Preparation and characterization of nylon 66/montmorillonite nanocomposites with co-treated montmorillonites

In this paper, a new type of organophilic montmorillonites, co-treated by octadecylammonium and aminoundecanoic acid, were synthesized and applied to prepare nylon 66/montmorillonite nanocomposites via melt compounding in a twin extruder. WAXD and TEM characterization indicate that a disordered structure was derived and the montmorillonite platelets dispersed in nanoscale in the nylon 66 matrix. The nanocomposites with co-treated montmorillonite display comparatively higher strength and modulus compared to nylon 66 matrix.     

Polyimide/montmorillonite nanocomposites with photolithographic properties

Polyimide/montmorillonite nanocomposites with photolithographic properties (PSPI/MMT) were prepared by in situ polymerization using an intrinsic photosensitive polyimide (PSPI) based on 4,4^′-diamino-3,3^′-dimethyldiphenylmethane (MMDA) and benzophenone-3,3^′,4,4^′-tetracarboxylic dianhydride (BTDA). XRD, TEM were used to obtain the information on morphological structure of PSPI/MMT nanocomposites. The exfoliated structure was obtained in the MMT content range studied. Satisfactory photolithographic patterns were obtained when the MMT content was below 2 wt.%. Universal tester, TGA, DSC were applied to characterize the mechanical and thermal properties of the nanocomposites. The introduction of MMT led to increase in tensile strength to the PSPI matrix while the elongation at break was not obviously effected. The introduction of MMT also resulted in improved thermal stability, marked decrease in coefficient of thermal expansion, decrease in solvent uptake, slight increase in glass transition temperature and increase in modulus.     

Structural design of imidazolium and its application in PP/montmorillonite nanocomposites

Four kinds of imidazolium surfactants with high thermal stability were designed and synthesized accordingly. The structures of these surfactants were characterized by ¹H NMR spectra. The TGA results indicated that the thermal stabilities of these surfactants with saturated alkyl groups were relatively high and the initial decomposition temperatures at 5% weight loss (T_0.05) were higher than 250 °C. Imidazolium(O) modified montmorillonite (MMT) was prepared by cation exchange. TGA results showed that the OMMT showed obviously higher thermal stability than the surfactants themselves and the T_0.05 values of OMMT were higher than 330 °C. The dihexadecane imidazolium (DHI) with two long tails has the ability to enlarge the interlayer spacing to a bigger degree compared with other imidazolium surfactants with only one long tail. Polypropylene(PP)/OMMT nanocomposites were prepared by solution blending and the effects of these surfactants with different structures on the silicate layer dispersion in PP matrix were measured.     

Preparation and characterization of poly(propylene carbonate)/montmorillonite nanocomposites by solution intercalation

Poly(propylene carbonate) (PPC) is a new biodegradable aliphatic polycarbonate. However, the poor thermal stability and low glass transition temperatures (T_g) have limited its applications. To improve the thermal properties of PPC, organophilic montmorillonite (OMMT) was mixed with PPC by a solution intercalation method to produce nanocomposites. An intercalated-and-flocculated structure of PPC/OMMT nanocomposites was confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The thermal and mechanical properties of PPC/OMMT nanocomposites were investigated by thermal gravimetric analysis (TGA), differential scanning calorimetric (DSC), and electronic tensile tester. Due to the nanometer-sized dispersion of layered silicate in polymer matrix, PPC/OMMT nanocomposites exhibit improved thermal and mechanical properties than pure PPC. When the OMMT content is 4 wt%, the PPC/OMMT nanocomposite shows the best thermal and mechanical properties. These results indicate that nanocomposition is an efficient and convenient method to improve the properties of PPC.     

Preparation of polystyrene/montmorillonite nanocomposites using a new radical initiator-montmorillonite hybrid via in situ intercalative polymerization

Polystyrene/montmorillonite (PS/MMT) nanocomposites were prepared by in situ free radical intercalative polymerization, using 1, 3 and 5 wt% of a new cationic radical initiator-MMT hybrid. The corresponding nanocomposites were designated as PS/MMT-1, PS/MMT-3 and PS/MMT-5, respectively. The silicate layers were well exfoliated and randomly dispersed in the PS/MMT-1 and PS/MMT-3, but were less exfoliated in the PS/MMT-5, due to the predominant extra-gallery polymerization over the intra-gallery polymerization. The unique properties of nanocomposites resulted from the strong interactions between the nano-sized silicate layer surfaces and the polymer chains. The onset temperature of thermal degradation, and the glass transition temperature, increased with increasing hybrid content, up to 3 wt%. The molecular weights of the PS in the PS/MMT-1 and PS/MMT-3 were less than those calculated theoretically, due to the predominant intra-gallery polymerization.     

