Influence of extrusion temperature on thermal properties of polyamide 6/MMT nanocomposites

Abstract

The effect of processing temperature on the melt flow and thermal behaviour of polyamide 6 (PA6)/organophillic montmorillonite (MMT) nanocomposite was investigated. PA6/MMT nanocomposites were prepared by melt extrusion at five different processing temperatures. Neat PA6 was also extruded as a reference. The composites were characterised by melt flow measurement, differential scanning calorimetry, dynamic mechanical analysis and X-ray diffraction.     

Effect of Organomodified Ni-Al Layered Double Hydroxide (OLDH) on the Properties of Polypropylene (PP)/LDH Nanocomposites

This work addresses the effect of organomodified layer double hydroxide (OLDH) on the properties of PP/LDH nanocomposites prepared by melt intercalation method using a single screw extruder with maleic anhydride grafted polypropylene (PP-g-MA) as a compatibilizer. For this, Ni-Al LDH was first prepared by the co-precipitation method at constant pH using their nitrate salts. The above synthesized pristine LDH was organically modified using sodium dodecyl sulphate (SDS) by the regeneration method. The structural and thermal properties of LDH and PP nanocomposites were performed by X-ray diffraction (XRD), FTIR spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The influence of LDH loading on the mechanical and thermal properties of the nanocomposite was also investigated. The XRD results confirmed the formation of exfoliated PP/LDH nanocomposites. PP/LDH nanocomposites exhibited enhanced thermal stability relative to the pure PP. When 10% weight loss was selected as a point of comparison, the decomposition temperature of PP/LDH (5 wt%) nanocomposite was 15.3°C higher than that of pure PP. The DSC result indicated an increase in crystallization and melting temperature of the PP/LDH nanocomposites compared to pure PP. Overall, the mechanical properties of the PP/LDH nanocomposites increased with an increase in the LDH content. The maximum improvement of tensile strength, Young's modulus, flexural strength, and flexural modulus for the PP/LDH nanocomposite was found to be 11, 22.5, 28, and 22%, respectively, over neat PP. For comparison purposes, a nanocomposite with 5 wt% modified bentonite (PP/B5) was also prepared under the same operating condition and there was no significant improvement in mechanical properties (tensile strength and modulus).     

Preparation and nonisothermal crystallization behavior of polypropylene/layered double hydroxide nanocomposites

Polypropylene (PP)/layered double hydroxide (LDH) nanocomposites were prepared via melt intercalation using dodecyl sulfate anion modified LDH and maleated PP as compatibilizing agent. Evidently the interlayer anions in LDH galleries react with maleic anhydride groups of PP-g-MA and lead to a finer dispersion of individual LDH layers in the PP matrix. The nanostructure was characterized by XRD and TEM; the examinations confirmed the nanocomposite formation with exfoliated/intercalated layered double hydroxides well distributed in the PP matrix. The nonisothermal crystallization behavior of resulting nanocomposites was extensively studied using differential scanning calorimetry (DSC) technique at various cooling rates. In nonisothermal crystallization kinetics, the Ozawa approach failed to describe the crystallization behavior of nanocomposites, whereas the Avrami analysis and Jeziorny method well define the crystallization behavior of PP/LDH nanocomposite. Combined Avrami and Ozawa analysis (Liu model) also found useful. The results revealed that very small amounts of LDH (1%) could accelerate the crystallization process relative to the pure PP and increase in the crystallization rates was attributed to the nucleating effect of the nanoparticles. Polarized optical microscopy (POM) observations also support the DSC results. The effective crystallization activation energy was estimated as a function of the relative degree of crystallinity using the isoconversional analysis. Overall, results indicated that the LDH particles in nanometer size might act as nucleating agent and distinctly change the type of nucleation, growth and geometry of PP crystals.     

One-step synthesized azo-dye modified Mg-Al LDH reinforced biobased semi-aromatic polyamide containing naphthalene ring; study on thermal stability and optical properties

A new series of polyamide Mg-Al layered double hydroxide (LDH) nanocomposites (PANC) were prepared using solution intercalation method. The biobased polyamide (PA) was synthesized using direct polycondensation reaction. Organo azo-dye modified Mg-Al LDH (OLDH) was prepared by one-step method and its effect on the thermal and optical properties of PA was investigated. The X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) results showed the uniform distribution of LDH sheets in the PA matrix. The UV-Vis spectra of PANC showed a blue shift as well as reduction in absorbance intensities and the photoluminescence studies revealed the higher emission intensities for PANC as compared to the neat PA. The results of thermogravimetric analysis (TGA) in both nitrogen and air atmospheres showed that the addition of OLDH up to 5 mass% was slightly improved thermal properties of PA.     

