Mechanical and Thermal Properties of PLLA/PCL Modified Clay Nanocomposites

Poly(l-lactic acid) (PLLA)/poly(caprolactone) (PCL) and two types of organoclay (OMMT) including a fatty amide and ocatdecylamine montmorillonite (FA-MMT and ODA-MMT) were employed to produce polymer nanocomposites by melt blending. Materials were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), elemental analysis, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Mechanical properties were also investigated for these nanocomposites. The nanocomposites showed increasing mechanical properties and thermal stability. XRD results indicated that the materials formed nanocomposites. SEM morphology showed that increasing content of OMMT reduced the domain size of phase separated particles. TEM outcomes have confirmed the intercalated type of nanocomposite. Additionally, a solution casting process has been used to prepare these nanocomposites and characterized to compare these results with the above process.     

Study on Biodegradable Starch/OMMT Nanocomposites for Packaging Applications

The thermoplastic starch (TPS) and nanocomposite(TPS/OMMT) was prepared with 15% carbamide, 15% ethanolamine and different contents of organic activated montmorillonite (OMMT) by twin-screw extruder with a 130 °C barrel temperature. Fourier transforms infrared spectroscopy and wide angle X-ray diffraction shown that the alkylamine in dodecyl benzyl dimethyl ammonium bromide could react with MMT via cation exchange reaction. After treated, the d(001)space distance of MMT increased from 1.5 to 1.7 nm. Scanning electron microscope revealed that the lower contents of OMMT could disperse well in the matrixes of TPS. The carbamide, ethanolamine and the OMMT could destroy the crystallization behavior of starch, but only the OMMT restrained this behavior for long-term storing. Mechanical properties investigation indicated that the tensile strength and modulus of TPS/OMMT nanocomposites were better than those of TPS, while the elongation at break was descended with the increasing of OMMT contents. When the content of OMMT was 4%, the tensile strength and modulus of TPS was improved from 4.2 and 42 MPa to 6.0 and 76 MPa, respectively.     

Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)/Organomodified Montmorillonite Nanocomposites for Potential Food Packaging Applications

Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) is a versatile, biobased and biodegradable copolymer from the family of polyhydroxyalkanoates. This study aims to further ameliorate its properties in order to enhance its applicability for food packaging purposes through preparation of organomodified montmorillonite clay (OMMT) nanocomposites. Nanocomposites based on pure PHBHHx as well as commercial PHBHHx granulate, after a previous dry-mixing with OMMT in concentrations of 1, 3, 5 and 10 wt%, were prepared using melt blending and compression molding. Investigation of the samples showed well dispersed nanofiller and highly intercalated nanocomposites, resulting in a continuous decrease in gas permeability, lowering O₂, CO₂ and water vapor permeability with about 5–7 % and approximately 40 % at OMMT concentration of 1 and 10 wt%, respectively. Besides gas permeability, other properties were affected as well. Thermal stability of the samples increased gradually up to 5 wt% nanofiller, but was reduced at 10 wt%. In order to investigate the effects of OMMT and molecular weights on PHBHHx crystallization, nanocomposites were also produced by solvent-casting and compared to those obtained by melt-blending. Crystallization was retarded, because of severe lowering of molecular weight due to processing-induced chain scission, catalyzed by OMMT moisture. However, this reduction was counteracted for a large part by using commercial PHBHHx granulate, which has shown better crystallization properties. The samples were rendered increasingly more brittle, displaying higher Young’s modulus and severely reduced elongation at break. From this study it appeared that, upon viewing all affected properties as a whole, the sample based on commercial PHBHHx and containing 3 wt% OMMT shows most promise for possible applications, however further research must be performed in order to exploit their fullest potential.     

Effect of Sequential Mixing and Compounding Conditions on Cellulose Acetate/Layered Silicate Nanocomposites

Injection molded nanocomposites have been successfully fabricated from cellulose acetate (CA), eco-friendly triethyl citrate (TEC) plasticizer, and organically modified clay with and without maleic anhydride grafted cellulose acetate butyrate (CAB-g-MA) as a compatibilizer. The effects of processing conditions such as mixing methods, pre-plasticizing times, extruder retention times (RT) and addition of compatibilizer on the performance of these nanocomposites have been evaluated. The cellulosic plastic with CA/TEC (80/20 wt%) was used as the polymer matrix for nanocomposite fabrication. The morphologies of these nanocomposites were evaluated through X-ray diffraction (XRD) and transmission electron microscopy (TEM) studies. The mechanical properties of the nanocomposites were measured and have been correlated with the XRD and TEM observations. From all of the sequential mixing methods used, powder–powder mixing leads to the most transparent nanocomposites. Cellulosic plastic-based nanocomposites obtained using increased pre-plasticizing times and RT showed better exfoliated structures. In the system containing compatibilizer, the minimum retention time required for obtaining almost completely exfoliated hybrid nanocomposites was shorter than in the system without compatibilizer.     

