New polylactide/layered silicate nanocomposites. 5. Designing of materials with desired properties

Understanding the structure/property relationship in polymer/layered silicate nanocomposites is of great importance in designing materials with desired properties. In order to understand these relations, a series of polylactide (PLA)/organically modified layered silicate (OMLS) nanocomposites have been prepared using a simple melt extrusion technique. Four different types of OMLS have been used for the preparation of nanocomposites, three were modified with functionalized ammonium salts while fourth one was a phosphonium salt modified OMLS. The structure of the nanocomposites in the nanometer scale was characterized by using wide-angle X-ray diffraction and transmission electron microscopic observations. Using four different types of layered silicates modified with four different types of surfactants, the effect of OMLS in nanocomposites was investigated by focusing on four major aspects: structural analysis, thermal properties and spherulite morphology, materials properties, and biodegradability. Finally, we draw conclusions about the structure/property relationship in the case of PLA/OMLS nanocomposites.     

Morphology and properties of thermoplastic polyurethane nanocomposites incorporating hydrophilic layered silicates

Hydrophilic layered silicate/polyurethane nanocomposites were prepared via twin screw extrusion and solvent casting. Good dispersion and delamination was achieved regardless of processing route, illustrating that the need for optimised processing conditions diminishes when there is a strong driving force for intercalation between the polymer and organosilicate. Evidence for altered polyurethane microphase morphology in the nanocomposites was provided by DMTA and DSC. WAXD results suggested that the appearance of an additional high temperature melting endotherm in some melt-compounded nanocomposites was not due to the formation of a second crystal polymorph, but rather due to more well-ordered hard microdomains. Solvent casting was found to be the preferred processing route due to the avoidance of polyurethane and surfactant degradation associated with melt processing. While tensile strength and elongation were not improved on organosilicate addition, large increases in stiffness were observed. At a 7 wt% organosilicate loading, a 3.2-fold increase in Young's modulus was achieved by solvent casting. The nanocomposites also displayed higher hysteresis and permanent set.     

Synthesis, structure, thermal and mechanical properties of nanocomposites based on linear polymers and layered silicates modified by polymeric quaternary ammonium salts (ionenes)

Polymer–clay composites has been prepared by melt blending an organo-bentonite with linear polymers (polyamide, polysterene and polypropylene) in a disk-screw extruder. In first time organo-clay was prepared by surface treatment of Na-forms bentonite with polymeric quaternary ammonium salts (PQAS). XRD indicated that organo-bentonite layers were exfoliated and dispersed into polyamide and polystyrene. Addition of 2 wt% organo-bentonites (optimal concentration) to polyamide increased tensile strength by 53% and Sharpy impact by 140%. With the incorporation of 2 wt% organo-bentonites (optimal concentration) into polystyrene the tensile strength increased to 28% and the Sharpy impact increased to 25%. For polypropylyne–organo-bentonites composites we did not observe delamination of layered structure, and as result absence of reinforcements. TGA showed that the polyamide and polystyrene nanocomposites have higher decomposition temperature in comparison with the original polymers.     

Morphology, thermal relaxations and mechanical properties of layered silicate nanocomposites based upon high-functionality epoxy resins

This paper investigates the possibility of improving the mechanical properties of high-functionality epoxy resins through dispersion of octadecyl ammonium ion-modified layered silicates within the polymer matrix. The different resins used are bifunctional diglycidyl ether of bisphenol-A (DGEBA), trifunctional triglycidyl p-amino phenol (TGAP) and tetrafunctional tetraglycidyldiamino diphenylmethane (TGDDM). All resins are cured with diethyltoluene diamine (DETDA). The morphology of the final, cured material was probed by wide-angle X-ray scattering, as well as optical and atomic force microscopy. The α- and β-relaxation temperatures of the cured systems were determined using dynamic mechanical thermal analysis. It was found that the presence of organoclay steadily decreased both transition temperatures with increasing filler concentration. Further, the effect of different concentrations of the alkyl ammonium-modified layered silicate on the toughness and stiffness of the different epoxy resins was analyzed. All resin systems have shown improvement in both toughness and stiffness of the materials through the incorporation of layered silicates, despite the fact that it is often found that these two properties cannot be simultaneously achieved.     