Regenerated cellulose/layered double hydroxide nanocomposite films with improved mechanical property

Construction of environment-friendly biomass-based nanocomposites with high performance is in great demand for developing of a sustainable low-carbon society. Here, transparent and flexible regenerated cellulose (RC)/layered double hydroxide (LDH) nanocomposite films were prepared from aqueous NaOH/urea solutions. The obtained nanocomposite films were characterized using AFM, SEM, FTIR, XRD, tensile testing, water contact angle, and thermogravimetric analysis. The results show that LDH nanoplatelets were individually dispersed with a thickness of 1 nm and surface diameter of 100 nm after ultrasonic treatment. Strong interaction existed between LDH nanoplatelets and cellulose molecules, leading to the improved thermal stability and mechanical strength of RC together with the original good properties of LDH. In particular, the nanocomposite films with 10 wt% LDH showed a 135% and 234% increase in the tensile strength and Young's modulus than those of the neat RC film. Meanwhile, the nanocomposite films exhibited high transparency. Therefore, these RC/LDH nanocomposites are promising in the fields of high-performance packaging materials, flexible display panels, and high-temperature dielectric materials.     

Synthesis and characterization of ethylene vinyl acetate/Mg–Al layered double hydroxide nanocomposites

Mg–Al layered double hydroxide (LDH)/Ethylene vinyl acetate (EVA‐28) nanocomposites were prepared through solution intercalation method using organically modified layered double hydroxide (DS‐LDH). DS‐LDH was made by the intercalation of sodium dodecyl sulfate (SDS) ion. The structure of DS‐LDH and its nanocomposites with EVA‐28 was determined by X‐ray diffraction (XRD) and transmission electron microscope (TEM) analysis. XRD analysis shows that the original peak of DS‐LDH shifted to lower 2θ range and supports the formation of intercalated nanocomposites while, TEM micrograph shows the presence of partially exfoliated LDH nanolayers in addition to orderly stacked LDH crystallites in the polymer matrix. The presence of LDH in the nanocomposites has been confirmed by Fourier transform infrared (FTIR) analysis. The mechanical properties show significant improvement for the nanocomposite with respect to neat EVA‐28. Thermogravimetric (TGA) analysis shows that thermal stability of the nanocomposites is higher than that of EVA‐28. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1845–1851, 2007     

Preparation and properties of layered double hydroxide/poly(ethylene terephthalate) nanocomposites by direct melt compounding

Thermal, rheological and mechanical properties of layered double hydroxide (LDHs)/PET nanocomposites were investigated. To enhance the compatibility between PET matrix and LDHs, organic modification of parent LDH having carbonate anion was carried out using various anionic surfactants such as dodecylsulfate (DS), dodecylbenzenesulfonate (DBS), and octylsulfate(OS) by rehydration process. Then, PET nanocomposites with LDH content of 0, 1.0, and 2.0 wt% were prepared by direct melt-compounding. The dispersion morphologies were observed by transmission electron microscopy and X-ray diffraction, indicating that LDH-DS were exfoliated in PET matrix. From the rheology study, there are some network structures owing to filler-filler and/or filler-matrix interactions in nanocomposite systems. Consequently, DS intercalated LDH provided good compatibility with PET molecules, resulting in exfoliated LDH-DS/PET nanocomposites having enhanced thermal and mechanical properties as compared to other nanocomposites as well as homo PET.     

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.     

Montmorillonite disperses in amorphous phase of RIM PA6 matrix via anionic ring opening polymerisation

The reaction injection moulding process was employed to prepare montmorillonite (O-MMT)/polyamide 6 (PA6) nanocomposites. O-MMT was functionalised by aminosilane in order to improve the compatibility and decrease the viscosity of caprolactam melts, which swell O-MMT. Small angle X-ray diffraction and transmission electron microscopy results demonstrated that PA6 was sufficiently polymerised via in situ anionic ring opening route at the interlayer of the premodified O-MMT that yields a disordered exfoliated structure. Wide angle X-ray diffraction, polarising optical microscopy and differential scanning calorimetry analysis indicated that the crystallinity of nanocomposites decreased as the loading of O-MMT increased. O-MMT can induce γ-phase crystals and eliminate perfect α-phase crystals into smaller imperfect crystals. The O-MMT primarily disperses in the amorphous phase of RIM PA6 matrix that improves the mechanical properties and heat distortion temperature (HDT) of nanocomposites. For the nanocomposite at 5 wt-% O-MMT, the HDT of neat RIM PA6 was improved from 78 to 163°C.     

