Biodegradable Polylactide and Its Nanocomposites: Opening a New Dimension for Plastics and Composites

The academic and industrial aspects of the preparation, characterization, mechanical and materials properties, crystallization behavior, melt rheology, and foam processing of pure polylactide (PLA) and PLA/layered silicate nanocomposites are described in this feature article. Recently, these materials have attracted considerable interest in polymer science research. PLA is linear aliphatic thermoplastic polyester and is made from agricultural products. Hectorite and montmorillonite are among the most commonly used smectite‐type layered silicates for the preparation of nanocomposites. Smectites are a valuable mineral class for industrial applications because of their high cation exchange capacities, surface area, surface reactivity, adsorptive properties, and, in the case of hectorite, high viscosity, and transparency in solution. In their pristine form, they are hydrophilic in nature, and this property makes them very difficult to disperse into a polymer matrix. The most common way to overcome this difficulty is to replace interlayer cations with quaternized ammonium or phosphonium cations, preferably with long alkyl chains. In general, polymer/layered silicate nanocomposites are of three different types: (1) intercalated nanocomposites, in which insertion of polymer chains into the layered silicate structure occurs in a crystallographically regular fashion, regardless of polymer to layered silicate ratio, with a repeat distance of few nanometer; (2) flocculated nanocomposites, in which intercalated and stacked silicate layers are sometimes flocculated due to the hydroxylated edge–edge interactions between the silicate layers; (3) exfoliated nanocomposites, in which individual silicate layers are uniformly distributed in the polymer matrix by average distances that totally depend on the layered silicate loading. This new family of composite materials frequently exhibits remarkable improvements in its material properties when compared with those of virgin PLA. Improved properties can include a high storage modulus both in the solid and melt states, increased flexural properties, a decrease in gas permeability, increased heat distortion temperature, an increase in the rate of biodegradability of pure PLA, and so forth.

Illustration of the biodegradability of PLA and various nanocomposites.     

Organically Modified Layered Titanate: A New Nanofiller to Improve the Performance of Biodegradable Polylactide

Summary: The preparation and characterization of a new type of nanocomposite material that is based on biodegradable polylactide (PLA) and organically modified layered titanate, is reported. Layered titanate, modified with a N‐(cocoalkyl)‐N,N‐[bis(2‐hydroxyethyl)]‐N‐methylammonium cation, was used as a new nanofiller (OHTO) for the nanocomposite preparation. Wide‐angle X‐ray diffraction and transmission electron microscopy (TEM) analyses confirmed that titanate layers were intercalated and nicely distributed in the PLA matrix. The materials properties of neat PLA improved remarkably after nanocomposite preparation.

UV/vis transmission spectra of neat PLA and a nanocomposite.     

New Insight into Biodegradation of Polylactide (PLA)/Clay Nanocomposites Using Molecular Ecological Techniques

Novel molecular ecological techniques were used to study changes in microbial community structure and population during degradation of polylactide (PLA)/organically modified layered silicates (OMLS) nanocomposites. Cloned gene sequences belonging to members of the phyla Actinobacteria and Ascomycota comprized the most dominant groups of microorganisms during biodegradation of PLA/OMLS nanocomposites. Due to their numerical abundance, members of these microbial groups are likely to play an important role during biodegradation process. This paper presents new insights into the biodegradability of PLA/OMLS nanocomposites and highlights the importance of using novel molecular ecological techniques for in situ identification of new microorganisms involved in biodegradation of polymeric materials.

     

Bacterial Cellulose Nanopaper as Reinforcement for Polylactide Composites: Renewable Thermoplastic NanoPaPreg

Bacterial cellulose (BC) is often regarded as a prime candidate nano‐reinforcement for the production of renewable nanocomposites. However, the mechanical performance of most BC nanocomposites is often inferior compared with commercially available polylactide (PLLA). Here, the manufacturing concept of paper‐based laminates is used, i.e., “PaPreg,” to produce BC nanopaper reinforced PLLA, which has been called “nanoPaPreg” by the authors. It is demon­strated that high‐performance nanoPaPreg (v_f = 65 vol%) with a tensile modulus and strength of 6.9 ± 0.5 GPa and 125 ± 10 MPa, respectively, can be fabricated. It is also shown that the tensile properties of nanoPaPreg are predominantly governed by the mechanical performance of BC nanopaper instead of the individual BC nanofibers, due to difficulties impregnating the dense nanofibrous BC network.

     

Polymer Layered Silicate/Carbon Nanotube Nanocomposites: Morphological and Rheological Properties

Morphological and rheological properties of new ternary nanocomposites based on ethylene vinyl acetate copolymers (EVA), commercial organo-modified clays (organoclays) and purified multi-walled carbon nanotubes (MWNTs), prepared via direct melt blending, have been evaluated. For sake of comparison, the corresponding binary compositions, i.e., EVA filled with either organoclays or MWNTs, have been investigated as well. While extensive exfoliation can be observed for binary EVA/clay nanocomposites, the addition of MWNTs appears to limit clay exfoliation. Rheological properties show that both clay and MWNTs increase the elastic modulus of the nanocomposites, reflecting the high degree of nanoparticle interconnectivity that can be found in these materials.     

