Understanding and controlling the structure of polypropylene/layered silicate nanocomposites

The miscibility and structure in polypropylene/layered silicate nanocomposites is systematically investigated utilizing a maleic-anhydride grafted polypropylene with a low degree of functionalization acting as the compatibilizer. The morphology of the hybrids can be modified from phase separated to almost completely exfoliated in a controlled way by varying the ratio α of the compatibilizer to the organophilized clay; this ratio α is found to be the most important parameter in determining the final structure whereas exfoliated structures can be obtained for α values of 9 or higher. Furthermore, utilization of a “masterbatch” procedure can enhance the degree of exfoliation even for smaller values of α; in that case, polypropylene is essentially mixed with the already dispersed “hairy” platelets. Investigation of the thermal stability of the micro- and nanocomposites shows that high degree of exfoliation is vital in increasing the temperature that the polymer starts to degrade. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2683–2695, 2008     

Estimation of interphase thickness and properties in PP/layered silicate nanocomposites

Nanocomposites were prepared from sodium montmorillonite (NaMMT) and organoclays (OMMT) with different particle sizes as a function of silicate content. Composite structure was characterized by various methods including X-ray diffraction (XRD), scanning electron microscopy (SEM) and rheology. Model calculations were carried out to estimate the thickness and yield stress of the interphase forming in the composites. The results proved the formation of an interphase, but the determination of interphase properties was hampered by several factors. First of all, the particle size of the filler changed quite considerably in PP/OMMT composites in spite of earlier observations and expectations. Particle characteristics changed even further when a relatively small amount (5 vol.%) of functionalized polymer (MAPP) was added to the composite. As a consequence, the estimation of the contact surface between the silicate and the polymer became extremely difficult. In spite of the uncertainties overall values of interphase properties were obtained using the results of all composites prepared. The prediction for the average thickness of the interphase is 0.23 μm and we obtained 51.2 MPa for interphase yield stress, but this estimate neglects the different interactions developing in composites containing the uncoated and the modified silicate, respectively.     

Polyolefin,olefin copolymers and polyolefin polyblend nanocomposites

This paper reviews recent studies done in academia or industrial laboratories on polymer nanocomposites based on various type of polyolefins like homopolymers, copolymers and polyblends reinforced with various mineral (montmorillonite, bentonite, closite, laponite, layered double hydroxide, etc.) carbon based (graphite, carbon nanotubes, carbon nanofibers, exfoliated graphite, graphene, carbon black, etc.) nanofillers. The review covers their preparation, their mechanical, thermal, flammability, gas barrier capability, electrical, dielectrical, antibacterial characteristics and their potential applications like low weight structural materials, part of optical devices, thermal interface materials, electric and electromagnetic components, absorption, antibacterial materials, etc.     

A novel comparative study of different layered silicate clay types on exfoliation process and final nanostructure of trifunctional epoxy nanocomposites

The effect of three different organically modified layered silicate clays (Nanomer I.30E, Cloisite 30B and Nanofil SE 3000) on the exfoliation process and on the thermal properties and nanostructure of cured trifunctional epoxy resin based nanocomposites was studied. Optical microscopy showed that the best and poorest qualities of clay distribution in the epoxy matrix were obtained with Nanofil SE 3000 and Nanomer I.30E, respectively. However, the isothermal differential scanning calorimetry scans show that, of the three systems, it is only the Nanomer clay that promotes intra-gallery reaction due to homopolymerisation, appearing as an initial rapid peak prior to the cross-linking reaction. This rapid intra-gallery reaction is not present in the curing curve for the Cloisite and Nanofil systems. This fact implies that the fully cured nanostructure of the Cloisite and Nanofil system is poorly exfoliated, which is confirmed by small angle X-ray scattering which shows a scattering peak for these systems at around 2.53°, corresponding to about 3.5 nm d-spacing.     