Polyethylene and polypropylene nanocomposites based upon an oligomerically modified clay

Montmorillonite clay was modified with an oligomeric surfactant, which was then melt blended with polyethylene and polypropylene in a Brabender mixer. The morphology was characterized by X-ray diffraction and transmission electron microscopy, while thermal stability was evaluated from thermogravimetric analysis and the fire properties by cone calorimetry. The nanocomposites are best described as mixed immiscible/intercalated/delaminated systems and the reduction in peak heat release rate is about 40% at 5% inorganic clay loading.     

Synthesis and characterization of UV-irradiated silver/montmorillonite nanocomposites

We have successfully developed a simple method for preparing silver nanoparticles (Ag NPs) using UV irradiation of AgNO₃ in the interlamellar space of a montmorillonite (MMT) without any reducing agent or heat treatment. The properties of Ag/MMT nanocomposites were studied as a function of the UV irradiation period. UV irradiation disintegrated the Ag NPs into smaller size until a relatively stable size and size distribution were achieved. The results from UV–vis spectroscopy show that particles size of Ag NPs decrease with the increase of irradiation period. The crystalline structure of Ag NPs was determined by powder X-ray diffraction (PXRD).     

Shear-induced crystallization of isotactic polypropylene based nanocomposites with montmorillonite

Shear-induced isothermal crystallization in iPP based nanocomposites with organo-modified montmorillonite was followed by light depolarization technique. Prior to the crystallization, samples were sheared at 1 or 2 s⁻¹ for 10 s in a plate-plate system at crystallization temperature of 136 °C. Structure of the solidified specimens was investigated by light microscopy and electron microscopy, X-ray techniques and IR spectroscopy. Strong enhancement of the nucleation and crystallization after shearing was observed in the compatibilized nanocomposites with the clay. Clay exfoliation was found to accelerate strongly the shear-induced nucleation and overall crystallization. However, the sheared samples exhibited only weak orientation of α crystals with (0 4 0) crystallographic planes parallel to shearing direction that resulted probably from a small population of oriented crystals that formed due to shear-induced orientation of iPP chains and served as nuclei for further nearly isotropic growth.     

Preparation and characterization of exfoliated polystyrene/clay nanocomposites using a cationic radical initiator-MMT hybrid

The exfoliated polystyrene (PS)/clay nanocomposites were prepared via in situ polymerization using a cationic radical initiator-intercalated montmorillonite hybrid. The exfoliated structure resulted from the predominant intra-gallery polymerization over the extra-gallery polymerization owing to the anchored radical initiator inside the clay galleries. Several critical properties of the nanocomposites such as the initial thermal degradation temperature, glass transition temperature, storage modulus, Young’s modulus, and tensile strength were estimated and compared with earlier reported literature values. The improvements in such properties were either comparable or much greater than the reported literature values, mainly due to the efficient exfoliation and dispersion of the clay in the PS matrix.     

Layered nanoparticles modified by chain end functional PE and their nanocomposites with PE

Layered materials (MMT,LDH) were successfully modified by chain end functionalized polyethylene via an ion exchange method.The samples were characterized by using elemental analysis,Fourier transform infrared (FTIR) spectrum,X-ray diffraction (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM) and thermogravimetric analysis (TGA).The XRD results demonstrated that MMT was successfully exfoliated with the disappearance of [001] peak.For the LDH,the peak [003] moved to a low angle and greatly weakened,indicating that LDH was successfully functionalized and completely intercalated or exfoliated.HDPE/layered nanocomposites were obtained between HDPE and different content of functional layered materials.The SEM and TEM results of nanocomposites showed the layered materials were well dispersed in the HDPE matrix,with a particle size of 100-200 nm.     

