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     

Spinning and properties of poly(ethylene terephthalate)/organomontmorillonite nanocomposite fibers

By in situ polycondensation, a intercalated poly(ethylene terephthalate)/organomontmorillonite nanocomposite was prepared after montmorillonite (MMT) had been treated with a water‐soluble polymer. This nanocomposite was produced to fibers through melt spinning. The resulting nanocomposite fibers were characterized by X‐ray diffraction (XRD), differential scanning calorimeter (DSC), and transmission electron microscopy (TEM). The interlayer distance of MMT dispersed in the nanocomposite fibers was further enlarged because of strong shear stress during processing of melt spinning. This was confirmed by XRD test and TEM images. DSC test results showed that incorporation of MMT accelerated the crystallization of poly(ethylene terephthalate) (PET), but the crystallinity of the drawn fibers just had a little increasing compared with that of neat PET drawn fibers. Also compared with pure PET drawn fibers, tensile strength at 5% elongation and thermal stability of the nanocomposite fibers were improved. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1443–1447, 2005     

Non‐isothermal crystallization kinetics of polyamide 1010/montmorillonite nanocomposite

The non‐isothermal crystallization kinetics of pure polyamide 1010 (PA1010) and PA1010/montmorillonite nanocomposite (PA1010/MMT) was investigated by differential scanning calorimetry (DSC) at various cooling rates. The Avrami analysis modified by Jeziorny and a new method developed by Mo can describe the non‐isothermal crystallization process of PA1010 and PA1010/MMT nanocomposite very well. The difference in the value of exponent n between PA1010 and PA1010/MMT nanocomposite suggests that the nano‐size montmorillonite layers act as nucleation agents of PA1010. The values of half‐time of crystallization and crystallization rate coefficient (CRC) show that the crystallization rate of PA1010/MMT nanocomposite is faster than that of PA1010 at a given cooling rate. Polym. Eng. Sci. 44:861–867, 2004. © 2004 Society of Plastics Engineers.     

Study on the dynamic self‐organization of montmorillonite in two phases

Polycarbonate (PC)/acrylonitrile–butadiene–styrene (ABS) polymer alloy/montmorillonite (MMT) and nylon 6 (PA6)/ABS polymer alloy/MMT nanocomposites were prepared using the direct melt intercalation technique. Their structures were characterized by XRD and TEM. The results of TEM show that the silicate layers dispersed differently in two phases. In the PC/ABS/MMT nanocomposite, the silicate layers were self‐organized in the ABS phase, whereas in the PA6/ABS/MMT nanocomposite, the silicate layers were dispersed in both phases but mainly in the PA6 phase. Furthermore, the PC/MMT nanocomposite was melt‐mixed with pure ABS, and the changed morphology of the hybrid with the change of melt‐mixing time was characterized by XRD and TEM, to study the dynamic self‐assembly of clay layers in two phases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1457–1462, 2004     

Surface modification of montmorillonite with novel modifier and preparation of polystyrene/montmorillonite nanocomposite by in situ radical polymerization

Exfoliated polystyrene/organo-modified montmorillonite nanocomposite was synthesized through in situ free radical polymerization by dispersing a modified reactive organophilic montmorillonite layered silicate in styrene monomers. The original montmorillonite (MMT) was modified by a novel cationic surfactant. A cationic initiator, consisting of a quaternary ammonium salt moiety, α-phenyl chloro acetyl chloride moiety, and 9-decen-1-ol moiety, was intercalated into the interlayer spacing of the layered silicate. Modified MMT clays were then dispersed in styrene monomers and subsequently polymerized by a free-radical in situ polymerization reaction to yield polystyrene/montmorillonite nanocomposite. The structure of obtained modifier was investigated by proton nuclear magnetic resonance (¹H NMR) and Fourier-transform infrared (FT-IR) spectroscopy. The exfoliating structure of nanocomposite was probed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Comparing with pure polystyrene, the nanocomposite showed much higher decomposition temperature and higher glass transition temperature (T_g).     

