Preparation and Characterization of Polycarbonate/Poly(propylene)/Attapulgite Ternary Nanocomposites with the Morphology of Encapsulation

Summary: Ternary nanocomposites based on polycarbonate (PC), poly(propylene) (PP), and attapulgite (AT) were prepared via the method of two‐step melt blending, by which the AT was blended with PP prior to compound with PC. Structure and properties of the ternary PC/PP/AT nanocomposites were investigated. The degradation of PC triggered by AT during direct blending process can be inhibited effectively by using two‐step melt blending. It was found that the morphology of encapsulation structure like sandbag was formed in PC matrix, where PP encapsulated AT fibrillar single crystals. DSC experiments showed that in PC/PP/AT ternary nanocomposites, AT had a strong heterophase nucleation effect on PP, resulting in the enhancement of crystallization degree and the crystallization temperature of PP. DMA and mechanical property results showed that the ternary nanocomposites exhibited good balanced toughness and stiffness.

TEM photograph of PC/PP/AT ternary nanocomposite.     

Bio‐Based Nanocomposites from Corn Oil and Functionalized Organoclay Prepared by Cationic Polymerization

A reactive organic montmorillonite clay (VMMT), modified with (4‐vinylbenzyl) triethylammonium cations, has been prepared and used as a nanofiller to reinforce a corn‐oil‐based polymer resin. The polymer resin was prepared by the cationic polymerization of conjugated corn oil, styrene and divinylbenzene, using boron trifluoride diethyl etherate modified with Norway fish oil as the initiator. The results indicate that the VMMT is intercalated in the corn‐oil‐based polymer resins. When compared with the pure polymers, these novel nanocomposites reinforced with 2 to 3 wt.‐% VMMT exhibit significant improvements in modulus, strength, strain and toughness. Furthermore, incorporating VMMT into the corn‐oil‐based polymer matrix also leads to improved thermal stability of the nanocomposites over the pure resins of up to 400 °C.

     

Foam Processing and Cellular Structure of Polycarbonate‐Based Nanocomposites

Summary: Via a batch process in an autoclave, foam processing of intercalated PC/clay nanocomposites, having different amounts of clay, has been conducted using supercritical CO₂ as a foaming agent. The cellular structures obtained from various foaming temperature‐CO₂ pressure ranges were investigated by SEM. The incorporation with nanoclay‐induced heterogeneous nucleation occurs because of a lower activation energy barrier compared with homogeneous nucleation as revealed by the characterization of the interfacial tension between bubble and matrix. The controlled structure of the PCCN foams changed from microcellular (d ? 20 µm and N_c ? 1.0 × 10⁹ cells · cm^?3) to nanocellular (d ? 600 nm and N_c ? 3.0 × 10¹³ cells · cm^?3). The mechanical properties of PCCN foams under compression test were discussed.

TEM micrograph for the structure of the cell wall foamed at 160 °C.     

New Polylactide/Layered Silicate Nanocomposites, 6

The measurement of rheological properties of any polymeric material under molten state is crucial to gain fundamental understanding of the processability of that material. In the case of polymer/layered silicate nanocomposites, the measurements of rheological properties are not only important to understand the knowledge of the processability of these materials, but is also helpful to find out the strength of polymer‐layered silicate interactions and the structure‐property relationship in nanocomposites. This is because rheological behaviors are strongly influenced by their nanoscale structure and interfacial characteristics. In order to get this knowledge in the case of polylactide/montmorillonite nanocomposites, we have studied melt rheological properties of these materials in detail. On the basis of rheological data, we have conducted foam processing of pure polylactide and one representative nanocomposite by a newly developed pressure cell technique using carbon dioxide as a physical‐blowing agent.

The time variation of the elongational viscosity of one of the intercalated polylactide/montmorillonite nanocomposites.     

Cover Picture: Macromol. Mater. Eng. 8/2005

Summary: Poly(butylene succinate‐co‐adipate) (PBSA) and organically modified montmorillonite (OMMT) nanocomposites of three different compositions were prepared by melt‐extrusion in a batch mixer. The structure of the nanocomposites was studied using X‐ray diffraction (XRD) and transmission electron microscopy (TEM) that revealed a coexistence of exfoliated and intercalated silicate layers dispersed in the PBSA matrix, regardless of the silicate loading. The degree of crystallinity of PBSA decreases with the addition of OMMT platelets. Dynamic mechanical analysis revealed remarkable increase in flexural storage modulus when compared with that of neat PBSA. Tensile property measurements exhibit substantial increase in stiffness with simultaneous increase in elongation at break of nanocomposites as compared to that of neat PBSA. The effect of clay loading on the melt‐state linear viscoelastic behavior of mixed intercalated/exfoliated nanocomposites was also investigated.

