Effect of epoxy resin on rheology of polycarbonate/clay nanocomposites

Polycarbonate/clay nanocomposites (PCNs) were prepared by melt intercalation using epoxy resin as a compatibilizer. The intercalated structure of PCNs was investigated using XRD and TEM. The linear and nonlinear dynamic rheological properties of PCNs were measured by the use of a parallel plate rheometer. The results reveal that the presence of epoxy influences rheological behavior of PCNs significantly. Addition of epoxy can improve dispersion of clay, enhancing the low-frequency viscoelastic responses; while high loadings of epoxy lead to a severe degradation of PC matrix, decreasing the high-frequency responses together with the plasticizing effect of excessive epoxy. Both of these two effects result in invalidity of time-temperature superposition. Moreover, all samples show high sensitivity to both the quiescent and large amplitude oscillatory shear (LAOS) deformation, despite enhanced percolation of tactoids due to the compatibilization of epoxy.     

Photoageing behaviour of epoxy nanocomposites: Comparison between spherical and lamellar nanofillers

The photochemical behaviour of a nanofilled epoxy resin has been studied. It has been shown that the filler content increases at the surface with irradiation time. Qualitative stiffness and adhesion measurements compare the surface properties of the filled and unfilled samples upon ageing. Depth profiling has been achieved by AFM nanoindentation and micro-FTIR. These two techniques allowed comparing stiffness and photooxidation of the aged samples. Both techniques showed an influence of nanofillers on thickness profiles. The relationship between the oxidation process and its consequences on the physical properties is explained taking into account oxygen permeability and light diffusion. Additionally, it has been shown that, whatever the content (5-10 wt%), the nature (silica or different organo-modified montmorillonites) or the shape of the filler (spherical or lamellar), the photoproducts were formed in comparable proportions and at similar rates as in the pristine matrix.     

Permanent antistatic phthalocyanine/epoxy nanocomposites - Influence of crosslinking agent, solvent and processing temperature

Cross-linked epoxy matrices containing small amounts of semi-conductive phthalocyanine (Phthalcon) nanoparticles were prepared using different crosslinking agents and processing temperatures. A starting mixture containing an optimum dispersion of these nanoparticles and with an almost equal and large Hamaker constant was always used. Nevertheless large differences in the relation between the volume conductivity σ_v and the particle concentration φ were found and this relation appeared to be sensitive to small changes in processing temperature and the application of a post-cure. Also the amine crosslinker chosen and the initial amount of solvent (catalyst) in the starting dispersion had a major effect. It was shown that these changes influence strongly the formation of and the final conductive fractal particle network morphology through the polymer matrix. During processing a local relaxation of the initially formed fractal particle network into another fractal particle network was often observed, which introduced or enlarged the amount of isolating material between the particles of the conductive network and changed the fractality and structure of the conductive backbone of the particle network. This local relaxation lowered the σ_v at each phthalcon concentration and enlarged φ_c by several orders of magnitude. The occurrence of local relaxation is dependent on the rate of viscosity change during the crosslinking of the polymer matrix components, the way the fractal conductive particle network is formed during processing (universal or non-universal) and the amount of solvent present. Local relaxation may even occur after the gel point of the polymer matrix. A severe post-cure may be needed to stop this local relaxation. To our knowledge local relaxation of a (fractal) nanoparticle network in a polymer matrix during processing is a new phenomenon, not reported before for polymer composites containing (conductive) nanoparticles.     

Layered silicate/epoxy nanocomposites: synthesis,characterization and properties

Novel epoxy‐clay nanocomposites have been prepared by epoxy and organoclays. Polyoxypropylene triamine (Jeffamine T‐403), primary polyethertriamine (Jeffamine T‐5000) and three types of polyoxypropylene diamine (Jeffamine D‐230, D‐400, D‐2000) with different molecular weight were used to treat Na‐montmorillonite (MMT) to form organoclays. The preparation involves the ion exchange of Na⁺ in MMT with the organic ammonium group in Jeffamine compounds. X‐ray diffraction (XRD) confirms the intercalation of these organic moieties to form Jeffamine‐MMT intercalates. Jeffamine D‐230 was used as a swelling agent for the organoclay and curing agent. It was established that the d₀₀₁ spacing of MMT in epoxy‐clay nanocomposites depends on the silicate modification. Although XRD data did not show any apparent order of the clay layers in the T5000‐MMT/epoxy nanocomposite, transmission electron microscopy (TEM) revealed the presence of multiplets with an average size of 5 nm and the average spacing between multiplets falls in the range of 100 Å. The multiplets clustered into mineral rich domains with an average size of 140 nm. Scanning electron microscopy (SEM) reveals the absence of mineral aggregate. Nanocomposites exhibit significant increase in thermal stability in comparison to the original epoxy. The effect of the organoclay on the hardness and toughness properties of crosslinked polymer matrix was studied. The hardness of all the resulting materials was enhanced with the inclusion of organoclay. A three‐fold increase in the energy required for breaking the test specimen was found for T5000‐MMT/epoxy containing 7 wt% of organoclay as compared to that of pure epoxy. Copyright © 2004 John Wiley & Sons, Ltd.     