Microstructure and crystallography in microcellular injection‐molded polyamide‐6 nanocomposite and neat resin

The effects of adding nanoclay to polyamide‐6 (PA‐6) neat resin, and the effects of processing parameters on cell density and size in microcellular injection‐molded components were investigated. In addition, the crystal sizes, structures, and orientation were analyzed with the use of x‐ray diffraction (XRD) and a polarized optical microscope. The standard ASTM D 638‐02 tensile bars for the analyses were molded according to a fractional four‐factor, three‐level, L9 Taguchi design of experiment (DOE) with varying melt temperature, injection speed, supercritical fluid (SCF) concentration, and shot size. It was found that the presence of montmorillonite (MMT) nanoclay greatly reduced the size of the cells and crystals, but increased their density in comparison with neat resin processed under identical molding conditions. In addition, at the sprue section downstream of the machine nozzle, cell size gradually decreased from the part center toward the skin for both the neat resin and the nanocomposite. It was also found that shot size was the most important processing parameter for both the neat resin and nanocomposite in affecting cell density and size in microcellular injection molding components. Weakly preferred crystal orientations were observed on the surface of microcellular injection‐molded PA‐6/MMT tensile bars. Finally, the addition of nanoclay in PA‐6 neat resin facilitated the formation of γ‐phase crystals in the molded components. Polym. Eng. Sci. 45:52–61, 2005. © 2004 Society of Plastics Engineers.     

Shear and extensional rheometry of PA6 reinforced with polyacrylic nanoparticles

Shear and extensional rheometry was carried out on polyamide 6 (PA6) reinforced with crosslinked polyacrylic nanoparticles (PNPs) with mean size of 8 nm. The PNPs were dispersed into a commercial, injection grade, PA6 matrix by melt extrusion, at a concentration of 3 wt%. Thermal analysis showed that the PNPs did not influence the melting and decomposition temperature of the polymer matrix. However, grafting of maleic anhydride to the PNPs (denoted PNP-g-MA) increased the decomposition temperature. On the other hand, X-ray scattering and small-angle light scattering showed that the degree of crystallinity and crystal size were reduced, relative to the neat PA6, i.e., the PNPs disrupted the ordering of the polymer chains. The shear rheological properties showed that the PA6/PNP nanocomposites exhibited a linear viscoelastic behavior. Small-strain oscillatory shear showed that PA6 exhibited a predominantly viscous behavior. However, addition of PNPs induced a predominantly elastic behavior, as measured by the mechanical damping tan δ (=G″/G′), and increased the zero-shear viscosity. The increase in melt elasticity and viscosity was greater for the PA6/PNP-g-MA nanocomposite. Extensional rheometry experiments demonstrated that when PNPs were added to PA6, they induced smaller extensional viscosity, η _ext, values in the matrix, at low strain rates. However, at higher strain rates the PNPs induced a strain hardening behavior. Whereas the neat polymer melt rapidly broke under extensional flow, the PA6/PNP nanocomposites first exhibited lower η _ext than the neat PA6, and then η _ext rapidly increased before breaking, i.e. a strain hardening behavior. The higher melt elasticity of the molten PA6 nanocomposites appears to arise from a jamming effect promoted by the PNPs.     

Polyamide-12 layered silicate nanocomposites by melt blending

Polyamide-12/tetrasilisic fluoromica (PA12-ME100) and polyamide-12/quaternary tallow ammonium chloride modified fluoromica nanocomposites (PA12-MAE) were prepared by melt compounding. The nanocomposite morphology and clay dispersion were investigated using wide angle X-ray diffraction (XRD), scanning electron microscopy (SEM), SEM-energy dispersive X-ray analysis (SEM-EDX), transmission electron miscroscopy (TEM), high resolution transmission electron microscopy (HRTEM) and atomic force microscopy (AFM). A predominantly intercalated morphology was observed for PA12-ME100, and a very high degree of exfoliation for PA12-MAE. HRTEM showed that the polymer crystallites lie perpendicular to the clay surface. The tensile and flexural properties of the PA12-MAE nanocomposite were significantly enhanced compared to neat polyamide-12, even with the addition of only 4 wt% nanoclay. Furthermore, the elongation at break (%) increased from 180% for polyamide-12 up to >500% for the PA12-MAE nanocomposite. In situ measurement of the heat generated in the test specimens during uniaxial tensile deformation using infra-red thermal imaging showed that the temperature of the dumbbell samples increased from room temperature (23 °C) to as high as 70 °C regardless of the strain rate used. This is considerably above the glass transition temperature (T_g) of PA12-MAE (30 °C), as measured by dynamic mechanical thermal analysis (DMTA). The mechanism of deformation is partially explained in terms of microvoid formation. The shear viscosity of the PA12-MAE nanocomposite determined by dual capillary rheometry was lower than both neat polyamide-12 and PA12-ME100. The reduction in shear viscosity of the nanocomposites was shown, from gel permeation chromatography (GPC) studies, not to originate from polymer degradation during melt blending. The coefficient of thermal expansion, decomposition temperature, and melting and crystallisation temperatures and relative crystalline content of the nanocomposite materials were measured by thermo-mechanical analysis (TMA), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) respectively—properties which can be related to polymer nanoclay interactions.     