Elongation at break of compression molded annealed samples of neat PBSA and various PBSACNs.     

Heat Induced Structure Modifications in Polymer‐Layered Silicate Nanocomposites

Summary: The success of the use of layered silicates in polymer nanocomposites, to improve physical and chemical properties is strictly related to a deeper knowledge of the mechanistic aspects on which the final features are grounded. This work shows the temperature induced structural rearrangements of nanocomposites based on poly[ethylene‐co‐(vinyl acetate)] (EVA) intercalated‐organomodified clay (at 3–30 wt.‐% silicate addition) which occur in the range between 75 and 350 °C. In situ high temperature X‐ray diffraction (HT‐XRD) studies have been performed under both nitrogen and air to monitor the modifications of the nanocomposite structure at increasing temperatures under inert/oxidative atmosphere. Heating between 75 and 225 °C, under nitrogen or air, causes the layered silicate to migrate towards the nanocomposite surface and to increase its interlayer distance. The degradation of both the clay organomodifier and the VA units of the EVA polymer seems to play a key role in driving the evolution of the silicate phase in the low temperature range. The structural modifications of the nanocomposites in the high temperature range (250–350 °C), depended on the atmosphere, either inert or oxidizing, in which the samples were heated. Heating under nitrogen led to deintercalation and thus a decrease of the silicate interlayer space, whereas exfoliation was the main process under air leading to an increase of the silicate interlayer space.

Heat induced structural modification of EVA‐clay nanocomposite under nitrogen and air.     

Direct Melt Extrusion Processing of Nylon 6/Clay Nanocomposites Based on Pristine Montmorillonite

Summary: An original direct melt extrusion processing of nylon 6/clay nanocomposites was reported based on pristine (Na⁺‐based) montmorillonite as well as a simple approach using a typical two‐screw extruder. By the application of intercalation agents as the thermodynamic assistants, this method is as an appropriate procedure for industrialized manufacture together with much lowered production cost. Interestingly enough, the synergistic effects of montmorillonite with other inorganic particulates was observed for the first time here.

X‐ray diffraction patterns of pristine MMT and nylon 6/MMT composites with grouped intercalation agents.     

Poly(propylene)/Clay Nanocomposites Prepared by Reactive Compounding with an Epoxy Based Masterbatch

Summary: Poly(propylene) (PP)/clay nanocomposites have been prepared via a novel reactive compounding approach, in which an epoxy based masterbatch consisting of 20 wt.‐% clay was introduced to poly(propylene) with the aid of a maleic anhydride grafted PP (MAPP). The masterbatch was prepared using a recently developed “slurry compounding” technique. After melt compounding, most clay particles have been exfoliated and dispersed into small stacks with several clay layers. WAXD data shows that the dispersion of clay is better at low clay content or high MAPP content. Due to the novelty of the preparation process and complication of the system, the tensile properties of nanocomposites exhibit some unique tendencies with varying the content of MAPP or masterbatch. It is believed that the yield strength and Young's modulus can be dramatically improved after minimizing the excess of unreacted epoxy and optimizing the dispersion of clay.

TEM micrograph of PP/clay nanocomposites prepared with epoxy based masterbatch.     

Effect of Comonomer Content on the Behavior of Propylene Copolymer/Compatibilizer/Clay Nanocomposites

A set of isotactic propylene copolymers with either 1‐hexene or 1‐octadecene were synthesized using a metallocene catalyst, and their nanocomposites with 5 wt.‐% of clay and 15 wt.‐% of compatibilizer were prepared and characterized. Clay intercalation and dispertion depend on the comonomer content in the matrix which improves at high short‐chain‐branching levels. The presence of both clay and compatibilizer increased the crystallization temperature of the matrix. A strong correlation between the elastic modulus of the matrix and its relative increase in the nanocomposite was observed. By adding clay and compatibilizer to the copolymer, the modulus can be increased by a factor of two. The results open new perspectives in the understanding of the effect of polyolefin topology on nanocomposites properties.

     

Intercalated PS/Na+‐MMT Nanocomposites Prepared by Ultrasonically Initiated In Situ Emulsion Polymerization

Summary: A new technique, ultrasonically initiated in situ emulsion polymerization, was employed to prepare intercalated polystyrene/Na⁺‐MMT nanocomposites. FTIR, XRD, and TEM results confirm that the hydrophobic PS can easily intercalate into the galleries of hydrophilic montmorillonite via ultrasonically initiated in situ emulsion polymerization, taking advantages of the multi‐effects of ultrasonic irradiation, such as dispersion, pulverization, activation, and initiation. Properly reducing SDS concentration is beneficial to widen the d‐spacing between clay layers. However, the Na⁺‐MMT amount has little effect on the d‐spacing of nanocomposites. The glass transition temperature of nanocomposites increased as the percentage of clay increased, although the average molecular weight of PS decreased, and the decomposition temperature of the 1obtained nanocomposites moves to higher temperature.

