of γ form crystal. Complex melting behaviors were observed for neat PA 6 and the nanocomposites. These complex behaviors are associated with different polymorphs and the ‘melting-recrystallization-remelting’ phenomenon. Moderate thermal stability enhancement of PA 6 after adding 30B and/or POEMA was confirmed using thermogravimetric analysis (TGA). The storage modulus, Young's modulus and tensile strength of PA 6 were increased after adding 30B. However, these properties declined after further incorporation of POEMA. The different-processed PA 6/30B/POEMA nanocomposites displayed balanced tensile properties and toughness between those of neat PA 6 and PA 6/30B nanocomposite.     

Effect of Type of Surfactants and Organoclay Loading on the Mechanical Properties of EVOH/Clay Nanocomposite Blown Films

EVOH/clay nanocomposite films were prepared by using four types of surfactants to treat surface of clay because the surfactants were expected to affect the degree of clay dispersion in the EVOH matrix, which would in turn affect the properties of film. The nanocomposite films that contained the single alkyl tail with two repeating units of oxyethylene surfactants or single alkyl tail surfactant showed higher tensile strength, tensile modulus and elongation at break than those with 15 repeating units of oxyethylene surfactants or those with double alkyl tail surfactant.     

Polymer matrix degradation and color formation in melt processed nylon 6/clay nanocomposites

Nylon 6 nanocomposites based on various quaternary alkyl ammonium organoclays were prepared by melt processing using a twin screw extruder. Dilute solution viscosity techniques were used to evaluate the level of polymer molecular weight degradation experienced during nanocomposite compounding; whereas colorimeter techniques were used to document color formation. In general, a significant reduction in nylon 6 matrix molecular weight was observed, which is believed to stem, in part, from reaction(s) between the surfactant of the organoclay and the polyamide chains. The level of degradation depends on both the type of nylon 6 material used and the surfactant chemistry in the organoclay. For a given organoclay, nanocomposites based on high molecular weight nylon 6 materials experience more matrix degradation, as well as color formation, than those based on low molecular weight materials; this is believed to arise from increased exposure of the organoclay surface to the nylon 6 owing to increased platelet exfoliation. Different organoclays lead to different levels of polymer degradation and color formation, depending upon the level of unsaturation present in the organic surfactant; the higher the number of double bonds the greater the degradation and the deeper the color formation. The primary mechanism of degradation is believed to be thermo-oxidative. Melt mixing of nylon 6 with model compounds, long-chain alkenes, shows that the same mode of degradation i.e. via double bonds can be replicated. In addition to unsaturation effects, the presence of hydroxyl-ethyl groups, opposed to methyl groups, in the organoclay surfactant, results in more color. Isothermal thermogravimetric analysis (TGA) was conducted on the organoclays to determine if thermal stability was a cause of molecular weight degradation; although, this relationship does not seem to exist, a direction correlation is observed between the organoclay degradation and nanocomposite modulus, or indirectly level of exfoliation. Use of antioxidant was found to reduce the amount of molecular weight loss. All evidence suggests that morphology and physical properties of nanocomposites formed from nylon 6 are not measurably affected by the reactions that lead to molecular weight degradation or color formation.     

Morphology, thermal stability and rheology of poly(propylene carbonate)/organoclay nanocomposites with different pillaring agents

Unpillared montmorillonite PGV and five organoclays (Nanocor's Nanomer I.44P, I.24TL and I.34TCN and Southern Clay Product's C25A and C30B) were high shear melt-blended (2.5 wt%) into poly(propylene carbonate) (PPC). Solubility parameters of the clay pillaring agents versus that of PPC were used to predict clay/PPC miscibilities and these were compared to XRD and TEM nanoclay dispersion measurements. Clays I.34TCN and C30B, with the highest predicted pillaring agent/PPC miscibilites, had partially exfoliated morphologies. Clays I.24TL, C25A and I.44P, with pillaring agents predicted to be less PPC miscible, were less highly nanodispersed. Quaternary ammonium pillars with two 2-hydroxyethyl groups promoted the best nanodispersion in PPC. 12-Aminododecanoic acid (in I.24TL) promoted the intercalation. Dimethyl dialkyl quaternary ammoniums (in I.44P and C25A) were less effective. Organoclay dispersion improved the thermal stability. The PPC/I.24TL nanocomposite, with the most stable 12-aminododecanoic acid pillar, was the most thermally stable (PPC/I.34TCN and PPC/C30B were the second and third). The nanocomposites exhibited narrower linear viscoelastic zones than PPC and solid-like behaviors in these linear zones.     

Influence of clay exfoliation on the physical properties of montmorillonite/polyethylene composites

Melt compounding was used to prepare conventional composites of montmorillonite clay and polyethylene (PE) as well as nanocomposites of exfoliated montmorillonite platelets dispersed in a maleated polyethylene (PE-g-MAn) matrix. The extent of clay platelet exfoliation in the PE-g-MAn nanocomposites was confirmed by X-ray diffraction and resulted in a significant reduction of the degree of crystallinity and increased polymer crystallization rates. Studies of non-isothermal crystallization kinetics suggested that the exfoliated clay promotes heterogeneous nucleation and two-dimensional crystallite growth.PE/clay composites behaved in a similar manner as conventional macrocomposites, exhibiting modest increases in their rheological properties and Young's modulus. Conversely, the nanoscale dimensions of the dispersed clay platelets in the nanocomposites led to significantly increased viscous and elastic properties and improved stiffness. This was attributed to the high surface area between the polymer matrix and the exfoliated clay, which resulted in enhanced phase adhesion.     