Swelling, intercalation, and exfoliation behavior of layered ruthenate derived from layered potassium ruthenate

The intercalation chemistry of a layered protonic ruthenate, H_0.2RuO_2.1·nH₂O, derived from a layered potassium ruthenate was studied in detail. Three phases with different hydration states were isolated, H_0.2RuO_2.1·nH₂O (n=0, 0.5, 0.9), and its reactivity with tetrabutylammonium ions (TBA⁺) was considered. The layered protonic ruthenate mono-hydrate readily reacted with TBA⁺, affording direct intercalation of bulky tetrabutylammonium ions into the interlayer gallery. Fine-tuning the reaction conditions allowed exfoliation of the layered ruthenate into elementary nanosheets and thereby a simplified one-step exfoliation was achieved. Microscopic observation by atomic force microscopy and transmission electron microscopy clearly showed the formation of unilamellar sheets with very high two-dimensional anisotropy, a thickness of only 1.3±0.1 nm. The nanosheets were characterized by two-dimensional crystallites with the oblique cell of a=0.5610(8) nm, b=0.5121(6) nm and γ=109.4(2)° on the basis of in-plane diffraction analysis.     

Thermo-oxidative stability of polypropylene/layered silicate nanocomposites

Several series of experiments were carried out to check the effect of components on the stability of PP/layered silicate nanocomposites. The amount of organophilic montmorillonite (OMMT) changed between 0 and 6, while that of maleated polypropylene (MAPP) between 0 and 50 vol%. The composites were prepared in an internal mixer at 190 °C. Mixing speed and time were changed to study the effect of processing conditions on stability. The structure of the samples was characterised by various methods, while stability by the induction time of oxidation (OIT), the onset temperature of degradation (OOT) and by colour. Contrary to numerous claims published in the literature, which indicate the positive effect of layered silicates on the stability of polymer nanocomposites, our results clearly proved that both OMMT and MAPP accelerate degradation during processing and deteriorate the properties of PP composites. Residual stability decreases drastically with increasing amounts of both components, chain scission leads to the decrease of viscosity and to inferior strength and deformability. In spite of expectations, the effect of the components is independent of each other. Discoloration is caused mainly by the inherent colour of the filler and it decreases with increasing exfoliation. The most probable reason for decreased stability is the reaction of the components with the stabilisers, but this explanation needs further verification. Processing conditions influence degradation considerably, increasing shear rate and longer residence times lead to more pronounced degradation. The basic stabilization of commercial grade polypropylenes is insufficient to protect the polymer against degradation and without additional stabilization processing under normal conditions results in products with inferior quality.     

Rheology of polymer layered silicate nanocomposites

Layered silicate based polymer nanocomposites have gained significant technological interest because of the recent commercialization of nylon 6 and polypropylene based materials. Aside from the natural interests in understanding and improving the processing of these hybrids, viscoelastic measurements have also proven to be a sensitive tool to probe the mesoscale structure and the strength of polymer–nanoparticle interactions.     

Isothermal crystallization of layered silicate/starch-polycaprolactone blend nanocomposites

The isothermal crystallization behavior of layered silicate/starch-polycaprolactone blend nanocomposites was studied by means of differential scanning calorimetry (DSC) measurements. The theoretical melting point was higher for the matrix than for nanocomposites. At low clay concentration, the induction time decreased and the overall crystallization rate increased acting as nucleating agent whereas at higher concentrations became retardants. Classical Avrami equation was used to analyze the crystallization kinetic of these materials. n values suggested that clay not only affected the crystallization rate but also influenced the mechanism of crystals growth. An Arrhenius type equation was used for the rate constant (k). Models correctly reproduced the experimental data.     

Fully exfoliated layered silicate epoxy nanocomposites

Fully exfoliated layered silicate epoxy nanocomposites are reported in this article. The processing route that resulted in these fully exfoliated layered silicate epoxies is based on a combination of high‐shear mixing in the presence of acetone and ultrasonication. Homomogeneous and random dispersion of the individual silicate nanolayers in the epoxy is confirmed through transmission electron microscopy images spanning low to high magnification as well as by X‐ray diffraction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3981–3986, 2004     

Evaluation of ammonium terminated PMMA as compatibilizers for monomer casting polyamide6/clay nanocomposites