Degradation Study of Biobased Polyester–Polyurethane and its Nanocomposite Under Natural Soil Burial,UV Radiation and Hydrolytic-Salt Water Circumstances

The current study focuses on the development of a formulation of polyester polyurethane (PEPU) samples using castor oil (CO) modified polyester polyol and partially biobased aliphatic isocyanate. The CO modified polyester polyol was synthesized employing transesterification reaction between CO and diethylene glycol in the presence litharge (PbO) catalyst. Subsequently, the modification of CO was confirmed using proton nuclear magnetic resonance (¹HNMR) spectra analysis. In the next stage, the biobased polyester polyurethane nanocomposites (PEPUNC) were prepared by incorporating 3 wt% OMMT nanoclay within PEPU through in situ polymerization technique. The produced PEPU was confirmed by Fourier transform infrared spectroscopy (FTIR) and ¹HNMR spectra analysis. Further, the degradation properties of developed PEPU subjected to soil-burial, UV exposure and hydrolytic-salt water medium were noted by FTIR spectroscopy. Corresponding weight loss, mechanical measurements and morphological studies through scanning electron microscopy (SEM) analysis were studied. The results showed that the addition of OMMT nanoclay within the PEPU matrix produces significant improvement in the degradation rate which indicated the susceptibility of OMMT nanoclay to humidity upon exposure to soil burial. The produced microorganisms from the soil resulted in significant chemical and morphological changes in the entire structure of the PEPU. Additionally, the highest degradation and percentage of weight loss was observed under soil burial as compared to UV exposure and hydrolytic-salt water medium.     

Characterization of Extruded Thermoplastic Starch Reinforced by Montmorillonite Nanoclay

The purpose of this study was to understand how the montmorillonite (MMT) nanoclay influences physical and mechanical properties of thermoplastic starch (TPS), which was produced by a conventional extrusion procedure. MMT nanoclay was added at 0, 4, and 8 % (w/w) concentrations. Transmission electron microscopy (TEM) showed most MMT platelets existed in tactoid structure in the starch matrix. In addition, FTIR spectra indicated TPS/MMT nanocomposites kept chemically stable after the extrusion. Tensile strength (TS) was about 7.0 MPa, while elongation-at-break (E) and elastic modulus (EM) were about 52 % and 32–41 MPa, respectively. Moisture sorption behaviour of the samples was well described by GAB and BET models. Thermal property tests exhibited the glass transition temperature (T _g ) of the nanocomposites decreased with increasing MMT from 0 to 8 %, indicating MMT nanoclay had a plasticization effect.     

Synthesis,Characterization and Application of α, β, and γ Cyclodextrin-Conjugated Graphene Oxide for Removing Cadmium Ions from Aqueous Media

In this study, a novel and facile route for the synthesis of cyclodextrin-conjugated graphene oxide (CDs–GO) nanocomposites by esterification reaction in the presence of EDC/DMAP as catalyst, was developed. The formation of CDs–GO was successfully approved by FT-IR, SEM, TEM, TGA and BET analyses. Then competitive adsorption capacity of cadmium ion by CDs–GO composites and the impact of different empirical parameters like contact time, initial metal ion concentration, and initial pH on the adsorption process were studied. The results showed that β-CD–GO at pH 7 is suitable for removing Cd(II) with 90?% removal efficiency. Also, the adsorption capacity experiment at constant concentration of 50 ppm of Cd(II) showed that more than 50?% of Cd(II) ions could be adsorbed by γ-CD–GO reaching an equilibrium within 2 h. Therefore, the γ-CD–GO and α-CD–GO showed high adsorption capacity toward Cd²⁺ (222.22 mg/g) which were pointedly more than that of β-CD–GO (208.33 mg/g). Furthermore, adsorption kinetics, isotherm studies, and thermodynamic analyses were evaluated. The adsorption data exhibited excellent fit to the pseudo-second-order (R²?>?0.99) and Freundlich isotherm models.

     

Life Cycle Analysis of Extruded Films Based on Poly(lactic acid)/Cellulose Nanocrystal/Limonene: A Comparative Study with ATBC Plasticized PLA/OMMT Systems

Life cycle analysis (LCA) of limonene plasticized poly(lactic acid) (PLA) films containing cellulose nanocrystals (CNC) extracted, by acid hydrolysis, from Phormium tenax leaf fibres, was assessed and compared with the results of acetyl tributyl citrate (ATBC) plasticized PLA films, having equivalent mechanical properties, containing organo-modified montmorillonite (OMMT). Eco-Indicator 99 tool has been adopted as the main method for life cycle assessment. Results indicated that, despite CNC are biobased fillers obtained by natural sources, the related chemical extraction leads to a large environmental footprint and a relatively relevant energy expense. LCA characterization of these films demonstrated that the environmental impact of PLA/limonene film reinforced with 1% in weight of CNC (PLA/CNC/limonene) is comparable to the environmental impact of polylactic acid films reinforced with OMMT and plasticized with a petroleum based plasticizer (ATBC) (PLA/OMTT/ATBC). A “cradle to gate” approach has been considered for both the film typologies.     