Synthesis and characterization of polyvinyl acetate/montmorillonite nanocomposite by in situ emulsion polymerization technique

Exfoliated polyvinyl acetate/montmorillonite nanocomposite (PVAc/MMT) was prepared via in situ emulsion polymerization. The resulting PVAc with various organophilic MMT contents was investigated. In the nanocomposite latex preparation, sodium lauryl sulfate (SLS), ammonium persulfate (APS), and poly (vinyl alcohol) (PVA) are used as anionic emulsifier, conventional anionic initiator, and stabilizer, respectively. The samples were characterized using elemental analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM). The XRD and AFM results demonstrate that the MMT well dispersed at molecular level in the PVAc matrix. Thermal properties of the nanocomposite were studied by using differential scanning calorimetric analysis (DSC). The exfoliated PVAc/MMT nanocomposite showed a higher glass transition temperature and a better thermal stability compared to the pure PVAc.     

Preparation,structure, and properties of poly(vinyl acetate‐co‐methyl methacrylate) nanocomposite microspheres with exfoliated montmorillonite through using two‐stage in situ suspension polymerization

Effective encapsulation of montmorillonite intermediate particles (I‐MMT) within poly (vinyl acetate‐co‐methyl methacrylate) (PVAMMA) copolymer by in situ suspension polymerization was performed. The I‐MMT encapsulation, layer exfoliation behavior, chemical composition, particle size distribution and thermostability of PVAMMA/I‐MMT nanocomposite microspheres were characterized by electron microscopies, X‐ray diffraction (XRD), laser particle analyzer, and thermogravimetric analysis (TGA). Swelling behaviors of the nanocomposite microspheres in various cationic salt solutions (NaCl and CaCl₂) and anionic salt solution (NaCl and Na₂SO₄) were also investigated. Results showed that the properties of layer dispersion surface and expansion of these nanocomposite microspheres were well achieved. The synthetic yields of the nanocomposites decreased as the I‐MMT loading increased. These nanocomposite microspheres had an average size from 96.8 μm to 138.4 μm with narrow particle size distribution, loose, and porous surface morphology. XRD patterns clearly proved the exfoliation of MMT layers in the copolymer matrix, which was consistent with TEM analysis. These nanocomposite microspheres showed higher negative zeta potential and higher thermal stability than those of the copolymer microspheres, which was due to the layer exfoliations in encapsulated microspheres. These selected microspheres with 10 to 70 μm diameters provided effectively plugging in the micrometer‐sized core channels through deformation and migration process in plugging experiments, which made them be the candidate materials for modifying the porous reservoir to enhance oil recovery in petroleum engineering. POLYM. COMPOS., 35:1104–1116, 2014. © 2013 Society of Plastics Engineers     

Structure and properties of polybutadiene/montmorillonite nanocomposites prepared by in situ polymerization

Polybutadiene (PB)/Montmorillonite nanocomposites (NCs) were prepared by in situ polymerization through the anionic polymerization technique. The effects of treating method of organophilic MMT (OMMT), the type of OMMT, and the solvent used in polymerization were studied. The structure and properties of NCs were characterized using X‐ray Diffraction (XRD), transmission electron micrograph (TEM), H‐NMR spectrum, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). The consumption of BuLi was varied with different treating methods. The molecular weight distribution of PB added with OMMT (DK1) was wide, and the molecular weight distribution became narrow when OMMT‐DK1B and DK4 were added. OMMT did not disperse stably in cyclohexane, but could form a homogeneous solution in toluene and xylene. XRD and TEM showed that exfoliated NCs were obtained by in situ polymerization through the anionic polymerization technique. From the H‐NMR spectrum of PB and PB/OMMT NCs, it could be seen that the content of 1, 2 units of PB increased ～100%, while 1, 4 units decreased when 6.2 wt % of OMMT was added. The results of DSC and DMA indicated that T_g and T_dc were increased when compared with those of PB. Both storage modulus and loss modulus were increased with the addition of OMMT, and tan δ was decreased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3615–3621, 2006     

超高相对分子质量聚乙烯／纳米蒙脱土复合材料的制备与表征

采用甲基丙烯酰氧乙基三甲基氯化铵(DMC)对微米尺度的蒙脱土(MMT)进行离子交换，所得有机蒙脱土(DMCMMT)及少量引发剂与超高相对分子质量聚乙烯(PE-UHMW)，在双螺杆挤出机上进行反应挤出，得到了具有一定流动性能的PE-UHMW／有机纳米蒙脱土复合材料。利用XRD、DSC、SEM及TEM等方法进行了复合材料结构表征。     