New Millable Polyurethane/Organoclay Nanocomposite: Preparation,Characterization and Properties

The preparation, characterization and properties of novel millable polyurethane/organoclay nanocomposites are reported. Clay treated with methyl tallow bis(2‐hydroxyethyl) quaternary ammonium chloride was used as an organoclay for nanocomposite preparation. X‐ray diffraction indicated the intercalation of polymer chains inside the interlayer spacings of the clay. Dynamic mechanical analysis showed a significant increase in storage modulus, and tensile strength increases with increased organoclay loading.

X‐ray diffraction patterns of millable polyurethane/organoclay nanocomposites.     

Cyanate Ester/Functionalized Silica Nanocomposite: Synthesis,Characterization and Properties

In this paper silica nanoparticles with covalently grafted polymer chains were incorporated into bisphenol A dicyanate ester (BADCy) to prepare composites which resulted in improvements in the mechanical and thermal properties. Fourier‐transform infrared (FT‐IR) spectroscopy transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) were employed to examine the surface functionalization of silica nanoparticles. The effects of functionalized SiO₂ (F‐SiO₂) on the curing reactivity mechanical and thermal properties of BADCy resin were investigated systematically. The curing reaction of the system was facilitated with the addition of F‐SiO₂. Meanwhile compared with the neat resin the incorporation of appropriate content of modified F‐SiO₂ can enhance the mechanical properties including impact flexural strengths and fracture toughness K_IC of BADCy resin. In addition the thermal stability of BADCy/F‐SiO₂ nanocomposites is also superior to that of pure BADCy resin.     

Tuning Mechanical Properties of Block Copolymer/Aluminosilicate Hybrid Materials

In this work the primary mechanical property profiles of a specific class of nano‐structured polymer/inorganic hybrid materials are characterized. By utilizing sol‐gel aluminosilicate synthesis with amphiphilic polyisoprene‐block‐poly(ethylene oxide) block copolymers as structure‐directing agents, block copolymer/aluminosilicate hybrid materials are prepared with nanometer scale hexagonally packed cylinders and lamellae of the inorganic hybrid components, as evidenced by small‐angle X‐ray scattering. Systematic thermal and dynamic mechanical analyses are performed on these hybrids as well as on the constituting components. Results reveal two transitions from the low temperature, glassy state of the hybrids into high temperature elastic plateau regions, with moduli that vary over orders of magnitude as a function of composition and morphology. The first transition can be assigned to the glass transition of the PI domains while the second is ascribed to a temperature induced softening of the organic components within the PEO/hybrid domains. The results suggest that in the present nanostructured block copolymer/aluminosilicate hybrid materials composition and morphology provide a powerful tool to tailor mechanical property profiles.

     

纳米晶复合Nd2Fe14B/α-Fe合金制备与磁性能的研究

采用熔体快淬及晶化处理工艺制备Nd11Fe71Co8V1.5Cr1B7.5纳米晶合金。经21m·s-1快淬及640℃ 4min晶化处理后,制成的粘结磁体的磁性能最佳,为:Br=0.64T,JHc=903.5kA·m-1,(BH)max=71kJ·m-3。添加Cr元素可提高内禀矫顽力,从而提高最大磁能积。     

Network Formation in PP/Layered Silicate Nanocomposites: Modeling and Analysis of Rheological Properties

PP/organophilic montmorillonite composites were prepared from PP homopolymer, maleinated polypropylene and a clay organophilized with octadecyl amine. Various approaches were used to analyze the rheological properties of the composites. Cole-Cole plots proved to be useful, since they detect the network very sensitively. The frequency dependence of the real part of complex viscosity was described with a series of Maxwel bodies coupled parallel to each other. The relaxation time of the melt changed in the range of 0.0005 and 200 sec. Under certain conditions long relaxation times appear in the spectrum, which indicate the formation of new structural units, probably a silicate network. A certain number of silicate layers are needed to create a house-of-cards structure. A threshold concentration of MAPP exists for network formation, which depends on silicate content.     

Preparation and characterization of vinylidene chloride‐co‐vinyl chloride copolymer/fluorinated synthetic mica nanocomposites I thermal and mechanical properties studies

