Preparation of new polymer nanocomposites based on poly(lactic acid)/fatty nitrogen compounds modified clay by a solution casting process

In this study, different organoclays (OMMTs) were prepared using various fatty nitrogen compounds (FNCs) and natural clay, sodium montmorillonite (MMT). The clay modification was carried out by stirring the clay particles in an aqueous solution of fatty amides (FA), fatty hydroxamic acids (FHA), and carbonyl difatty amides (CDFA). These OMMTs were then used for nanocomposites production to improve the property balance of poly(lactic acid) (PLA) by solution casting process. All sets of OMMTs and nanocomposites were characterized using various apparatuses. In the nanocomposites, where the clay surface is pretreated with FA, FHA and CDFA, the basal spacing of the clay increased to 2.94, 3.26 and 3.80 nm, respectively The X-ray diffraction (XRD) and transmission electron microscopy (TEM) results confirmed the production of nanocomposites. PLA modified clay nanocomposites show higher thermal stability and significant improvement of mechanical properties in comparison with pure PLA.     

Effects ofIn Vitro degradation on the weight loss and tensile properties of PLA/LPCL/HPCL blend fibers

PLA/LPCL/HPCL blend fibers composed of poly (lactic acid) (PLA), low molecular weight poly (ɛ-caprolactone) (LPCL), and high molecular weight poly (ɛ-caprolactone) (HPCL) were prepared by melt blending and spinning for bioabsorbable filament sutures. The effects of blending time and blend composition on the X-ray diffraction patterns and tensile properties of PLA/LPCL/HPCL blend fibers were characterized by WAXD and UTM. In addition, the effect ofin vitro degradation on the weight loss and tensile properties of the blend fibers hydrolyzed during immersion in a phosphate buffer solution at pH 7.4 and 37°C for 1–8 weeks was investigated. The peak intensities of PLA/LPCL/HPCL blend fibers in X-ray diffraction patterns decreased with an increase of blending time and LPCL contents in the blend fibers. The weight loss of PLA/LPCL/HPCL blend fibers increased with an increase of blending time, LPCL contents, and hydrolysis time while the tensile strength and modulus of the blend fibers decreased. The tensile strength and modulus of the blend fibers were also found to be increased with an increase of HPCL contents in the blend fibers. The optimum conditions to prepare PLA/LPCL/HPCL blend fibers for bioabsorbable sutures are LPCL contents of 5 wt%, HPCL contents of 35 wt%, and blending time of 30 min. The strength retention of the PLA/LPCL/HPCL blend fiber prepared under optimum conditions was about 93.5% even at hydrolysis time of 2 weeks.     

Preparation and crystallization behavior of polylactide nanocomposites reinforced with POSS-modified montmorillonite

We herein report the preparation and crystallization behavior of polylactide (PLA) nanocomposites reinforced with polyhedral oligomeric silsesquioxane-modified montmorillonite (POSS-MMT), which is prepared by exchanging sodium cations of pristine sodium montmorillonite (Na-MMT) with protonated aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS-NH₃ ⁺). PLA nanocomposites with 1–10 wt% POSS-MMT contents are manufactured via melt-compounding, and their structures and melt-crystallization behavior are investigated. It is characterized that POSS-MMT nanoparticles in the nanocomposites have an exfoliated structure of MMT silicates with POSS-NH₃ ⁺ and partial POSS-NH₂ crystals. DSC cooling thermograms suggest that the overall melt-crystallization rates of the nanocomposite with only 3 wt% POSS-MMT are remarkably enhanced in comparison with the neat PLA. From the isothermal crystallization analysis based on the Avrami model, the overall melt-crystallization of PLA/POSS-MMT nanocomposites is found to be dominated by the heterogeneous nucleation and three-dimensional spherulite growth. Isothermal melt-crystallization experiments using a polarized optical microscope show that the spherulite nucleation density of PLA/POSS-MMT nanocomposites is much higher than that of the neat PLA, whereas the spherulite growth rates of all the nanocomposites are almost identical with the rate of the neat PLA. It is concluded that the highly enhanced melt-crystallization rates of PLA/POSS-MMT nanocomposites stem from the dominant nucleation effect of POSS-MMT nanoparticles for PLA crystals.     