Preparation and properties of polyethylene–clay nanocomposites by an in situ graft method

The polyethylene–clay nanocomposites were prepared by the in situ graft copolymerization of styrene containing twin‐benzyldimethyldioctadecylammonium bromine modified montmorillonite (TBDO‐MMT) in polyethylene with dicumyl peroxide (DCP) as an initiator in molten state. XRD and TEM analysis indicated that intercalated polyethylene/MMT nanocomposites are obtained. The mechanics performance, crystal behavior, thermal properties, and the effect of MMT contents on PE/MMT nanocomposite were also studied. As comparison, polyethylene/montmorillonite composites prepared by a simply melt compounding without styrene were studied as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4921–4927, 2006     

In situ fibrillar reinforced PET/PA‐6/PA‐66 blend

Ternary fibrillar reinforced blends are obtained by melt‐blending of poly(ethylene terephthalate) (PET), polyamide 6 (PA‐6) and polyamide 66 (PA‐66) (20/60/20 by weight) in the presence of a catalyst, followed by cold drawing of the extruded bristles to a draw ratio of about 3.4 and additional annealing of the drawn blend at 220 or 240°C for 4 or 8 h. The blend samples are studied by DSC, X‐ray diffraction, SEM, and static and dynamic mechanical testing (DMA). SEM and DMA show that PA‐6 and PA‐66 form a homogeneous, continuous matrix in which PET regions are dispersed. X‐ray and DSC measurements of the drawn and annealed at 220°C samples suggest mixed crystallization (solid solubility) of PA‐6 and PA‐66, and cooperative crystallization of PET with the two polyamides. After annealing at 240°C (above the melting point of PA‐6 and below that of PET), the polyamide matrix becomes partially disoriented, while the oriented, fibrillar PET is preserved and plays the role of a reinforcing element. The DSC results for the same samples suggest in situ generation of an additional amount of copolymer. This additional copolymerization, together with that generated during blend mixing in the extruder, improves the compatibility of the blend components (mostly at the PET‐polyamide interface) and alters the chemical composition of the blend.     

Montmorillonite nanoclay filler effects on electrical conductivity,thermal and mechanical properties of epoxy‐based nanocomposites

Epoxy‐based nanocomposites with 2, 5, and 7 wt% of montmorillonite (MMT) nanoclay were prepared using high shear melt mixing technique. The microstructural features of the nanocomposites were investigated by transmission electron microscopy (TEM). The thermal and mechanical properties were measured using differential scanning calorimetry (DSC), thermogravimetric analyzer (TGA), and dynamic mechanical analyzer (DMA). Further, the effect of voltage, temperature, seawater aging on the electrical conductivity (σ_DC) of the nanocomposites was also measured. To understand the free volume behavior upon filler loading, and to observe the connectivity between microstructure and other properties, positron annihilation lifetime spectroscopy was used. The TEM results revealed that MMT nanoparticles were uniformly dispersed in the epoxy matrix. Experimental results showed that the inclusion of 2 wt% MMT nanofiller increased the T_g, electrical conductivity, thermal stability, modulus, free volume of the epoxy nanocomposite significantly. This is well explained from the results of T_g (DSC and DMA), thermal stability, TGA residue, free volume analysis, and electrical conductivity. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Synthesis and study of mechanical and fire retardant properties of (carboxymethyl cellulose -g-polyacrylonitrile)/montmorillonite biodegradable nanocomposite

Despite abundant researches on petroleum based polymer nanocomposites over micro and macro composites, these nanocomposites suffer from deprived biodegradability, highly inherent flammability and less mechanical strength. The present work describes the preparation of a biodegradable nanocomposite based on carboxymethyl cellulose-g-polyacrylonitrile (CMC-g-PAN) and montmorillonite (MMT) nanoclay by using ammonium persulfate (APS) as an initiator, methylene bis-acrylamide (MBA) as a crosslinker via emulsifier free emulsion polymerisation. The formation of the nanocomposites was confirmed by Fourier transform infrared (FTIR), X-ray diffraction (XRD) and Transmission electron microscope (TEM) analysis. The formation of CMC-g-PAN copolymer was confirmed by means of proton nuclear magnetic resonance (¹H NMR) spectra. The improvement in thermal stability of the nanocomposites over copolymer was outstanding. More importantly, incorporating MMT enables the nanocomposite to achieve a dramatically reduced peak heat release rate of 536?±?03 kW m^?2 shown in cone calorimetry tests and higher limiting oxygen index (LOI) value indicating improved fire retardancy. In addition, the tensile strength of the nanocomposite was also increased by around 41% with 5% w/v MMT contents. This is explained on the basis of strong interfacial adhesion between CMC and MMT through PAN. Meanwhile for its better commercialization, the eco-friendly nature was studied via biodegradation.     