Natural rubber-based nanocomposites by latex compounding with layered silicates

Natural rubber (NR) based nanocomposites with 10 wt% natural and synthetic layered silicates were produced via the latex compounding method. As layered silicates, sodium bentonite (natural) and sodium fluorohectorite (synthetic) were selected in addition to a non-layered inert filler (English India clay or commercial clay) as reference material. The nanocomposites were prepared by compounding the dispersions of clays and other latex chemicals necessary for vulcanization. The vulcanized nanocomposites were subjected to mechanical, thermal and swelling tests. The silicate dispersion was studied by transmission electron microscopy. Layered silicates outperformed the reference material (commercial clay) in all aspects. This was attributed to the intercalation/exfoliation of the silicates and to the formation of a skeleton ‘(house of cards)’ silicate network in the NR matrix.     

Modification of polylactide upon physical properties by solution-cast blends from polylactide and polylactide-grafted dextran

Polylactide (PLA)-grafted polysaccharides with various lengths and numbers of graft chains were synthesized using a trimethylsilyl protection method. The properties of the cast films prepared from graft-copolymers were investigated through thermal and dynamic mechanical analyses. The graft-copolymer films exhibited a lower glass transition temperature (T_g), melting temperature, and crystallinity, and higher viscosity properties compared to PLA films. Moreover, the usefulness of graft-copolymer as a plasticizer was investigated with 1:4 blend films prepared from the graft-copolymers and PLA. The blend films showed lower T_g and crystallinity, and higher viscosity properties compared to PLA films.     

Morphology, rheology and crystallization behavior of polylactide composites prepared through addition of five-armed star polylactide grafted multiwalled carbon nanotubes

Functionalized multiwalled carbon nanotubes (F-MWNTs) were prepared by covalent grafting of five-armed star polylactide (fa-PLA), and were characterized by thermogravimetric analysis (TGA), nuclear magnetic resonance (NMR) spectroscopy and Raman spectroscopy. A series of polylactide (PLA)/F-MWNTs composites was prepared via coagulation method. Several techniques were applied to investigate the effects of F-MWNTs on the morphology, melt rheology, and crystallization and melting behaviors of the PLA composites. The optical microscope (OM), field-emission scanning electron microscope (FE-SEM) and transmission electron microscopy (TEM) observations demonstrated that, in comparison with the case of PLA filled with pristine MWNTs, F-MWNTs case showed improved dispersion and interfacial adhesion. Oscillatory frequency sweep measurements showed that addition of about 2.0 wt% F-MWNTs led to a solidlike response where a percolated network structure formed, and the composites exhibited remarkable improvement of rheological properties in the melt state as compared with that of neat PLA. DSC measurements showed that F-MWNTs acted as a nucleating agent to enhance crystallization when below the percolation concentration, while also acted as a hindrance to retard crystallization above the percolation concentration. The double melting peaks on the DSC curves were attributed to melting of the crystals formed in the cold crystallization stage and the melting-recrystallization-remelting (mrr) event during heating, respectively.     

Miscibility and viscoelastic properties of acrylic polyhedral oligomeric silsesquioxane-poly(methyl methacrylate) blends

We investigate the miscibility of acrylic polyhedral oligomeric silsesquioxanes (POSS) [characteristic size d≈2 nm] and poly(methyl methacrylate)(PMMA) in order to determine the effect of well-dispersed POSS nanoparticles on the thermomechanical properties of PMMA. Two different acrylic POSS species (unmodified and hydrogenated) were blended separately with PMMA at volume fractions up to ?=0.30. Both POSS species have a plasticizing effect on PMMA by lowering the glass transition temperature T_g and decreasing the melt-state linear viscoelastic moduli measured in small amplitude oscillatory shear flow. The unmodified acrylic-POSS has better miscibility with PMMA than the hydrogenated form, approaching complete miscibility for loadings ?<0.10. At a loading ?=0.05, the unmodified acrylic POSS induces a 4.9 °C decrease in the T_g of PMMA, far less than the 17.4 °C decrease in the glass transition temperature observed in a blend of 5 vol% dioctyl phthalate (DOP) in PMMA; however, the decrease in the glass transition temperature per added plasticizer molecule is nearly the same in the unmodified acrylic-POSS-PMMA blend compared with the DOP-PMMA blend. Time-temperature superposition (TTS) was applied successfully to the storage and loss moduli data and the resulting shift factors were correlated with a significant increase in free volume of the blends. The fractional free volume f₀=0.046 for PMMA at T₀=170 °C while for a blend of 5 vol% unmodified acrylic-POSS in PMMA f₀=0.057, which corresponds to an addition of 0.47 nm³ per added POSS molecule at ?=0.05. The degree of dispersion was characterized using both wide-angle X-ray diffraction (WAXD) and dynamic mechanical analysis (DMA). Diffraction patterns for both blend systems show clear evidence of phase separation at ?=0.20 and higher, but no significant phase separation is evident at ?=0.10 and lower. The storage modulus measured in DMA indicates appreciable phase separation for unmodified acrylic POSS loadings ?≥0.10, while no evidence of phase separation is present in the ?=0.05 blend in DMA.     