Functionalization of graphene nanosheets and its dispersion in PMMA/PEO blend: Thermal,electrical, morphological and rheological analyses

Graphene nanoplatelet (GnP) was chemically functionalized by amine groups for improvement of compatibility in poly(methyl methacrylate) (PMMA)/poly(ethylene oxide) (PEO) blend. PMMA/PEO (90/10) nanocomposites with non-functionalized GnP and functionalized GnP (FGnP) were prepared by solution casting method. Successful grafting of amine groups on the GnP surface was confirmed by Fourier transform infrared (FT-IR) and X-ray diffraction (XRD) analysis. The Transmission electron microscopy (TEM) images showed that the dispersion state of FGnP was better than that of GnP in PMMA/PEO nanocomposites. The effects of FGnP and GnP on rheological, thermal and electrical properties of PMMA/PEO nanocomposites were investigated by various methods. The results indicated that the FGnP-based nanocomposites had higher storage modulus, glass transition temperature and thermal stability as compared to the GnP-based nanocomposites. The electrical conductivity of the nanocomposites with FGnP was better than that of GnP-based nanocomposites. The higher conductivity was attributed to homogeneous and well dispersion state of FGnP in PMMA/PEO nanocomposites.     

Unique crystallization behavior of multi-walled carbon nanotube filled poly(lactic acid)

Although poly(lactic acid) (PLA) possesses many desirable properties such as miscible, reproducible, nontoxic, and biodegradable properties, extremely slow crystallization rate is a weak point in comparison with other commercial thermoplastics. Addition of nucleating agents can be a good method to increase the overall crystallization rate and multi-walled carbon nanotube (MWCNT) is generally known as a good nucleating agent as well as reinforcement. MWCNT reinforced PLA nanocomposites were prepared by melt blending and the unique nucleation and crystallization behaviors of pure PLA and MWCNT/PLA nanocomposites were investigated. Slow homogeneous nucleation and crystallization behavior of the pure PLA and fast heterogeneous crystallization behavior of MWCNT/PLA nanocomposites were observed. Crystallization behavior of MWCNT/PLA nanocomposites was irrespective of cooling rate and the peculiar behavior was due to fast heterogeneous crystallization caused by the nucleating effect of MWCNT and fast PLA chain mobility.     

The effects of blend composition and blending time on the ester interchange reaction and tensile properties of PLA/LPCL/HPCL blends

PLA/LPCL/HPCL blends composed of poly(lactic acid) (PLA), low molecular weight poly(ε-caprolactone) (LPCL), and high molecular weight poly(ε-caprolactone) (HPCL) were prepared by melt blending for bioabsorbable filament sutures. The effects of blend composition and blending time on the ester interchange reaction by alcoholysis in the PLA/LPCL/HPCL blends were studied. Their thermal properties and the miscibility due to the ester interchange reaction were investigated by¹H-NMR, DSC, X-ray, and UTM analyses. The hydroxyl group contents of LPCL in the blends decreased by the ester interchange reaction due to alcoholysis. Thus, the copolymer was formed by the ester interchange reaction at 220 °C for 30–60 minutes. The thermal properties of PLA/LPCL/HPCL blends such as melting temperature and heat of fusion decreased with increasing ester interchange reaction levels. However, the miscibility among the three polymers was improved greatly by ester interchange reaction. Tensile strength and modulus of PLA/LPCL/HPCL blend fibers increased with increasing HPCL content, while the elongation at break of the blend fibers increased with increasing LPCL content.     

Miscibility and performance evaluation of natural-flour-filled PP/PBS and PP/PLA bio-composites

This research evaluates the miscibility and performance of polypropylene (PP)/polybutylene succinate (PBS) and PP/polylactic acid (PLA) blend and natural-flour-filled, PP/PLA and PP/PBS blend bio-composites. The melting temperature (T _m ) and glass transition temperature (T _g ) of pure PP, PBS and PLA showed a single peak but differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) presented two peaks for the T _m and T _g of the PP/PBS and PP/PLA blends. These results indicated that the PP/PBS and PP/PLA blend systems existed as immiscible blends. These results were also confirmed by the scanning electron microscopy (SEM) micrographs of the tensile fracture surface of the PP/PBS and PP/ PLA blends. At a PP/PBS and PP/PLA blend ratio of 70/30, the tensile and flexural strengths of bamboo flour (BF)- and wood flour (WF)-filled, PP/PBS and PP/PLA blend bio-composites were similar to those of BF- and WF-filled, PP and PBS bio-composites. In addition, these strengths of maleic anhydride-grafted PP (MAPP)- and acrylic acid-grafted PP (AAPP)-treated, BF- and WF-filled, PP/PBS and PP/PLA blend bio-composites were higher than those of non-treated bio-composites.     