Preparation and characterization of exfoliated layered double hydroxide/silicone rubber nanocomposites

Silicone rubber (SR)/Mg–Al layered double hydroxide (LDH) nanocomposites were prepared by the solution intercalation of SR crosslinked by a platinum‐catalyzed hydrosilylation reaction into the galleries of dodecyl sulfate intercalated layered double hydroxide (DS–LDH). X‐ray diffraction and transmission electron microscopy analysis showed the formation of exfoliated structures of organomodified LDH layers in the SR matrix. The tensile strength and elongation at break of SR/DS–LDH (5 wt %) were maximally improved by 53 and 38%, respectively, in comparison with those of the neat polymer. Thermogravimetric analysis indicated that the thermal degradation temperature of the exfoliated SR/DS–LDH (1 wt %) nanocomposites at 50% weight loss was 20°C higher than that of pure SR. Differential scanning calorimetry analysis data confirmed that the melting temperature of the nanocomposites increased at lower filler loadings (1, 3, and 5 wt %), whereas it decreased at a higher filler loading (8 wt %). The relative improvements in the solvent‐uptake resistance behavior of the SR/DS–LDH nanocomposites were also observed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Exfoliated polymer nanocomposites by in situ coprecipitation of layered double hydroxides in a polymer matrix

Polyvinylalcohol (PVA) nanocomposites were prepared by a “one step” method based on the coprecipitation of layered double hydroxide (LDH) platelets in the polymer aqueous solution. The PVA/LDH nanocomposites displayed an exfoliated morphology and the concentration of LDH in the nanocomposite was evaluated by IR analysis. Moreover, it was shown that the PVA/LDH nanocomposites had an improved photostability over PVA, which makes this material a good candidate for coating applications. Further optimization will be considered to tune the polymer/LDH properties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of polypropylene/layered silicate nanocomposites using an antioxidant

Polypropylene (PP)/layered silicate nanocomposites were prepared via simple melt mixing of three components, PP, layered silicates modified with octadecylamine (C18-MMT) and antioxidant, to investigate the role of antioxidant. TEM and X-ray scattering results confirmed the intercalated state of silicates in PP/layered silicate nanocomposites with antioxidant. In rheological and mechanical study, the nanocomposites with antioxidant showed higher properties than those of the unfilled PP. The nanocomposite with 5 wt% C18-MMT and 0.5 phr antioxidant exhibited about 1.4 times higher tensile modulus and 1.3 times higher storage modulus than the unfilled PP. However, PP/C18-MMT without antioxidant showed lower rheological values owing to the thermal decomposition of PP and the poor compatibility between PP and C18-MMT. It could be concluded that antioxidants played an important role in enhancing the compatibility between PP and C18-MMT. According to the real time X-ray diffraction, the nanocomposite showed the weak ordering of PP crystals than the unfilled PP in the load-extension plateau region of elongation.     

Crystallization behavior of poly(ε‐caprolactone)/layered double hydroxide nanocomposites

Poly(?‐caprolactone) (PCL)/layered double hydroxide (LDH) nanocomposites were prepared successfully via simple solution intercalation. The nonisothermal melt crystallization kinetics of neat PCL and its LDH nanocomposites was investigated with the Ozawa, Avrami, and combined Avrami–Ozawa methods. The Ozawa method failed to describe the crystallization kinetics of the studied systems. The Avrami method was found to be useful for describing the nonisothermal crystallization behavior, but the parameters in this method do not have explicit meaning for nonisothermal crystallization. The combined Avrami–Ozawa method explained the nonisothermal crystallization behavior of PCL and its LDH nanocomposites effectively. The kinetic results and polarized optical microscopy observations indicated that the addition of LDH could affect the mechanism of nucleation and growth of the PCL matrix. The Takhor model was used to analyze the activation energies of nonisothermal crystallization. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ethylene vinyl acetate/ethylene propylene diene terpolymer‐blend‐layered double hydroxide nanocomposites