Polymer dispersed liquid crystals: relation between formulation, electro-optical properties and morphology

Polymer Dispersed Liquid Crystal (PDLC) films investigated in this work are obtained by phase separation induced by photopolymerization of a homogeneous 'prepolymer/liquid crystal' mixture. We show a close relation between the formulation/conditions of preparation of the materials, their morphology and their electro-optical properties. The effect of the mutual compatibility of the prepolymer and the liquid crystal on film performances is investigated using 'model systems' that consist of pure components. Finally, both SALS experiments and a Fourier Transform procedure lead to a simple model in which LC domains are separated by polymer walls.     

Influence of processing technique on morphology and mechanical properties of PVC nanocomposites

This study aims to compare the influence of processing techniques and procedures on the morphology and mechanical properties of polyvinyl chloride (PVC) nanocomposites. PVC nanocomposites with 5 phr montmorillonite (MMT) clay were prepared on a two-roll mill or in a microcompounder, both were either processed once or via a masterbatch containing 20 phr MMT. The MMT was treated with non-ionic surfactants and analysed by thermo gravimetric analysis and X-ray diffraction prior to being added. The final composites were analysed and tested using X-ray diffraction, scanning and transmission electron microscopy (SEM/TEM), tensile test, and Charpy impact test. The dispersion was found to be best in the roll milled samples prepared via the masterbatch and the elongation at break and impact strength was also better for the roll milled samples. E-modulus and tensile strength, on the other hand, were significantly better for the microcompounded samples despite the larger particle size. This can be explained by a higher degree of orientation in these samples. Finally, it must be stated that the change in properties are not satisfactory. Although we see an increase in E-modulus, the decreased impact properties are not acceptable. The main reason for this is the lack of compatibility between the clay particles as observed by high resolution SEM.     

Boron nitride/epoxy resin nanocomposites: development,characterization and functionality

Journal of Thermal Analysis and Calorimetry - Polymer matrix composites with embedded ceramic nanoparticles receive not only enhanced scientific but also technological interest, due to their...     

A look inside the extruder: evolution of chemistry,morphology and rheology along the extruder axis during reactive processing and blending

A simple device was recently developed for fast sampling (within a few seconds) of representative melt samples (about 2 g) on a running extruder. An array of such devices has been mounted on a twin‐screw extruder. The goal of this study was to de‐black‐box reactive processing of polymers by studying some typical examples. ‐ Processing of polyolefins in the presence of peroxides: when the polymer is molten and the melt temperature is sufficiently high branching/cross‐linking of PE and degradation of PP occurs; the conversion follows a convex profile along the screw axis, which profile is similar to the exponential profile calculated for peroxide decomposition. ‐ Free‐radical grafting of maleic anhydride (MA) onto polyolefins: MA grafting onto PE and PP also follows a convex profile with branching/cross‐linking as parallel side reaction for PE and degradation for PP; for PE degradation of the formed grafted/cross‐linked gel is observed at the end of the extruder. ‐ Reactive blending of PA‐6 with EPM‐g‐MA: within a few seconds the in‐situ compatibilization reaction, resulting in PA‐6/EPM graft copolymers, is completed and the degree of rubber dispersion has changed from the mm to the sub‐μm range, regardless of the MA content of EPM‐g‐MA and the EPM‐g‐MA content of the blend; PA degradation occurs along the whole extruder.     

Oral processing,texture and mouthfeel: From rheology to tribology and beyond

Texture and mouthfeel arising from the consumption of food and beverages are critical to consumer choice and acceptability. While the food structure design rules for many existing products have been well established, although not necessarily understood, the current drive to produce healthy consumer acceptable food and beverages is pushing products into a formulation space whereby these design rules no longer apply. Both subtle and large scale alterations to formulations can result in significant changes in texture and mouthfeel, even when measurable texture-related quantities such as rheology are the same. However, we are only able to predict sensations at the initial stages of consumption from knowledge of material properties of intact food.Research is now on going to develop strategies to capture the dynamic aspects of oral processing, including: from a sensory perspective, the recent development of Temporal Dominance Sensation; from a material science perspective, development of new in vitro techniques in thin film rheology and tribology as well as consideration of the multifaceted effect of saliva. While in vivo, ex vivo, imitative and empirical approaches to studying oral processing are very insightful, they either do not lend themselves to routine use or are too complex to be able to ascertain the mechanism for an observed behaviour or correlation with sensory. For these reasons, we consider that fundamental in vitro techniques are vital for rational design of food, provided they are designed appropriately to capture the important physics taking place during oral processing. We map the oral breakdown trajectory through 6 stages and suggest a dynamic multi-scale approach to capture underlying physics. The ultimate goal is to use fundamental insights and techniques to design new food and beverages that are healthy yet acceptable to consumers.     