Mechanical characterization of clay reinforced polypropylene nanocomposites at high temperature

This paper focuses on the influence of temperature conditions and the clay contents on enhancement of mechanical characterization of polypropylene (PP) nanocomposites. The nanocomposites were prepared using the melt mixing technique in a co-rotating intermeshing twin screw extruder followed by injection moulding. Nanocomposites properties such as impact strength and ultimate tensile strength, yield strength, failure strain, Young’s modulus and toughness are calculated. The addition of clay to PP matrix was showed remarkable enhancement in mechanical properties at the temperature of 25 oC and 120 °C. Nearly 36 % and 160 % increase in the Young’s modulus and about 45 % and 62 % increase in the impact strength were observed at both room temperature (RT) and high temperature (HT), respectively. But, the tensile strength was not affected much. The basal spacing of clay in the composites was measured by X-ray diffraction (XRD). Scanning electron microscopy (SEM) was used to assess the surface morphology of the fractured surfaces and dispersion of the nanoclay.     

Thermal and structure properties of biobased cellulose nanowhiskers/poly (lactic acid) nanocomposites

Cellulose nanowhiskers were used to improve the performance of poly (lactic acid) (PLA). The nanocomposites mixed with three different molecular weight of poly (ethylene glycol) (PEG) were characterized by mechanical testing, thermal gravimetry and differential scanning calorimetry. The tensile test showed an increase in tensile strength and elongation at break with the addition of PEG to PLA/CNW nanocomposites, the thermal analysis results showed an increase of crystallization temperature (T _c) and crystallization compatibility (larger crystallization and melting areas), which indicated that the cellulose nanowhiskers (CNW) and PEG or CNW alone should not be considered as nucleating agents for the PLA matrix; The CNW was homo-dispersed which contributed to decreasing mobility of polymer chain segments. The compatibility between hydrophobic PLA matrix and the hydrophilic CNW was improved by the addition of different molecular weight polymeric-PEG. The thermo gravimetric analysis indicated that the thermal stability of the different composites were reflected well in the region between 25 °C and 245 oC. The structure of the PLA/CNW/PEG composites was characterized by AFM, which showed that the CNW dispersed in the PLA matrix evenly.     

Effects of nanoclay and short nylon fiber on morphology and mechanical properties of nanocomposites based on NR/SBR

Natural rubber and styrene butadiene rubber (NR/SBR) reinforced with both short nylon fibers and nanoclay (Cloisite 15A) nanocomposites were prepared in an internal and a two roll-mill mixer by a three-step mixing process. The effects of fiber loading and different loading of nanoclay (1, 3 and 5 wt. %) were studied on the microstructure and mechanical properties of the nanocomposites. The adhesion between the fiber and the matrix was improved by the addition of a dry bonding system consisting of resorcinol, hexamethylene tetramine and hydrated silica (HRH). This silicate clay layers was used in place of hydrated silica in a HRH bonding system for SBR/NR-short nylon fiber composite. Nanoclay was also used as a reinforcing filler in the matrix-short fiber hybrid composite. The cure and scorch times of the composites decreased while cure rate increased when the short fiber and nanoclay were added. The mechanical properties of the composites showed improvement in both longitudinal and transverse directions with increasing short fiber and nanoclay content. The structure of the nanocomposites was characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM). X-ray diffraction results of nanocomposites indicated that the interlayer distance of silicate layers increased. The mechanical properties of nanocomposites (tensile, hardness and tear strength) are examined and the outcome of these results is discussed in this paper.     

Compatibilization of poly(lactic acid)/polycarbonate blends by different coupling agents

In this study, PLA/PC blends were prepared in order to investigate the effects of the addition of PC loading level into PLA matrix on the mechanical properties of these blends. After that, PLA/PC (70/30), which has the lowest tensile strength value, was selected as a control sample for the compatibilization study. Commercial styrene-acrylic multi-functional-epoxide oligomeric agent (SAmfE), styrene maleic anhydride copolymer (SMA), tetrasilanol phenyl polyhedral oligomeric silsesquioxane (T-POSS) and glycidyl isooctyl-polyhedral oligomeric silsesquioxane (G-POSS) were used as compatibilizers for PLA/PC blends. The variation of mechanical, thermal, structural and morphological properties were examined by conducting tensile tests, dynamic mechanical analyses, differential scanning calorimetry, Fourier Transform IR and scanning electron microscope analyses. Tensile test results showed that the tensile strength and elongation at break values of the PLA/PC blend compatibilized with SAmfE were higher than those of the other blends. DSC analyses revealed that T_g and T_m values of the blends were not significantly affected by compatibilizer but, degree of crystallinity was found to be sensitive to compatibilizer type. DMA results showed that the best mechanical properties were obtained for the PLA/PC/SAmfE blend. When all of the results evaluated, it was found that the SAmfE is the most effective compatibilizer among the using compatibilizer types for PLA/PC blends.     