Synthesis and characterization of partially hydrolyzed polyacrylamide nanocomposite weak gels with high molecular weights

High‐molecular‐weight partially hydrolyzed polyacrylamide nanocomposite (HPAMNC) weak gels were synthesized and evaluated for their flooding behaviors in oil‐recovery applications. The structure, morphology, and properties of the obtained HPAMNC samples and their weak gels were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). XRD patterns clearly proved the exfoliation of the montmorillonite (MMT) layers in the polymer matrix; this was consistent with TEM analysis. The morphology of the HPAMNC was proven to be in a cross‐wire aggregated form by SEM analysis. The viscosity‐average molecular mass of the obtained HPAMNC was approximately 8.51 × 10⁶ under the optimized MMT load at 1.0 wt %. The flooding experiments showed that the oil‐recovery rates in sand pack tubes with low and high permeability were enhanced by approximately 35.1 and 46.2%, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42626.     

Preparation and characterization of anionically polymerized butadiene‐isoprene copolymer/clay nanocomposites

Butadiene‐isoprene copolymer/montmorillonite (BIR/MMT) nanocomposites were synthesized successfully via in situ anionic polymerization. The results of transmission electron microscopy and X‐ray diffractometer showed that the clay layers were exfoliated and high reaction temperature benefited the exfoliation of layers in BIR/MMT. The polymerization still exhibited “living” characteristics with the addition of organophilic montmorillonite (OMMT). However, the contents of 1,2‐polybutadiene and 3,4‐polyisoprene of the copolymer decreased with the addition of OMMT, because of its absorption effect on N,N,N′,N′‐tetramethylethanediamine as revealed by ¹H NMR. Moreover, it was observed that the glass‐transition temperature of the BIR/MMT nanocomposites also decreased when compared with the BIR copolymers. The thermal stability of the nanocomposites was improved, because of the barrier property of exfoliated clay layers. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 1167–1172, 2006     

Curing kinetics and thermal property characterization of o‐CFER/MeTHPA/O‐MMT nanocomposite

The kinetics of the cure reaction for a system of o‐cresol‐formaldehyde epoxy resin (o‐CFER), 3‐methyl‐tetrahydrophthalic anhydride (MeTHPA), N,N‐dimethyl‐benzylamine, and organic montmorillonite(O‐MMT) were investigated by means of X‐ray diffraction (XRD) and differential scanning calorimetry (DSC). The XRD result indicates that an exfoliated nanocomposite was obtained. The analysis of DSC data indicated the behavior was shown in the first stages of the cure for the system, which could be well described by the model proposed by Kamal. In the later stages, the reaction is mainly controlled by diffusion, and diffusion factor, f(α), was introduced into Kamal's equation. In this way, the curing kinetics was predicted well over the entire range of conversion. Molecular mechanism for curing reaction was discussed. The thermal degradation kinetics of the system were investigated by thermogravimetric analysis (TGA), which revealed that with the increase of O‐MMT content, TG curves shift to higher temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3023–3032, 2006     

Development of a gelatin-g-poly(acrylic acid-co-acrylamide)–montmorillonite superabsorbent hydrogels for in vitro controlled release of vitamin B12

Gelatin (Ge)-g-poly(acrylic acid-co-acrylamide) and montmorillonite (MMT)-clay-based nanocomposite hydrogels were fabricated to study the controlled release of vitamin B₁₂. Polymeric hydrogels were characterized with Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). FTIR spectroscopy confirmed the grafting of partially neutralized acrylic acid on a Ge backbone. The incorporation of MMT fillers inside the nanocomposite hydrogels and their increased crystallinity were established by XRD analysis. The rough surface morphologies of the composite hydrogels shown by SEM resulted from the assimilation of MMT inside the same. TEM confirmed the formation of nanosized composites. The average length and width of the MMT platelets were found to be 184.37 and 20.48 nm, respectively. The maximum swelling of the hydrogel was 375 g/g, and the results were established with Design-Expert software. The biodegradability of the nanocomposite increased in comparison to that of the copolymer hydrogel. Biocompatibility and cytotoxicity studies were also performed. During different time intervals, the controlled release of vitamin B₁₂ in artificial gastric fluid (AGF) and artificial intestinal fluid (AIF) was evaluated with a UV–visible spectrophotometer; this resulted in different controlled release curves. The release in AGF was 42%, and in AIF, the cumulative release was 80% over 6 h. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47596.     