Morphology and rheology of polystyrene nanocomposites based upon organoclay

A correlation between morphology development and rheology of polystyrene nanocomposites based upon organophilic layered silicates (organoclay) such as fluoromicas was found as a function of the silicate modification. Organoclay was obtained by means of ion exchange of clay with protonated amine‐terminated polystyrenes with molar mass of M_n = 121 and 5 800 g/mol. Only when applying shear forces during melt compounding of organoclay modified with high molar mass polystyrene (PS), individual silicate platelets of 1 nm diameter and 600 nm length were obtained. Dispersions of such in‐situ formed nanoparticles with aspect ratio of 600 accounted for unique elastic properties observed in the low frequency range of the dynamic modulus, whereas organoclay modified with low molecular PS did not exfoliate and exhibited rheological behavior very similar to that of conventional fillers.     

Poly(3-hexylthiophene)/gold nanoparticle nanocomposites: relationship between morphology and electrical conductivity

The morphology and electrical properties of gold nanoparticles (AuNP) layer vacuum-deposited onto spin-cast thin films of poly(3-hexylthiophene), P3HT, were studied. The electrical conductivity was measured during temperature cycling and related to the morphology of the same composite structures, which was monitored by transmission electron microscopy (TEM) and extra-high resolution scanning electron microscopy (XHR SEM). Comparison to the analogous polystyrene/AuNP layers was made to distinguish the role of the polymer support on the morphology and electrical properties of the nanoparticles assembly. Gold deposited in a very thin layer formed a nanoparticles-like island structure with the morphology depending on the effective thickness of the deposited layer and on its subsequent thermal treatment. A stabilizing effect of the thiophene–gold interaction on the nanoparticles morphology was observed.     

Glass transition and relaxation behavior of epoxy nanocomposites

With advances in nanoscience and nanotechnology, there is increasing interest in polymer nanocomposites, both in scientific research and for engineering applications. Because of the small size of nanoparticles, the polymer–filler interface property becomes a dominant factor in determining the macroscopic material properties of the nanocomposites. The glass‐transition behaviors of several epoxy nanocomposites have been investigated with modulated differential scanning calorimetry. The effect of the filler size, filler loading, and dispersion conditions of the nanofillers on the glass‐transition temperature (T_g) have been studied. In comparison with their counterparts with micrometer‐sized fillers, the nanocomposites show a T_g depression. For the determination of the reason for the T_g depression, the thermomechanical and dielectric relaxation processes of the silica nanocomposites have been investigated with dynamic mechanical analysis and dielectric analysis. The T_g depression is related to the enhanced polymer dynamics due to the extra free volume at the resin–filler interface. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3849–3858, 2004     

Structural formation and physicomechanical characteristics of epoxy nanocomposites

The effect of nanofiller particles with various shapes and chemical nature on the physical and mechanical characteristics of the cured epoxy oligomer-based composites has been considered. As is established, the highest physical and mechanical characteristics of epoxy nanocomposites are enriched independently on the origin of the initial nanoparticles at the aggregate size of ~140–300 nm. Herewith, the strength increases by ~1.5 times, the elastic modulus is 2.5 times higher, and the shock viscosity (the crack resistance) of nanosystems in the optimum amount redoubles the shock viscosity.     

Preparation, thermal properties, morphology, and microstructure of phosphorus-containing epoxy/SiO2 and polyimide/SiO2 nanocomposites

A phosphorus-containing tri-ethoxysilane (dopo-icteos) reacting from the nucleophilic addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (dopo) and 3-(trieoxysilyl) isocyanate (icteos) was synthesized. The structure of dopo-icteos was confirmed by ¹H, ¹³C, ³¹P NMR and IR spectra. A triethylamine catalyzed mechanism for the dopo-icteos synthesis was proposed and verified by NMR spectra. The phosphorus-containing epoxy/SiO₂ and polyimide/SiO₂ nanocomposites were prepared from the in-situ curing of diglycidyl ether of bisphenol A (DGEBA)/4,4-diaminodiphenylmethane(DDM)/dopo-icteos, and imidization of poly(amic acid) of pyromellitic dianhydride (PMDA)/4,4′-oxydianiline (ODA)/dopo-icteos, respectively. The microstructure and morphology were investigated by ²⁹Si NMR, scanning electron microscope (SEM), EDS (Si and P mapping) analysis and atomic force microscope (AFM). The thermal properties, flame retardancy and dielectric properties of the organic-inorganic hybrids were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), limiting oxygen index (LOI), thermal gravimetric analysis (TGA) and dielectric analyzer (DEA).     