New strategies in the preparation of exfoliated thermoplastic starch-montmorillonite nanocomposites

A simple method based on the combination of the intercalation from solution and melt-processing preparation methods was used to prepare highly exfoliated and compatible thermoplastic starch (TPS) and montmorillonite clay (MMT) nanocomposites. The effects of the MMT content on the thermal, structural, and mechanical properties of the nanocomposites were investigated. XRD diffraction was used to investigate the MMT exfoliation/intercalation degrees in the TPS matrix. Data from thermogravimetric analysis and differential scanning calorimetry revealed that the addition of MMT increased the thermal stabilities of TPS nanocomposites. Young's modulus and tensile strength increased from 8.0 to 23.8 MPa and 1.5 to 2.8 MPa with an increasing MMT content from 0 to 5 wt% without diminishing their flexibility. The improvement in such properties can be attributed to the good dispersion/exfoliation of MMT in the TPS matrix. Combining both methods, it was possible to obtain homogenous and transparent nanocomposites with excellent thermal and mechanical properties for application as packaging materials.     

Degradation and rheological properties of biodegradable nanocomposites prepared by melt intercalation method

Biodegradable nanocomposites were prepared by mixing a polymer resin and layered silicates by the melt intercalation method. Internal structure of the nanocomposite was characterized by using the small angle X-ray scattering (SAXS) and transmission electron microscope (TEM). Nanocomposites having exfoliated and intercalated structures were obtained by employing two different organically modified nanoclays. Rheological properties in shear and extensional flows and biodegradability of nanocomposites were measured. In shear flow, shear thinning behavior and increased storage modulus were observed as the clay loading increased. In extensional flow, strain hardening behavior was observed in well dispersed system. Nanocomposites with the exfoliated structure had better biodegradability than nanocomposites with the intercalated structure or pure polymer.     

Incorporation of surface modified graphene nanoplatelets for development of shape memory PLA nanocomposite

In this study, a temperature sensitive shape memory polymer (SMP) system based on polylactic acid (PLA) has been developed and the effect of graphene nanoplatelets (GNPs) on the shape memory properties was evaluated. Dispersion of GNPs in PLA was improved with the aid of a zwitterionic surfactant. X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that the surface modified graphene nanoplatelets (SMGNPs) were exfoliated and homogenously dispersed in the PLA matrix due to enhancement of the polymer-graphene interaction. Mechanical properties of the samples namely stiffness and elasticity were increased upon incorporation of graphene nanoplatelets accompanied by their good dispersion in the PLA matrix. Furthermore, differential scanning calorimetry (DSC) revealed that the nucleation effect of graphene promote the crystallization and noticeably enhanced the degree of crystallinity. Finally, prominent mechanical properties along with high degree of crystallization due to fine dispersion of surface modified graphenes, resulted in drastic improvement in shape memory performance.     

Polystyrene nanocomposites viaIn-situ intercalated free radical polymerization

Organically modified montmorillonite (C₈PPh-MMT) was obtained using the ion exchange reaction between Na⁺-montmorillonite (Na⁺-MMT) and 1-octenyltriphenyl phosphonium chloride (C₈PPh-Cl⁻). Polystyrene nanocomposites were then prepared by in-situ free-radical polymerization of the styrene containing intercalated C₈PPh-MMT. The resulting polystyrene hybrids with various organoclay contents were investigated with FT-IR, which confirmed that PS hybrids were successfully prepared via the reaction of styrene monomer in the interlayers of the clays. The variations of the thermal behaviors of the hybrids with increases in the organoclay content from 0 to 8 wt% were determined. The glass transition temperatures (T_g) and initial thermal degradation temperatures (T_D ⁱ) of the PS hybrids were found to increase linearly with increases in the organoclay loading. Regardless of the organoclay content of the hybrids, the clay was found to be dispersed homogeneously in the matrix polymer. This is direct evidence that the PS hybrids formed nanocomposites. This result was confirmed with XRD and TEM.     