TEM of PS/Na⁺‐MMT nanocomposite prepared by ultrasonically initiated in situ emulsion polymerization.     

Modification of Polycarbonate and Glycol Modified Poly(ethylene terephthalate) by Addition of Silica‐Nanoparticles Grafted with SAN Copolymer Using “Classical” and ARGET ATRP

This study presents a nanocomposite manufacturing route starting from non‐functionalized nanosilica and SAN surface modification via “grafting from” ATRP up to processing of transparent polycarbonate and glycol modified poly(ethylene terephthalate) nanocomposites. Synthesis limitations of low molecular weight graft SAN derived from “classical” ATRP are overcome by employment of the emerging ARGET ATRP. Mechanical investigations of polycarbonate and glycol modified poly(ethylene terephthalate) nanocomposites present up to 80% enhancement of creep performance and additionally 70% enhancement against wear abrasion for glycol modified poly(ethylene terephthalate) nanocomposites. Strength and tensile modulus are only moderately influenced by the addition of nanoparticles. Morphological studies confirm that the present modification route is able to create uniform dispersions of single particles and small particle aggregates in polymer matrices.

     

Preparation of Polystyrene/Clay Nanocomposites by Free‐Radical Polymerization in Dispersion

Fully exfoliated PS/clay nanocomposites were prepared via FRP in dispersion. Na‐MMT clay was pre‐modified using MPTMS before being used in a dispersion polymerization process. The objective of this study was to determine the impact of the clay concentrations on the monomer conversion, the polymer molecular weight, and the morphology and thermal stability of the nanocomposites prepared via dispersion polymerization. DLS and SEM revealed that the particle size decreased and became more uniformly distributed with increasing clay loading. XRD and TEM revealed that nanocomposites at low clay loading yielded exfoliated structures, while intercalated structures were obtained at higher clay loading.

     

Oxygen Barrier Properties of Poly(ethylene terephthalate) Nanocomposite Films

Nanocomposites of poly(ethylene terephthalate) and two different montmorillonite‐based organoclays were prepared by a co‐rotating twin screw extruder. Dispersion of nanoclays in the polymer matrix was examined by TEM and XRD. Nanocomposites with lower content of organoclay showed exfoliated morphology while by increasing the amount of organoclay the intercalated morphology was more prevalent. Both organoclays had a good intercalation with PET and were uniformly dispersed within the polymer. Oxygen permeability of thin films of nanocomposites showed that the nanocomposites had better oxygen barrier properties than the neat PET. Tensile and impact properties of the nanocomposites also were measured.

     

The Effect of Clay Loading on the Morphology and Properties of Poly(styrene‐co‐butyl acrylate)/Clay Nanocomposites

This paper investigates the effect of both the clay loading and the monomer feed rate on the morphology and properties of poly(styrene‐co‐butyl acrylate)‐clay nanocomposites prepared in emulsion polymerization. Analysis by X‐ray diffraction (XRD) and transmission electron microscopy (TEM) of the nanocomposites prepared by batch polymerization showed that the polymer clay nanocomposites (PCNs) with 1–3 wt.‐% clay loading resulted in intercalated structures, while exfoliated structures were obtained at 10 wt.‐% clay loading. The polymerization was also carried out with semi‐batch polymerization. The morphology, thermal stability, and mechanical properties of nanocomposites obtained were found to be more strongly dependent on the clay/polymer ratio than the monomer feed rate.

     

Preparing Exfoliated MMT/Polymer Nanocomposites by Combined Latex Compounding and Spray‐Drying

A facile and easily industrialized approach for preparing highly dispersed MMT/polymer nanocomposites is developed by combining the latex compounding method and a spray‐drying process. Clay particles are successfully delaminated into layers, and layer re‐stacking is effectively prevented. HR‐TEM and XRD results confirm that MMT layers achieve exfoliated or nearly exfoliated dispersion in both MMT/styrene‐butadiene rubber and MMT/PS nanocomposites. Compared with melt‐blended MMT/SBR composites, MMT/SBR nanocomposites prepared by this new strategy exhibit extremely high dynamic modulus.

     

Combining In‐Situ Organic Modification of Montmorillonite and the Latex Compounding Method to Prepare High‐Performance Rubber‐Montmorillonite Nanocomposites

Summary: To improve the interfacial interaction in MMT‐SBR nanocomposites, one type of UOAC was introduced to in‐situ modified MMT before latex compounding with SBR. The influence of the UOAC/MMT ratio on the structure and properties of MMT/SBR nanocomposites were carefully studied by XRD, TEM, and mechanical testing. It was found that through the in‐situ organic modification, a rubber‐intercalated structure of MMT was obtained in the nanocomposites, and the amount of rubber‐intercalated structure strongly depended on the UOAC/MMT ratio. The tensile strength of MMT‐SBR nanocomposites was enhanced dramatically from 4 to 18 MPa by in‐situ organic modification of MMT.