Ethylene vinyl acetate (EVA‐45)/ethylene propylene diene terpolymer (EPDM) blend‐layered double hydroxide (LDH) nanocomposites have been prepared by solution blending of 1:1 weight ratio of EVA and EPDM with varying amounts of organo LDH (DS‐LDH). X‐ray diffraction and transmission electron microscopy analysis suggest the formation of partially exfoliated EVA/EPDM/DS‐LDH nanocomposites. Measurement of mechanical properties of the nanocomposites (3 wt% DS‐LDH content) show that the improvement in tensile strength and elongation at break are 35 and 12% higher than neat EVA/EPDM blends. Dynamic mechanical thermal analysis also shows that the storage modulus of the nanocomposites at glass transition temperature is higher compared to the pure blend. Such improvements in mechanical properties have been correlated in terms of fracture behavior of the nanocomposites using scanning electron microscopy analysis. Thermal stability of the prepared nanocomposites is substantially higher compared to neat EVA/EPDM blend, confirming the formation of high‐performance polymer nanocomposites. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

New polylactide-layered silicate nanocomposites. 2. Concurrent improvements of material properties, biodegradability and melt rheology

Our continuing research on the preparation, characterization, materials properties, and biodegradability of polylactide (PLA)-layered silicate nanocomposites has yielded results for PLA-montmorillonite nanocomposites. Montmorillonite modified with trimethyl octadecylammonium cation was used as an organically modified layered silicate for the nanocomposites preparation. The internal structure of the nanocomposites in the nanometer range has been established by using wide-angle X-ray diffraction and transmission electron microscope analyses. All the nanocomposites exhibited superior improvement of practical materials properties such as storage modulus, flexural modulus, flexural strength, heat distortion temperature, and gas barrier property as compared to that of neat PLA. The biodegradability of neat PLA and a representative nanocomposite was also studied under compost, and the rate of biodegradation of neat PLA significantly increased after nanocomposites preparation. The melt rheology of neat PLA and various PLACNs was also studied.     

Ethylene vinyl acetate/Mg‐Al LDH nanocomposites by solution blending

Partially exfoliated ethylene vinyl acetate (EVA‐40, 40% vinyl acetate content)/layered double hydroxide (LDH) nanocomposites using organically modified layered double hydroxide (DS‐LDH) have been synthesized by solution intercalation method. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) studies of nanocomposites shows the formation of exfoliated LDH nanolayers in EVA‐40 matrix at lower DS‐LDH contents and partially intercalated/exfoliated EVA‐40/MgAl LDH nanocomposites at higher DS‐LDH contents. These EVA‐40/MgAl LDH nanocomposites demonstrate a significant improvement in tensile strength and elongation at break for 3 wt% of DS‐LDH filler loading compare to neat EVA‐40 matrix. Thermogravimetric analysis also shows that the thermal stability of the nanocomposites increases with DS‐LDH content in EVA‐40. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Effect of clay modification on the morphological,mechanical, and thermal properties of polyamide 6/polypropylene/montmorillonite nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic montmorillonite (OMMT) were prepared by melt compounding. The sodium montmorillonite (Na‐MMT) was modified using three different types of alkyl ammonium salts, namely dodecylamine, 12‐aminolauric acid, and stearylamine. The effect of clay modification on the morphological and mechanical properties of PA6/PP nanocomposites was investigated using x‐ray diffraction (XRD), transmission electron microscopy (TEM), tensile, flexural, and impact tests. The thermal properties of PA6/PP nanocomposites were characterized using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and heat distortion temperature (HDT). XRD and TEM results indicated the formation of exfoliated structure for the PA6/PP nanocomposites prepared using stearylamine modified montmorillonite. On the other hand, a mixture of intercalated and exfoliated structures was found for the PA6/PP nanocomposites prepared using 12‐aminolauric acid and dodecylamine modified montmorillonite. Incorporation of OMMT increased the stiffness but decreased the ductility and toughness of PA6/PP blend. The PA6/PP nanocomposite containing stearylamine modified montmorillonite showed the highest tensile, flexural, and thermal properties among all nanocomposites. This could be attributed to better exfoliated structure in the PA6/PP nanocomposite containing stearylamine modified montmorillonite. The storage modulus and HDT of PA6/PP blend were increased significantly with the incorporation of both Na‐MMT and OMMT. The highest value in both storage modulus and HDT was found in the PA6/PP nanocomposite containing stearylamine modified montmorillonite due to its better exfoliated structure. POLYM. COMPOS., 31:1156–1167, 2010. © 2009 Society of Plastics Engineers