Enhanced mechanical and dielectric properties of poly(vinylidene fluoride)/polyurethane/multi-walled carbon nanotube nanocomposites

Multi-walled carbon nanotubes (MWNTs) nanocomposites with the polymer matrix composed of blends of poly(vinylidene fluoride) (PVDF) and polyurethane (PU) were prepared via functionalization of 3,4,5-triflouroaniline (TFA) on MWNTs. The MWNTs/polymer nanocomposites showed a dominantly enhanced elongation due to incorporation of PU molecules in PVDF matrix and the improved MWNTs dispersion in the polymer matrix resulting from functionalization of MWNTs with TFA. The functionalization of TFA on MWNTs was confirmed by the measurements of Raman, FT-IR spectra, SEM, and TEM images. In addition, the dielectric constant of nanocomposites increased with an increase of TFA-functionalized MWNTs in PVDF/PU/MWNTs nanocomposites. The polymer blend nanocomposites incorporating MWNTs may be available as an alternative potential route for the actuator materials.     

Marine Macroalgae as Sources of Polyunsaturated Fatty Acids

Algae from cold water (Canada) and warm water (China) were analysed for the total lipid content, and for their fatty acid (FA) composition and content. The major findings are that fatty acids (FA) from Canadian algae are generally richer in polyunsaturated FA (PUFA), with a higher n–3/n–6 FA ratio, and a higher degree of total unsaturation. The C 18:4 FA (stearidonic acid, morotic acid as synonym) was detected in greater amounts in cold water samples. The high levels of total PUFA, and especially of n–3 FA in Canadian algae, suggests possible utilization for nutritional purposes.     

Morphological, optical and electromagnetic characterization of polybutylene terephthalate/silica nanocomposites

Polybutylene terephthalate (PBT) composites containing 1 %, 3 % and 5 % silica nanoparticles were prepared by melt compounding method. The characteristics of the nanocomposites were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), tensile strength test (TST), reflectance spectroscopy (RS), electromagnetic transition test (ETT) and atomic force microscopy (AFM). XRD method showed successful incorporation of silica into the polymer matrix. SEM and AFM results showed the presence of silica aggregates on the surface of PBT sheets. Thermal analysis results demonstrated some changes in crystallinity of PBT after addition of silica. The PBT/silica nanocomposites were found to have higher electromagnetic reflection compared with the pure PBT. Silica nanoparticle is thus suggested as a good candidate for electromagnetic shielding purposes.     

Fabrication and characterization of dense Chitosan/polyvinyl-alcohol/poly-lactic-acid blend membranes

Dense membranes of Chitosan (CS)/Poly(vinyl alcohol) (PVA)/Poly(lactic acid) (PLA) blend were successfully fabricated using casting technique. The mechanical properties, moisture regain and water vapor permeability of polymer blend membranes were estimated by tensile test, moisture regain rate and dish method test respectively. The microstructures, morphology, chemical composition and thermal properties were also characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC) respectively. Results indicated that there were interactions and good compatibility among CS, PLA and PVA. And the blend membranes have good breaking elongation and slightly decreased breaking strength, and show best moisture regain at the case of CS60 (the content of CS in the blends is 60 %). They also have excellent porous structure, which is beneficial to their air permeability and may also contribute to cell regeneration. With the adding of PVA content, the melting peaks of blend membranes reduce and gradually close to that of PVA, demonstrating that the regularity of CS molecular chain may be destroyed and hydrogen bonds of macromolecules in polymers were newly formed. As a result, solution blending of the three polymers could complement their disadvantages and significantly improve the membrane performance of a single polymer, thus promote the mechanical and biological properties of blend membrane.     

Preparation,characterization of antibacterial PLA/TP nanofibers

Polylactic acid (PLA)/Tea polyphenol (TP) composite nanofilms were prepared using an electrospinning process. The mixed dichloromethane (DCM) and N,N-dinethylformamide (DMF) (70:30, v/v) was found to be the most suitable solvent for electrospinning. Various blends of PLA/TP solutions were formed. The morphology of the electrospun nano-scale fibers was investigated by scanning electron microscope (SEM), and the antibacterial performance was tested using shake flask method. The average diameter of the fibers is between 380 and 850 nm. It was found that the fiber diameter decreases as TP content increases, however the fibers may become brittle when the blend ratio of PLA and TP reached 50/50 (w/w). The antibacterial performance can be improved at the beginning when TP content increased. But it gradually gets impaired when TP content surpasses a certain value. The highest inhibitory rate against Escherichia coli and Staphylococcus aureus are 96.9 and 97.6 % respectively.