Effect of polymethylmethacrylate–montmorillonite nanocomposite on the release of some biologically active 1,2,4‐triazine derivatives

Methylmethacrylate chloromethylstyrene copolymer–montmorillonite (PMMA–MMT) intercalated nanocomposite was prepared by bulk copolymerization of methylmethacrylate (MMA) and chloromethylstyrene (2 wt%) followed by phosphonium salt formation. The intercalation of polymeric phosphonium salt into montmorillonite was achieved through an ion exchange process between sodium cations in MMT and phosphonium groups attached to the copolymer. Thermogravimetric analysis (TGA) showed improved thermal stability for the intercalated nanocomposite in comparison with the pure PMMA. Biologically active compounds including 4‐amino‐6‐methyl‐3‐thioxo‐3,4‐dihydro‐2H‐[1,2,4]triazin‐ 5‐one (I), 4‐amino‐6‐methyl‐3,4‐dihydro‐2H‐[1,2,4]triazin‐3,5‐dithione (II), 4‐amino‐6‐(4‐methoxystyryl)‐3‐thioxo‐3,4‐dihydro‐2H‐[1,2,4]triazin‐5‐one (III), and 4‐amino‐6‐styryl‐3‐thioxo‐3,4‐dihydro‐2H‐[1,2,4]triazin‐5‐one (IV) have been prepared and reacted with PMMA–MMT intercalates and ion exchanged with sodium montmorillonite (MMT) in the presence of HCl. Infrared spectra (IR) show bands characteristic to amide linkage between triazine derivatives and PMMA. These nanocomposites have been characterized by X‐ray diffraction (XRD) and transmission electron microscope (TEM). The release of biologically active compounds intercalated layered silicates is controllable and these materials have a great potential as a delivery host in the pharmaceutical field. The effect of temperature and presence of saline solution on the release was studied. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

PVC/montmorillonite nanocomposites based on a thermally stable,rigid‐rod aromatic amine modifier

Two kinds of polyvinyl chloride (PVC)/montmorillonite (MMT) nanocomposites were prepared by the melt intercalation method based on a thermally stable, rigid‐rod aromatic amine modifier and a commonly used 1‐hexadecylamine. The information on morphological structure of PVC/MMT nanocomposites was obtained using XRD and TEM. The mechanical, thermal, and flame retardant properties of the nanocomposites were characterized by universal tester, DMA, TGA, and cone calorimeter. The degree of degradation of PVC was studied by ¹H‐NMR. MMT treated by the aromatic amine exhibited better dispersibility than that treated by 1‐hexadecylamine. The nanocomposites, based on this MMT, consequently exhibited better mechanical, thermal, and flame retardant properties and lower degradation degree than those based on 1‐hexadecylamine‐treated MMT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 567–575, 2004     

Effect of Layered Silicates on the Crystallinity and Mechanical Properties of HDPE/MMT Nanocomposite Blown Films

Summary The highdensitypolyethylene (HDPE)/montmorillonite (MMT) nanocomposites were prepared by melt blending using twin screw extruder with two step process. The master batches were manufactured by melt compounding with maleic anhydride grafted HDPE (HDPE-g-MAH) and MMT. The HPDE/MMT master batches were subsequently mixed with HDPE. The blown nanocomposite films were obtained by a single screw extruder attached film blowing and take-off unit. The MMT dispersion in the nanocomposite films was characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM). The influence of MMT on the crystallinity, thermal properties and mechanical properties as a function of compatibilizer was investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and universal testing machine, respectively. X-ray and TEM images showed the partially exfoliated nanocomposites which have the 5:1 – 20:1 ratios of HPDE-g-MAH and MMT. The thermal and mechanical properties of nanocomposites were enhanced by increasing the contents of MMT and in the presence of compatibilizer.