Mesophase formation and its thermal transition in the stretched glassy polylactide revealed by infrared spectroscopy

The structural development in the glassy polylactide during stretching and subsequent heating has been investigated by Fourier transform infrared spectroscopy. It is indicated that only when molecular chains in the amorphous phase approach their finite extensibility beyond a critical strain of about 1, accompanied by remarkable conformational ordering, can cohesive mesophase with certain molecular ordering be brought out to trigger strain-induced crystallization. Upon heating cohesive mesophase endures melting during glass transition region where an endothermic peak is observed, and the extent of melting relies on its initial thermal stability and is in particular affected by the subsequent advent of strain-induced crystallization.     

Morphology and properties of thermoplastic polyurethane composites incorporating hydrophobic layered silicates

Polyurethane (PU) composites incorporating Cloisite 15A (15A) were prepared via melt compounding and solvent casting. The melt‐compounded composites had better dispersion and a smaller silicate stack size as a result of the higher shear forces associated with twin‐screw extrusion. The PU microphase separation and hard domain order were greater in the melt‐processed materials. At the concentrations of 15A employed in this study (≤7 wt %), the filler did not have an observable effect on the microphase texture of either the solvent‐ or melt‐processed PU. The tensile properties of the melt‐compounded materials were lower than those of their solvent‐cast counterparts because of thermal degradation. The solvent‐cast composite containing a 3 wt % loading of 15A displayed improved tensile strength and elongation, primarily because of plasticization by the silicate organic treatment. The addition of layered silicates with high aspect ratios increased the hysteresis and permanent set of this PU elastomer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 300–309, 2005     

Structure and mechanical properties of polylactide copolymer microspheres and capsules

Polylactide homopolymers, polylactide and poly(ethylene oxide) diblock and triblock copolymers are used to prepare spherical microparticles by using the single oil-in-water emulsion and solvent evaporation technique. We are able to create both bulk and hollow microspheres by altering the conditions of preparation. The experiments are carried out at two fixed temperatures of 15 and 22 °C. We show, from scanning electron microscopy data, that the microspheres produced from the homopolymers are bulk and homogeneous at both temperatures whereas they are hollow when the triblock copolymers are used. The diblock copolymers yield bulk microspheres at 15 °C and microcapsules at 22 °C. Compression experiments emphasize once more the inner morphology of the spheres. As it is expected, bulk microspheres have higher Young’s modulus than the microcapsules. Nevertheless, comparative compression analysis of both morphologies shows that the microcapsules retain relatively high compressive moduli. These results have implications for the design of rigid and biodegradable microcapsules.     

Morphology and properties of UV-curing epoxy acrylate coatings modified with methacryl-POSS

In this work, the morphology and properties of UV-curing epoxy acrylate (EA) coatings modified with methacryl polyhedral oligomeric silsesquioxanes (M-POSS) were studied. The M-POSS nanocages were introduced into EA UV-curing system via copolymerization at loadings between 0% and 10 wt%. The XRD and FTIR analysis indicated that M-POSS chemically incorporated into the hybrid materials and formed a cross-linked network between M-POSS and EA. The morphological analysis showed that the discrete spherical POSS-rich particles were dispersed in the EA matrix uniformly, and both of the number and mean diameter of POSS-rich particles increased with the increasing M-POSS loadings. The influence of M-POSS on the kinetics of the photopolymerization was determined by real time FTIR spectroscopy and the result showed that the addition of POSS enhanced both of the UV-curing rates and final double bond conversion. The DMA analysis showed that increasing the amount of M-POSS nanocages caused an increase on the nanocomposite's T_g. TGA curves showed that at the later period of degradation process, the thermal stability of nanocomposites was enhanced by M-POSS. With respect to the mechanical properties, the most remarkable trend was an improvement on the impact resistance of nanocomposites with the increasing POSS contents. Because both of the craze and plasticity deformation caused by POSS nanocages would absorb impact energy, hinder the growth of craze.     