Accelerating effect of montmorillonite on oxidative degradation of polyethylene nanocomposites

Polyethylene, one of the most widely used packaging materials, can be made biodegradable by blending it with biopolymers such as starch and/or pro-oxidants which are metal complexes (e.g. cobalt stearate, cerium stearate). Recent studies on polyethylene degradation have found that addition of nanoclay, which is used as a filler in polymer composites mainly to enhance their mechanical properties, also increases their photo-oxidative degradation. The present study aims to investigate the degradation of low density polyethylene (LDPE) formulated with nanoclay and evaluate the effect of nanoclay compositions on the overall photo-oxidation process. Photo-oxidative aging of polyethylene and its nanocomposites were carried out in a QUV weathering tester for a maximum period of two weeks. The degradation progress was followed by monitoring the chemical changes of the samples using Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The results indicate that the incorporation of nanoclay significantly enhances the degradation of polyethylene.     

Preparation and properties of compatibilized LDPE/organo-modified montmorillonite nanocomposites

Nanocomposites based on low density polyethylene, containing of 3 or 6 wt.% of organo-modified montmorillonite nanoclay (MMT-ODA) and maleic anhydride grafted low density polyethylene as a compatibilizer were prepared by melt mixing and characterized. Exfoliation of silicate layers was achieved, as confirmed by X-ray diffraction and transmission electron microscopy. The compatibilized nanocomposites exhibit improved thermal stability in air as compared to neat polyethylene and nonexfoliated MMT-ODA composite. The crystallinity and crystallization kinetics of polyethylene matrix is not affected significantly by the presence of MMT-ODA clay. Drawability of the compatibilized nanocomposite with 6 wt.% of MMT-ODA is similar to neat polyethylene, whereas the composition having the same amount of MMT-ODA, without compatibilizer, exhibits poorer drawability. Scanning electron microscopy and density measurements of drawn samples indicate the existence of pores in noncompatibilized composite while no pores and good adhesion to MMT-ODA are found in compatibilized nanocomposites.     

Preparation, characterization and application of polymeric diols with comb-branched structure and their nanocomposites containing montmorillonites

The polymeric diols with comb-branched structure (CPD) and their nanocomposites containing montmorillonites (MMT) were prepared through three-step reaction on basis of molecular design. The effect of experimental parameters, such as molar mass of oligomer polyols, catalysts and MMT on conversion of -NCO group during polymerization was investigated by utilizing FTIR to measure content of -NCO group varied as reaction time. In addition, the structure of comb-branched polymeric diols was characterized by FTIR and ¹H NMR. The results show that the comb-branched chains contain reactive CC double bonds in CPD. The nature of dispersion of montmorillonites in CPD was characterized by X-ray diffraction. The results show that Na⁺-MMT is exfoliated and organo-MMT is intercalated in CPD via in-situ polymerization. Finally, the properties of water-borne polyurethane modified with CPD or CPD/2T-MMT nanocomposite were compared with those of common water-borne polyurethane, and the comb-branched chains and 2T-MMT improve the properties of water-borne polyurethane.     

Non-isothermal crystallization kinetics of exfoliated and intercalated polyethylene/montmorillonite nanocomposites prepared by in situ polymerization

Polyethylene/montmorillonite (PE/MMT) nanocomposites, one intercalated sample with higher MMT content and one exfoliated sample with lower MMT content, were prepared by in situ polymerization using MMT-supported metallocene as catalyst. Non-isothermal crystallization behaviors of these two nanocomposites were investigated and compared. The exfoliated sample exhibits higher crystallization temperature (T_c) than the neat PE, showing nucleation effect of MMT. The intercalated sample has lower T_c than the neat PE due to the confinement of MMT. It is observed that the intercalated sample has longer induction period and faster overall crystallization rate, indicating co-existence of suppression and nucleation effects in this sample. The Avrami plots show that the crystal growth of PE in the intercalated sample is two-dimensional, while it is three-dimensional in the exfoliated sample. The crystallization activation energy of the intercalated sample is slightly smaller than that of the exfoliated sample.     

A novel phosphorus-containing copolyester/montmorillonite nanocomposites with improved flame retardancy

A novel phosphorus-containing flame-retardant copolyester/montmorillonite nanocomposite (PET-co-HPPPA/O-MMT) was synthesized by the in situ intercalation polycondensation of terephthalic acid, ethylene glycol, and 2-carboxyethyl(phenylphosphinic) acid (HPPPA) with montmorillonite (O-MMT). The morphology was characterized by wide-angle X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The effects of organoclay on the thermal properties and melting behaviors of the nanocomposites were investigated by thermogravimetric analysis and differential scanning calorimetry. The flammability of the nanocomposites was characterized by the limiting oxygen index test and the UL-94 vertical test. The results showed that a small amount of organoclay was able to improve the thermal stabilities and the flame retardancy of PET-co-HPPPA copolyesters, and however there was no significant increase in the melting points of nanocomposites when the content of diethylene glycol was controlled as a certain value. The overall crystallization rate of the nanocomposites is greater than that of neat copolyester. The nanocomposites have better flame retardancy than PET-co-HPPPA.     