Poly(vinylidene chloride‐co‐vinylchloride)/organically modified fluorinated synthetic mica (MEE) (VDC‐VC/MEE) nanocomposites were prepared by melt blending of VDC‐VC copolymer with MEE, in the presence of dioctyl phthalate (DOP) which acted as a plasticizer and a cointercalating agent. The nanostructure, thermal, and dynamic mechanical properties of the VDC‐VC/MEE nanocomposites were studied by wide angle X‐ray diffractometer (WAXD), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analyzer (TGA), and dynamic mechanical analyzer (DMA). It was found that partially intercalated and partially exfoliated structures coexisted in VDC‐VC/MEE nanocomposities. Below 8 wt % MEE content, the intercalation effect of nanocomposites decreased with increasing the MEE content. Under a nitrogen atmosphere, VDC‐VC/MEE nanocomposites exhibited a single step thermal degradation behavior. The nanostructure of VDC‐VC/MEE can effectively prevent volatile gases from being released, and thus enhances its thermal stability. The thermal stability of VDC‐VC/MEE nanocomposites is strongly related to the morphology of nanocomposites and the degraded composites structure. DMA revealed a significant improvement in the storage modulus within the testing temperature range. The increase in storage modulus depends on the MEE content, which is attributed to the dispersed phase morphology. The glass transition temperature of VDC‐VC/MEE nanocomposites is affected by the chain mobility in the nanocomposites rather than the aggregative morphology. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1214–1225, 2008     

iPP Based Nanocomposites Filled with Calcium Carbonate Nanoparticles: Structure/Properties Relationships

Isotactic polypropylene (iPP) based nanocomposites filled with calcium carbonate nanoparticles (CaCO₃) were prepared by melt mixing and structure-properties relationships of the nanomaterials were studied. Elongated CaCO₃ nanopowders coated with two different coating agents, polypropylene-maleic anhydride graft copolymer (iPP-g-MA) and fatty acids (FA), were tested as nanoreinforced phases. The influence of surface treatment of the nanoparticles on the polymer/nanofillers interfacial adhesion and on the final materials properties was investigated. Morphological analysis showed that the selected coating agents induce different iPP/nanofiller adhesion degrees. Young's modulus increases as a function of the nanoparticles content and the coating agent nature. Finally, all the prepared nanocomposites showed a significant improvement of iPP barrier properties either to oxygen or to carbon dioxide.     

New poly(butylene succinate)/layered silicate nanocomposites. II. Effect of organically modified layered silicates on structure,properties, melt rheology,and biodegradability

A series of new poly(butylene succinate) (PBS)/layered silicate nanocomposites were prepared successfully by simple melt extrusion of PBS and organically modified layered silicates (OMLS). Three different types of OMLS were used for the preparation of nanocomposites: two functionalized ammonium salts modified montmorillonite and a phosphonium salt modified saponite. The structure of the nanocomposites in the nanometer scale was characterized with wide-angle X-ray diffraction and transmission electron microscopic observations. With three different types of layered silicates modified with three different types of surfactants, the effect of OMLS in nanocomposites was investigated by focusing on four major aspects: structural analysis, materials properties, melt rheological behavior, and biodegradability. Interestingly, all these nanocomposites exhibited concurrent improvements of material properties when compared with pure PBS. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3160–3172, 2003     

Preparation of Isotactic Polypropylene/Organoclay Nanocomposites by Solution Mixing Methodology: Structure and Properties Relationships

Isotactic Polypropylene (iPP) based nanocomposites filled with organo-clay nanoparticles were prepared and the relationships between their structure and properties were investigated. Modified C₁₆-C₁₈ smectite clay nanoparticles were used in order to promote matrix/filler compatibilization and to improve interfacial adhesion. X-Ray analysis performed on the nanocomposites demonstrated that at low organo-clay content (1 and 3% by weight) a nanostructure has been obtained, while in presence of 5% by weight of organoclay cluster regions have been formed. Mechanical tests showed that the elastic modulus increases of about 20% compared to the neat polymeric matrix value when 1 and 3% of nanofiller is added.     

Thermal and thermomechanical properties of poly[(butylene succinate)-co-adipate] nanocomposite

In this article the thermal and thermomechanical properties of neat poly[(butylene succinate)-co-adipate] (PBSA) and its nanocomposite are reported. Nanocomposite of PBSA with organically modified synthetic fluorine mica (OSFM) has been prepared by melt-mixing in a batch mixer. The structure of nanocomposite is characterized by X-ray diffraction patterns and transmission electron microscopic (TEM) observations that reveal homogeneous dispersion of intercalated silicate layers in the PBSA matrix. The melting behavior of pure polymer and nanocomposite samples are analyzed by differential scanning calorimetry (DSC), which shows multiple melting behavior of the PBSA matrix. The multiple melting behavior of the PBSA matrix is also studied by temperature modulated DSC (TMDSC) and wide-angle XRD (WXRD) measurements. All results show that the multiple melting behavior of PBSA is due to the partial melting, re-crystallization, and re-melting phenomena. The investigation of the thermomechanical behavior is performed by dynamic mechanical thermal analysis. Results demonstrate substantial enhancement in the mechanical properties of PBS, for example, at room temperature, storage flexural modulus increased from 0.5 GPa for pure PBS to 1.2 GPa for the nanocomposite, an increase of about 120% in the value of the elastic modulus. The thermal stability of nanocomposite compared to that of neat PBSA is also examined in pyrolytic and thermo-oxidative conditions. It is then studied using kinetic analysis. It is shown that the stability of PBSA is increased moderately in the presence of OSFM.