Boehmite-based polyethylene nanocomposites prepared by in-situ polymerization

Polyethylene (PE)-boehmite nanocomposites were prepared by means of metallocene/MAO-catalyzed in-situ polymerization of ethylene in the presence of boehmites, which were rendered organophilic by modification with carboxylic acids such as stearic acid and undecylenic acid. Such organoboehmites are readily dispersed in the polymerization media such as toluene. Polymerization activity, filler dispersion and mechanical properties of the nanocomposites were investigated as a function of type and concentration of the organoboehmites. The catalyst activity of different metallocenes (Cp₂ZrCl₂ and rac-Me₂Si(2-Me-benz[e]-Ind)₂ZrCl₂) was increased up to 100% in the presence of organoboehmite fillers. The dispersion of nanoboehmites, as evidenced by TEM studies, was dependent upon the content of the carboxylate modifier. At 20 wt.% carboxylate content uniform dispersions of organoboehmite particles with average particle sizes smaller than 100 nm were obtained. According to stress-strain measurements, the Young's modulus increased with increasing boehmite content without sacrificing high elongation at break.     

Effect of organoclay purity and degradation on nanocomposite performance, Part 1: Surfactant degradation

The alkylammonium surfactants used to form commercial organoclays are known to begin to degrade at temperatures below the typical melt processing temperatures of some polymers. In this study, the thermal stability and degradation of various surfactants and their corresponding organoclays were investigated. Several factors, such as surfactant type and excess surfactant in the organoclay, that affect the thermal stability of surfactants on organoclays are explored. Nuclear magnetic resonance (NMR) spectroscopy was used to analyze the decomposition products. Thermogravimetric analysis (TGA) was used as the primary method to characterize the thermal stability of these surfactants and organoclays; the neat surfactants lose mass more rapidly, at a given temperature, than the corresponding organoclay. Washing the organoclay with methanol proved to be an effective way to remove the excess surfactant from the clay galleries. Such purification generally improves the thermal stability of the as-received organoclays. Depending on the availability of residual halide anions in the organoclay, the organoclays decompose via either S_N2 nucleophilic substitution or Hoffmann elimination pathways.     

Graphene/polyethylene nanocomposites: Effect of polyethylene functionalization and blending methods

Since its recent successful isolation, graphene has attracted an enormous amount of scientific interest due to its exceptional physical properties. Graphene incorporation can improve electrical and mechanical properties of polymers including polyethylene (PE). However, the hydrophobic nature and low polarity of PE have made effective dispersion of nano-fillers difficult without compatibilization. Graphene was derived from graphite oxide (GO) via rapid thermal exfoliation and reduction. This thermally reduced graphene oxide (TRG) was blended via melt and solvent blending with linear low density PE (LLDPE) and its functionalized analogs (amine, nitrile and isocyanate) produced using a ring-opening metathesis polymerization (ROMP) strategy. TRG was well exfoliated in functionalized LLDPE while phase separated morphology was observed in the un-modified LLDPE. Transmission electron micrographs showed that solvent based blending more effectively dispersed these exfoliated carbon sheets than did melt compounding. Tensile modulus was higher for composites with functionalized polyethylenes when solvent blending was used. However, at less than 3 wt.% of TRG, electrical conductivity of the un-modified LLDPE was higher than that of the functionalized ones. This may be due to phase segregation between graphene and PE, and electrical percolation within the continuous filler-rich phase.     

Visible light induced methylene blue dye degradation photo-catalyzed by WO3/graphene nanocomposites and the mechanism

Graphene incorporated WO₃ nanocomposites with different graphene contents were synthesized in the present study using the hydrothermal approach. The results showed nano-structured WO₃ sticks were uniformly dispersed within the graphene sheets. The incorporation of the graphene significantly decreased the band gap energy of the pristine WO₃. Due to this reason, the prepared WO₃/Graphene nanocomposites had much higher photodegradation efficiency to the methylene blue dye than the pristine WO₃. More importantly, it was found that the prepared nanocomposites could initiate dye degradation with a very desirable efficiency under visible light, and the methylene blue molecules could be converted to some small molecules during this process. This study provides an effective photocatalyst which can initiate dyestuff degradation in the wastewater under visible light.     

Controlled silylation of montmorillonite and its polyethylene nanocomposites

An alkylammonium modified montmorillonite, Cloisite 20A, was reacted with trimethylchlorosilane in order to replace the edge hydroxyl groups of the clay. Since the reaction will liberate HCl, reactions were performed both in the presence and absence of sodium hydrogencarbonate. Without sodium hydrogencarbonate, the proton, which was generated in situ, could replace a portion of the alkylammonium ions and further react with trimethylchlorosilane. The product, TMS-20H, has a smaller basal spacing than Cloisite 20A itself. If the proton was trapped by the hydrogencarbonate ions, only the edge silanol groups react with trimethylchlorosilane. The product, TMS-20A, maintained the same basal spacing as the precursor. The presence of the edge trimethylsilyl groups were confirmed by thermogravimetric analysis and infrared spectroscopy. Intercalated polyethylene nanocomposite could be fabricated by melt blending polyethylene with TMS-20A, while only microcomposites could be formed using TMS-20H. The structure of the hybrid was characterized by X-ray diffraction and transmission electron microscopy.