Morphology and crystallization kinetics in a mixture of low-molecular weight aliphatic amide and polylactide

Polylactide (PLA)/N,N-ethylenebis(12-hydroxystearamide) mixture was prepared by using melt extrusion. The detailed crystallization kinetics and morphology of neat PLA and a mixture were studied by using polarized optical microscopy, light scattering, differential scanning calorimetry, and wide-angle X-ray diffraction analyses. The overall crystallization rate and spherulitic texture of PLA were strongly influenced in presence of the organic additive. The overall crystallization rate of matrix PLA increased with addition of WX1. These behaviors indicated that WX1 crystallites, which crystallized at the very early stage of PLA crystallization act as a nucleating agent for PLA crystallization.     

Morphology, thermal behavior and mechanical properties of binary blends of compatible biosourced polymers: Polylactide/polyamide11

Blends of entirely biosourced polymers, namely polylactide (PLA) and polyamide11 (PA11), have been melt-compounded by twin-screw extrusion without the use of any compatibilizing agent. The crystallization and melting behavior, the morphology and mechanical properties of the melt-compounded binary blends have been investigated over the whole composition range. Albeit immiscibility prevails in all blends, the micronic and sub-micronic dispersion of the minor phase reveals a self-compatibilization behavior of the PLA/PA11 system as directly evidenced via scanning electron microscopy. For PLA compositions below 50%, PLA appears to be dispersed as globules in the PA11 matrix. With increasing PLA content beyond 50%, the blends exhibit co-continuous intertwined phases, then thread-like PA11 phase dispersed in a PLA matrix. For PLA composition greater than 80%, PA11 displays globular dispersion. In the case of PLA-rich blends, the crystallization of PA11 from the melt displayed a contribution of “homogeneous nucleation” corroborating the high degree of dispersion of the minor phase. However, the earlier crystallization of PA11 upon cooling did not promote that of PLA suggesting low interfacial free energy at the boundaries of the phase-separated domains, i.e. roughly neutral interactions between the unlike species. The non-symmetric structural behavior of the blends over the whole composition range was found to influence the mechanical properties. If the elastic modulus of the blends roughly obeys an additive mixture law at room temperature (RT), this is not the case above the Tg of both PLA and PA11. More particularly in the PLA-rich range, the thread-like dispersion of the stiff PA11 component plays the role of in situ fibrillar reinforcement of the soft PLA matrix. The strain at break and the yield stress also do not obey a simple mixture law, both at RT and above Tg. Perspectives of morphological and mechanical improvements of PLA/PA11 blends are discussed.     

Long chain branching polylactide: Structures and properties

Long chain branching (LCB) of polylactide (PLA) was successfully prepared by the successive reactions of the end hydroxyl groups of PLA with pyromellitic dianhydride (PMDA) and triglycidyl isocyanurate (TGIC) together. The topological structures of the LCB generated from functional group reactions as well as free radical reactions were investigated thoroughly by gel permeation chromatography (GPC) and rheology. Qualitative information about the branching structures could be readily obtained from linear viscoelasticity, non-linear oscillatory shear experiments and strain hardening in elongational experiments. For quantitative information on chain structure, linear viscoelasticity combined with branch-on-branch (BOB) dynamic model was used to predict exact compositions and chain topologies of the products, which were reasonably explained by the suggested mechanism of functional group reactions. It was found out that the tree-like LCB structure generated in these reactions contributed remarkably to the enhancement of strain hardening under elongational flow, which improves the foaming ability substantially.     

Morphology and rheological properties of nanocomposites based on nitrile rubber and organophilic layered silicates

Organo‐montmorillonite/nitrile rubber (NBR) nanocomposites were prepared by a melt intercalation process. The characteristics of NBR nanocomposites were determined by an oscillating disk rheometer and transmission electron microscopy. The cure characteristics were investigated according to the change in clay content and clay types. This study confirmed that organo‐montmorillonite/NBR nanocomposites have various cure characteristics, namely minimum torque, maximum torque, scorch time and curing time, according to the change in clay content and clay types. In particular, as the chain length of the modifier used for the treatment of Na⁺‐MMT following vulcanization increases, scorch time and optimum curing time are reduced. This is because, as the chain length of the modifier increases, organo‐MMT is distributed more equally during the formation of the nanocomposites. As swelling increases, the chain length of the clay modifier expands and then constitutes a better barrier. Copyright © 2003 Society of Chemical Industry     

Quantitative estimation of the reinforcing effect of layered silicates in PP nanocomposites