The compatibilization effects provided by ammonium terminated PMMA(PMMA‐t‐NH₃⁺) on monomer casting polyamide6 (MCPA6)/clay(pristine sodium montmorillonite) nanocomposites were studied in this article. PMMA‐t‐NH₃⁺ used in this study was prepared by radical polymerization using 2‐aminoethanethiol hydrochloride as chain transfer agent. MCPA6/clay/PMMA‐t‐NH₃⁺ nanocomposites were prepared by in situ anionic ring‐opening polymerization of ε‐caprolactam. X‐ray diffraction and transmission electron microscopy plus rheological measurement were used to characterize those nanocomposites. The results indicated that PMMA‐t‐NH₃⁺ would be a good compatibilizer for this system. With PMMA‐t‐NH₃⁺ content increasing, a better dispersion of clay was successfully achieved in the MCPA6 matrix. Furthermore, analysis using differential scanning calorimetry indicated that well dispersed clay layers limited the mobility of the MCPA6 molecule chains to crystallize, reduce the crystalline degree, and favor the formation of the γ‐crystalline form of the MCPA6 matrix. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1802–1810, 2008     

Predictive modeling of creep in polymer/layered silicate nanocomposites

A predictive creep model is developed which uses the properties of matrix and reinforcement to predict the creep of polymer/layered silicate nanocomposites. Up to this point, primarily empirical creep models such as Findley and Burgers models have been used for creep of polymer/clay nanocomposites. The proposed creep model is based on the elastic-viscoelastic correspondence principle and a stiffness model of these nanocomposites. Also, the added stiffness of polymeric matrix due to the constraining effect of layered silicates on polymer chains in the nanocomposite is considered by a parameter termed constraint factor. The results of the proposed model show good agreement with experimental creep data for different clay contents, stresses and temperatures. Comparing the model predictions with experimental data, a logical relationship between the method of processing and the constraint factor is discovered which shows that in-situ polymerization can be more efficient for improving creep resistance of polymer/layered silicate nanocomposites relative to melt processing.     

A new approach for the synthesis of layered niobium sulfide and restacking route of NbS2 nanosheet

We have developed a new process for the synthesis of a layered niobium sulfide that involves heating K₄Nb₆O₁₇·3H₂O with a H₂S/N₂ gas mixture. It was confirmed that heating the starting layered oxide at 750 °C for 10 h under the gas flow yielded a highly crystalline, single-phase K_0.34(H₂O)_0.7NbS₂. The layered sulfide slabs had a large plate-like shape. Potassium ions in the interlayer of K_0.34(H₂O)_0.7NbS₂ could be exchanged with protons by stirring in 2 M H₂SO₄. It was found that the proton in the proton-exchanged form can be easily exchanged with other cations. The proton-exchanged form was exfoliated into NbS₂ nanosheets by ultrasonication in water. According to the atomic force microscopy (AFM) images, NbS₂ nanosheets had a thickness of around 4 Å, which roughly corresponded to the thickness of a single NbS₂ host layer. NbS₂ nanosheets could be restacked with the intercalation of Eu³⁺ or tetrabutylammonium ions by an electrostatic self-assembly deposition (ESD) technique.     

Nanostructure and properties of polysiloxane‐layered silicate nanocomposites

The relationship between nanostructure and properties in polysiloxane layered silicate nanocomposites is presented. Solvent uptake (swelling) in dispersed nanocomposites was dramatically decreased as compared to conventional composites, though intercalated nanocomposites and immiscible hybrids exhibited more conventional behavior. The swelling behavior is correlated to the amount of bound polymer (bound rubber) in the nanocomposites. Thermal analysis of the bound polymer chains showed an increase and broadening of the glass‐transition temperature and loss of the crystallization transition. Both modulus and solvent uptake could be related to the amount of bound polymer formed in the system. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1595–1604, 2000     

Synthesis and barrier properties of poly(ε-caprolactone)-layered silicate nanocomposites

A new polymer-ceramic nanocomposite has been synthesized consisting of well-dispersed, two-dimensional layers of an organically modified mica-type silicate (MTS) within a degradable poly(ε-caprolactone) matrix. A protonated amino acid derivative of MTS was used to promote delamination/dispersion of the host layers and initiate ring-opening polymerization of ε-caprolactone monomer, resulting in poly(ε-caprolactone) chains that are ionically bound to the silicate layers. The polymer chains can be released from the silicate surface by a reverse ion-exchange reaction and were shown to be spectroscopically similar to pure poly(ε-caprolactone). Thick films of the polymer nanocomposite exhibit a significant reduction in water vapor permeability that shows a linear dependence on silicate content. The permeability of nanocomposite containing as low as 4.8% silicate by volume was reduced by nearly an order of magnitude compared to pure poly(ε-caprolactone). © 1995 John Wiley & Sons, Inc.     