Stress‐strain diagram of SBR/clay nanocomposites.     

Nanoindentation and Morphological Studies of Epoxy Nanocomposites

Summary: This paper investigates the mechanical properties of the epoxy–organoclay nanocomposites by the nanoindentation technique. The nanocomposites were prepared by in situ polymerization and a mixture of exfoliated and intercalated composites structure was obtained as evidenced by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The hardness, elastic modulus, and the creep behavior of the nanocomposites have been evaluated as a function of clay concentration. It has been found that incorporation of 7.5 wt.‐% of clay nanofiller enhances the elastic modulus and hardness of the epoxy matrix by about 20 and 6%, respectively. The elastic modulus data calculated from indentation experiments are comparable with those obtained from a tensile test. An optimum clay loading level was found to be 2.5 wt.‐% to maximum enhance the creep resistance of the epoxy matrix. The lowered creep resistance with higher clay loading could be due to the reduced crosslinking density near the clay surface caused by the plasticizing effect from the pending of alkyl ammonium chains on the clay surface. An attempt has been made to correlate the fracture toughness of the nanocomposites with the ratio of modulus to hardness obtained from nanoindentation experiments.

Ratio of modulus to hardness (E/H) and the fracture toughness (K_IC) versus clay loading for the epoxy nanocomposites.     

Effects of Temperature and Surfactants on the Equilibrium Swelling Behavior of Poly[acrylamide‐co‐(itaconic acid)] Hydrogels

Summary: The swelling equilibrium of poly(acrylamide) [PAAm] and poly[acrylamide‐co‐(itaconic acid)] [P(AAm/IA)] hydrogels was studied as a function of temperature and IA content in aqueous solutions of surfactants: sodium dodecyl sulfate (SDS, anionic) and hexadecyltrimethylammonium bromide (HTAB, cationic). P(AAm/IA) hydrogels in water exhibited reentrant conformational transitions depending on temperature, whereas PAAm hydrogels were not affected with the change of temperature. The equilibrium‐volume‐swelling ratio of P(AAm/IA) hydrogels increased sharply in SDS solutions, with an increase of the mole percent of IA. However, in HTAB solution, the equilibrium‐volume‐swelling ratio of these hydrogels decreased with an increase of IA content.

The equilibrium volume‐swelling ratios of the hydrogels in water shown as a function of temperature.     

Metallized Organoclays as New Intermediates for Aqueous Nanohybrid Dispersions,Nanohybrid Catalysts and Antimicrobial Polymer Hybrid Nanocomposites

Summary: The chemical metallization of aqueous bentonite dispersions afforded stable aqueous hybrid nanoparticle dispersions containing simultaneously dispersed sodium bentonite nanoplatelets together with bentonite supported silver, palladium, or copper nanoparticles with average metal nanoparticle diameters varying between 14 and 40 nm. Such aqueous bentonite/metal hybrid nanoparticle dispersions were blended with cationic PMMA latex to produce PMMA hybrid nanocomposites containing exfoliated polymer‐grafted organoclay together with bentonite supported metal nanoparticles. This dispersion blend formation was investigated with respect to the role of nanostructure formation and mechanical properties. Palladium/bentonite hybrid dispersions were used as catalysts for hydrogenation reactions and the electroless plating of copper. In contrast to the conventional organoclay nanocomposites, the PMMA hybrid nanocomposites, containing simultaneously dispersed organoclay nanoplatelets together with organoclay supported silver nanoparticles, exhibited high antimicrobial activity against the ubiquitous bacterium Staphylococcus aureus, even at low silver content.

Preparation of a polymer hybrid nanocomposite.     

Preparation and Combustion Properties of Flame Retardant Nylon 6/Montmorillonite Nanocomposite

Flame retardant Nylon 6 (PA6)/montmorillonite (MMT) nanocomposites have been prepared using direct melt intercalation technique by blending PA6, organophilic clay and conventional fire retardants, such as the melamine cyanurate (MCA) and the combination of decabromodiphenyl oxide (DB) and antimony oxide (AO). Their morphology and combustion properties are characterized by XRD, transmission electron microscopy (TEM), UL‐94 test and Cone Calorimeter experiments. The flame retardant nanocomposites with MCA or DB and AO show lower heat release rate (HRR) peak compared to that of conventional flame retardant PA6. Meanwhile, the synergetic effect was studied between clay and DB‐AO.

TEM of PA‐n nanocomposite.