Various polypropylene/layered silicate composites were prepared with different silicate contents. Montmorillonites with and without organophilization as well as three maleinated polypropylenes were used to change the extent of exfoliation and hence the properties of the composites. Structure was characterized by X-ray diffraction (XRD), scanning (SEM) as well as transmission electron microscopy (TEM) and tensile properties were also measured. The analysis of the tensile yield stress values of a large number of composites showed a broad range of variation in mechanical properties. XRD and TEM results do not reflect the differences in properties and they usually do not give quantitative information about the extent of exfoliation either. PP/clay composites containing maleinated PP, which do not exhibit a silicate reflection in XRD, may have very poor mechanical properties indicating small extent of exfoliation. The composition dependence of tensile yield stress of these composites may be described and evaluated quantitatively by a simple model developed earlier for particulate filled polymers. The use of a few simple assumptions most of which are supported by previous results allows us to estimate the extent of exfoliation quantitatively. The tensile yield stress of about 40 composites was analyzed with the model. Some of the composites were prepared by us, while results on others were taken from papers published in the literature. The analysis indicated that the extent of exfoliation is very low in most composites; it reaches maximum 8% of the theoretically possible value in the best case. This result is in agreement with our observation that complete exfoliation can be seldom reached in thermoplastic/clay composites; the structure is complex and hierarchical including large particles and individual silicate layers. The results prove that further efforts must be done to increase the extent of exfoliation in order to achieve reinforcement levels forecasted earlier.     

New nanocomposite materials based on plasticized poly(l-lactide) and organo-modified montmorillonites: thermal and morphological study

Plasticized poly(l-lactide) (PLA) based nanocomposites were prepared by melt blending of the matrix with 20 wt% of poly(ethyleneglycol) 1000 (PEG 1000) and different amounts of montmorillonite, organo-modified or not. The intercalation of the polymer chains between the aluminosilicates layers and morphological structure of the filled PLAs were analysed by wide-angle X-ray scattering (WAXS). Thermogravimetric analyses (TGA) and differential scanning calorimetry (DSC) were performed to study the thermal behaviour of the prepared composites. At constant filler level, it appears that from all the clays studied, the montmorillonite organo-modified by bis-(2-hydroxyethyl)methyl (hydrogenated tallowalkyl) ammonium cations brings the greater effect in terms of thermal stability. Increasing the amount of clay allows to delay the onset of thermal degradation of the plasticized polymer matrix. It was also pointed out, by WAXS and DSC analyses, that it exists a real competition between PEG 1000 and PLA for the intercalation into the interlayer spacing of the clay.     

Binary and ternary blends of polylactide, polycaprolactone and thermoplastic starch

In this study binary and ternary blends of polylactide (PLA), polycaprolactone (PCL) and thermoplastic starch (TPS) are prepared using a one-step extrusion process and the morphology, rheology and physical properties are examined. The morphology and quantitative image analysis of the 50/50 PLA/TPS blend transverse phase size demonstrate a bimodal distribution and the addition of PCL to form a ternary blend results in a substantial number of fine dispersed particles present in the system. Focused ion beam irradiation, followed by atomic force microscopy (AFM) shows that dispersed PCL forms particles with a size of 370 nm in PLA. The TPS phase in the ternary blends shows some low level coalescence after a subsequent shaping operation. Dynamic mechanical analysis indicates that the temperature of the tan δ peak for the PLA is independent of TPS blend composition and that the addition of PCL in the ternary blend has little influence on the blend transitions. Both the α and β transitions for the thermoplastic starch are highly sensitive to glycerol content. When TPS of high glycerol content is blended with PLA, an increase in the ductility of the samples is achieved and this effect increases with increasing volume fraction of TPS. The ternary blend results in an even greater ductility with an elongation at break of 55% as compared to 5% for the pure PLA. A substantial increase in the notched Izod impact energy is also observed with some blends demonstrating three times the impact energy of pure PLA. The mechanical properties for the ternary blend clearly indicate a synergistic effect that exceeds the results obtained for any of the binary pairs. Overall, the ternary blend approach with PLA/TPS/PCL is an interesting technique to expand the property range of PLA materials.     

Effect of modified layered silicates and compatibilizer on properties of PMP/clay nanocomposites

The preparation and properties of poly(4‐methyl‐1‐pentene) (PMP)/clay nano‐composites are described for the first time. The effect of clay modification and compatibilizer on the formation and properties of the nanocomposites is studied. Layered silicates modified with two types of quaternary ammonium salts are used. The X‐ray diffraction results indicate intercalation of the polymer into the intergallery spacing of the clay. Thermogravimetric analysis shows a delay in the degradation process. Dynamic mechanical analysis shows an increase in the storage modulus for the nanocomposites. The use of compatibilizer containing maleic anhydride and acrylic ester groups is explored. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3233–3238, 2003