Extruder processing for nanoblends and nanocomposites

Structuring multiphase polymer materials to a micrometer scale (micro-structuration) is a facile engineering practice. However, structuring them to a nanometer scale (nano-structuration) is a formidable engineering challenge. In this paper, it is shown first why traditional extruder compounding processes only lead to micro-structuration and then how one may use the extruder type of mixer to structure multiphase polymer materials at a nano-meter scale to obtain nanostructured polymer blends (nanoblends) and nanostructured polymer composites (nanocomposites).     

Phase state and rheology of organosilicon nanocomposites with functionalized hyperbranched nanoparticles

The phase equilibrium in a system of linear polydimethylsiloxane–functionalized nanoparticles 1.2–2.2 nm in size with a core made of hyperbranched silica and a periphery of decyl groups has been studied by laser interferometry method. Phase diagrams of the studied systems fit the amorphous phase equilibrium with UCST increasing with the nanoparticle size. The mixtures present nanoparticle solutions in the linear polymer or emulsions of a saturated solution of one component in a saturated solution of other component depending on the components ratio. Dilute, concentrated, or highly concentrated dispersions show individual features of the rheological behavior. For each colloid chemical and phase states of mixtures, the viscosity and viscoelastic properties have been investigated in a wide temperature range. The obtained results have been compared with the previous data for mixtures of decylated nanoparticles and polyisobutylene.     

Synthesis,rheology, and morphology of nylon‐11/layered silicate nanocomposite

Exfoliated nylon‐11/layered silicate nanocomposites were prepared via in situ polymerization by dispersing organoclay in 11‐aminoundecanoic acid monomer. The original clay was modified by a novel method with 11‐aminoundecanoic acid. In situ Fourier transform infrared spectroscopy results show that stronger hydrogen bonds exist between nylon‐11 and organoclay than that of between nylon‐11 and original clay. The linear dynamic viscoelasticity of organoclay nanocomposites was investigated. Before taking rheological measurements, the exfoliated and intercalating structures and the thermal properties were characterized using X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis. The results show that the clay was uniformly distributed in nylon‐11 matrix during in situ polymerization of clay with 4 wt % or less. The presence of clay in nylon‐11 matrix increased the crystallization temperature and the thermal stability of nanocomposites prepared. Rheological properties such as storage modulus, loss modulus, and relative viscosity have close relationship with the dispersion favorably compatible with the organically modified clay. Comparing with neat nylon‐11, the nanocomposites show much higher dynamic modulus and stronger shear thinning behavior. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2161–2172, 2006     

Aspects on nanofibrillated cellulose (NFC) processing,rheology and NFC-film properties

This communication summarizes the salient features and mechanisms in high-pressure homogenization of wood fibres in order to make nanofibrillar cellulose (NFC).The energy-efficiency of delamination of fibres and the clogging tendency of fibres in high-pressure homogenizers/microfluidizers during delamination are critical and ways to alleviate these problems are reviewed.It is shown that the mechanical properties of NFC-films can be estimated from the Page equation. Usually, the evolution of the tensile strength properties of NFC-films increases with the extent of film delamination to reach a saturation value, which can be deduced from first principles using the Page equation.Finally, the evolution of the rheological features of NFC-gels and the barrier properties are reviewed and the estimation the nanofraction content in NFC-gels is being discussed.     

Flammability and morphology of HDPE/clay nanocomposites

High-density polyethylene/modified bentonite clay/polar compatibilizer nanocomposites were prepared through the melt intercalation process. The clay was organophilizated using different percentages of quaternary ammonium salt 100, 125, and 150 % based cation exchange capacity of the clay. The nanocomposites were prepared in a counter-rotating twin-screw extruder and then specimens were injection molded. For the evaluation of flammability of the test system was used for burning in the horizontal position according to the norm (Underwriters Laboratories, UL94HB) and to the method of cone calorimeter. The thermal behavior of nanocomposites was evaluated by thermogravimetry and X-ray diffraction techniques, and transmission electron microscopy were used to characterize the morphology and analyze the degree of expansion of the clays prepared and the degree of exfoliation of nanocomposites. It was observed that the percentage of ammonium salt and the compatibilizer polar influence on the final properties of the systems and consequently improving the thermal stability and reducing the flammability of the matrix.