Morphology and properties of polypropylene/ethylene–octene copolymer/clay nanocomposites with double compatibilizers

The influence of nanoclay on the morphology and properties of the polypropylene (PP)/ethylene–octene block copolymer (EOC) blend with double compatibilizers of maleated PP (PP‐g‐MA) and maleated EOC (EOC‐g‐MA) was investigated and compared with the nanocomposites containing either PP‐g‐MA or EOC‐g‐MA as a compatibilizer. X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy were utilized for morphological characterization in conjunction with dynamic mechanical thermal analysis, mechanical testing, and rheological evaluation of these nanocomposites. The results suggested that in the nanocomposite including both compatibilizers of PP‐g‐MA and EOC‐g‐MA, clay was dispersed as a mixed structure of intercalation and exfoliation in both phases of the polymer blend. Comparing the mechanical properties of the studied nanocomposite with nanocomposites of PP/EOC/PP‐g‐MA/clay and PP/EOC/EOC‐g‐MA/clay also indicated that the nanocomposite containing mixed compatibilizers displayed higher tensile modulus, tensile strength, and complex viscosity because of the better dispersion of clay in both phases. The results also confirmed the increased structural stability and reduced dispersed phase size of PP/EOC/PP‐g‐MA/EOC‐g‐MA blend in the presence of clay that proposed the compatibilization role of clay in this nanocomposite. Copyright © 2014 John Wiley & Sons, Ltd.     

Preparation and properties of aramid/layered silicate nanocomposites by solution intercalation technique

Polymer—clay nanocomposites were synthesized from aromatic polyamide and organoclay using the solution intercalation technique. Polyamide chains were produced through the reaction of 4,4′‐oxydianiline (ODA) and isophthaloyl chloride (IPC) in N, N′‐dimethyl acetamide, using stoichiometry yielding chains with carbonyl chloride end groups. The intercalation of sodium montmorillonite (Na‐MMT) was carried out using p‐phenylene diamine as a swelling agent through an ion exchange reaction. Different concentrations of organoclay were blended with the polyamide solution for complete dispersion of clay throughout the matrix. The resulting composite films were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), mechanical testing, thermogravimetry (TGA), differential scanning calorimetry (DSC) and water absorption measurements. The XRD pattern and morphology of the nanocomposites revealed the formation of exfoliated and intercalated clay platelets in the matrix. The film containing a small amount of clay was semitransparent and had a tensile strength of the order of 70 MPa (relative to the 52 MPa of the pure aramid). Thermal decomposition temperatures were in the range of 300–450°C and the weight of the samples remaining after heating to 900°C was found to be roughly proportional to the clay loading. DSC showed a systematic increase in the glass transition temperature with increase in clay content. Water absorption of the pristine aramid film was rather high (5.7%), which reduced upon loading of organoclay. Copyright © 2008 John Wiley & Sons, Ltd.     

Structure and dehydration of layered perovskite niobate with bilayer hydrates prepared by exfoliation/self-assembly process