Synthesis and characterization of exfoliated MEH-PPV/clay nanocomposites by in situ polymerization

In this article, we demonstrate the synthesis of a conjugated polymer, poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene) (MEH-PPV) in the presence of organophilic montmorillonite (OMMT) and the properties of the MEH-PPV/OMMT composites produced herefrom. By controlling the reaction conditions, such as the ratio of monomeric precursors to montmorillonite, exfoliated MEH-PPV/OMMT nanocomposites were synthesized via in situ polymerization. These materials exhibit higher electroluminescent properties and enhanced performance of thermal stability than that of the pure polymer. Additionally, based on the solid-state ¹³C NMR measurement results, the possible origin of the optoelectronic property improvement is discussed from the point of view of segmental mobility.     

Preparation and characterization of waterborne polyurethane/attapulgite nanocomposites

In this paper, waterbrone polyurethane (WPU)/attapulgite (AT) nanocomposites have been prepared by direct emulsion blending. The WPU was synthesized from poly(tetramethylene glycol), 4,4-diphenylmethane diisocyanate, dimethylol butanic acid, and neutralized by triethylamine. SEM examination of fractured surfaces showed that AT particles were irregularly dispersed in the WPU matrix. FTIR analysis suggested no major chemical structural changed in the presence of a small amount of AT. DMA results showed that the storage modulus of WPU/AT nanocomposites was increased and the glass transition temperatures of both soft and hard segments shifted to higher temperature compared to the pristine WPU. Thermal resistance of the samples measured by TGA was improved with the addition of AT. The mechanical properties of the nanocomposites, examined by tensile tests, showed higher tensile strength and elongation at break than that of the pristine WPU.     

Effective preparation of montmorillonite/polyurethane nanocomposites by introducing cationic groups into the polyurethane main chain

In this study, the effect of introducing a small amount of cationic groups into the polymer main chain on the exfoliation of montmorillonite (MMT) and the physical properties of the subsequent MMT/polymer nanocomposites were investigated. As a matrix polymer, a polyurethane cationomer (PUC) containing 3 mol% of quaternary ammonium groups was synthesized and MMT/PUC nanocomposites containing various amounts of MMT were prepared by the solution intercalation method. From the WAXS and TEM analyses, it was found that the MMT layers were completely exfoliated and dispersed in the PUC matrix. The Young’s modulus of the MMT/PUC nanocomposites significantly increased with increasing MMT content, but their elongation at break and maximum stress were maintained at a level close to that of the PU only at an MMT content of 1 wt% and decreased as the content of MMT increased above this level. The phase separation of the MMT/PUC nanocomposites was retarded with increasing content of MMT, due to the strong interactions between the PUC chains and the exfoliated MMT layers. It was found that the presence of small amounts of cationic groups in the main chain of the matrix polymer was very effective in facilitating the preparation of the MMT/polymer nanocomposites.     

Study on rheological behaviour of poly(butylene terephthalate)/montmorillonite nanocomposites

Poly(butylene terephthalate)/montmorillonite composites (PBT/MMT) were prepared by melt intercalation and then investigated using X-ray diffractometer (XRD) and transmission electron microscope (TEM) as well as parallel plate rheometer. It was found that the composites had various phase morphologies with nanoscales and distinct behaviours of a percolation network structure under certain conditions. The linear viscoelastic region of the composites is much narrower than that for PBT matrix, the percolation threshold of the composites is near 3 wt.%, and the percolation network structure is not stable under a shear as well as in a quiescent annealing process. Moreover, PBT/MMT presents the nature of temperature independence of G′ versus G″ whether the internal percolated tactoids network formed or not. The magnitudes of the stress overshoots observed in the reverse flow experiments were strongly dependent on the rest time, which could be inferred that the ruptured network is reorganized under the quiescent annealing process. Furthermore, PBT/MMT shows a strain-scaling stress response to the startup of steady shear, indicating that the formation of the liquid crystalline-like phase structure in the nanocomposites may be the major drive force for the reorganization of the internal network.