The crystals of an H-form niobate of HCa₂Nb₃O₁₀·xH₂O (x=0.5) being tetragonal symmetry (space group P4/mbm) with unit cell parameters a=5.4521(6) and c=14.414(2) Å were exfoliated into nanosheets with the triple-layered perovskite structure. The colloid suspension of the nanosheets was put into dialysis membrane tubing and allowed self-assembly in a dilute KCl solution. By this method, a novel layered K-form niobate KCa₂Nb₃O₁₀·xH₂O (x=1.3, typically) with bilayer hydrates in the interlayer was produced. The Rieveld refinement and transmission electron microscope (TEM)/selected-area electron diffraction (SAED) observation indicated that the orientations of the a-/b-axis of each nanosheet as well as the c-axis are uniform, and the self-assembled compound had the same symmetry, tetragonal (P4/mbm) with a=5.453(2) and c=16.876(5) Å, as the H-form precursor; the exfoliation/self-assembly process does not markedly affect the two-dimensional lattice of the layer. The large basal spacing resulted from the interlayer K⁺ ions solvated by two layers of water molecules. The interlayer bilayers-water was gradually changed to monolayer when the temperatures higher than 100 °C, and all the water molecules lost when over 600 °C. Accompanying the dehydration, the crystal structure transformed from tetragonal to orthorhombic symmetry. Water molecules may take an important role for the layer layered compound to adjust the unit cell to tetragonal symmetry.     

Intercalation effects in LDPE/o-montmorillonites nanocomposites

Typical montmorillonite clays (Cloisite^® Na⁺, Cloisite^® 30B) were modified by treatment with octadecyl ammonium chloride (ODC) and successive additions of octadecylamine (ODA). XRD analyses of the modified clays indicated an increase of the basal spacing of the (0 0 1) planes depending on the ODC or ODA additions.Nanocomposites were prepared by dispersing the modified clays (3% w/w concentration) in LDPE, using a Brabender mixer. XRD measurements of the obtained products indicated in some cases the achievement of intercalation effects, which were confirmed by TEM analysis.Some thermal, mechanical, dynamic-mechanical and rheological properties were evaluated and correlated to the degree of intercalation.     

Morphology and mechanical response of S–B star block copolymer – Layered silicate nanocomposites

The influence on the mechanical response by incorporation of oligostyrene-modified montmorillonite (MMT) and oligostyrene-modified bentonite (BET) into star shaped styrene–butadiene block copolymer has been investigated. The modified silicates are highly intercalated with a gallery distance of more than 9 nm and partly exfoliated. The array of tactoids consisting of 1–8 layers showing uniform state of distribution as revealed from TEM. The layers of the modified MMT and BET are observed to undergo nano-confinement, i.e. restricted to the PS-domains of the styrene–butadiene star block copolymer with impinging/bridging effects of silicate layers through the SB soft phase. DMA studies have showed an appreciable shift of the glass transition temperatures of PB- and PS-rich phases towards higher temperatures in addition to an increase of the storage modulus due to nanoclay reinforcement. Generally the Young’s modulus and yield stress was strongly increased with the incorporation of modified nanoparticles whereas at the same time the strain at break reduces slightly. The elastic–plastic hysteresis–stress and the hysteresis–work are largely increased due to effective interfacial effect; an effect that is largely attributed to the presence of highly intercalated and partially exfoliated silicate layers. The extent of increase was more in the modified MMT than in the modified BET based nanocomposites. The stress-decay and the strain-recovery aspects have also been critically analyzed in relation to their micro-structural attributes. Our study fundamentally demonstrates two critical aspects related to mechanical properties and particularly with regard to elastic–plastic hysteresis response. Firstly, partial confinement of the silicate layers is promoted by PS-aided surface modification facilitating enhancement in mechanical properties and secondly, the nano-confinement of modified MMT seems to be more effective in improving the hysteresis performance when compared to BET with higher charge density.     

Bio‐based nanocomposites from functionalized plant oils and layered silicate

Some discovery work was done on the synthesis of clay nanocomposites based on renewable plant oils. Functionalized triglycerides, such as acrylated epoxidized soybean oil, maleinized acrylated epoxidized soybean oil, and soybean oil pentaerythritol maleates, combined with styrene were used as the polymer matrix. The miscibility of these monomers and clay organomodifier was assessed by solubility parameters. The formation of nanocomposites was confirmed by both X‐ray data and transmission electron microscopy. The morphology showed a mix of intercalated and partially exfoliated sheets. The flexural modulus increased 30% at only 4 vol % clay content, but there was no significant effect on flexural strength, glass‐transition temperature, and thermal stability. Property enhancement was related to the degree of exfoliation that depends on both the polarity and flexibility of the monomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1441–1450, 2004