Biodegradable nanocomposites based on poly(butylene succinate)/organoclay

In this work, we try to incorporate the inorganic system into the biodegradable polymers to compose an organic/inorganic polymer hybrid. Various nanocomposites of poly(butylene succinates) (PBS) with different ratios of organically modified layered silicates (OMLS) prepared by solution blending were investigated. The OMLS used for the preparation of nanocomposites were functionalized ammonium salts modified montmorillonite. The effects of OMLS on the nanocomposites were investigated by XRD, TEM, DMA and TGA in the aspect of the d-spacing of clay, mechanical and thermal properties. Interestingly, all these nanocomposites exhibited improved properties when compared with the pristine PBS sample. XRD indicates that the layers of clay were intercalated by the modifiers, and the interlayer distance of organoclay in the nanocomposites could be extended to about 29.4 Å. Moreover, the thermal stability of the nanocomposites was enhanced by the addition of organoclay via TGA study, closely related to the organoclay content in the PBS matrix. DMA data shows that the storage and loss moduli were concurrently enhanced by the addition of organoclay as compared to the pristine PBS sample. Moreover, the glass transition temperatures also increased about 5 to 20 °C (from DMA, peak of tanδ) for the various organoclay-containing samples. The enhanced mechanical and thermal properties can be achieved from these organoclay modified-nanocomposites.     

The Effect of Acetylation on the Hydrolytic Degradation of PLA/Clay Nanocomposites

In this study, the hydrolytic degradation of Poly(lactic acid) (PLA) and acetylated PLA (PLA-Ac)–clay nanocomposites were investigated. The organo clay was obtained by ion exchange reaction using cetyl tri methyl ammonium bromide (CTAB). Nanocomposites containing 2, 5 and 8% mass ratio of organo clay (CTAB-O) were prepared. PLA and its organo clay nanocomposites were characterized by scanning electron microscope (SEM), thermo gravimetric analysis (TGA) and X-ray diffraction (XRD) to determine the morphology before and after hydrolytic degradation. Fourier transform infrared (FTIR) analyses of PLA and PLA-Ac were also obtained. The hydrolytic degradation of polymers and their composites were investigated in the phosphate buffered saline solution (PBS). The results showed that controlled hydrolytic degradation was observed in the samples with end group modification of PLA. While weight loss of PLA films was 28%, that of PLA-Ac films was 18% after 60 days degradation time. The weight loss was obtained as 29.5 and 25.5% for PLA-5 wt% organo clay (PLA/5CTAB-O) and PLA-Ac-5 wt% organo clay (PLA-Ac/5CTAB-O) nanocomposites films, respectively. It was also observed that thermal degradation of PLA-Ac was much more than that of PLA. Hydrolytic degradation increased depending on organo clay content. The end group modificated PLA results in controlled hydrolytic degradation. While hydrolytic degradation in polymer films occurred as surface erosion, bulk erosion was observed in composite films.     

Thermal and Flame Retardancy Behavior of Oil Palm Based Epoxy Nanocomposites

The aim of present study was to investigate the thermal properties and flame retardancy behavior of flame retardant (FR) epoxy nanocomposites from chemically treated (bromine water and tin chloride) oil palm empty fruit bunch (OPEFB) nano filler at different filler loading (1, 3, 5%). Thermal properties were evaluated through thermogravimetry analyzer, derivative thermogravimetry and differential scanning calorimetry. FR properties of nanocomposites are evaluated through UL-94 vertical burning test and limiting oxygen index (LOI). The functional group analysis of all composites was made by FTIR spectroscopy. Thermal analysis shows that degradation temperature of epoxy composites shifts from 370 to 410 °C and char yield also increases for 3% loading. Furthermore LOI value of 29% and UL-94 rating of V-0 with no flame dripping and cotton ignition, revealed that 3% oil palm nano filler filled epoxy nanocomposites display satisfactory flame retardancy. The superior flame retardancy of epoxy nanocomposites are attributed to the chemical reactions occurred in the gaseous phases and the profound synergistic flame retardation effect of tin with bromine in the treated nano OPEFB filler. All the epoxy nanocomposites displayed almost similar FTIR spectra with the characteristics metal-halogen bond supporting the synergism. Homogeneous dispersion of 3% oil palm nano filler act as highly effective combustion chain terminating agent compared with 1 and 5% nano OPEFB/epoxy nanocomposites.     

PLA and Organoclays Nanocomposites: Degradation Process and Evaluation of ecotoxicity Using Allium cepa as Test Organism

In this study, nanocomposites of PLA and organoclays Cloisite 20A and Cloisite 30B were prepared by the melt intercalation method and the obtained samples were characterized by transmission electron microscopy (TEM). Since composting is an important proposal to the final disposal of biopolymers, the influence of clays on the hydrolytic degradation process of PLA was evaluated by visual analysis and monitoring of molecular weight after periods of 15 and 30 days of degradation in compost. After degradation of the materials in composting environment, the evaluation of cytotoxic, genotoxic and mutagenic effects of compost aqueous extract was carried out using a bioassay with Allium cepa as test organism. The TEM micrographs permitted the observation of different levels of dispersion, including exfoliated regions. In the evaluation of hydrolytic degradation it was noted that the presence of organoclays can decrease the rate of degradation possibly due to the barrier effect of clay layers and/or the higher degree of crystallinity in the nanocomposite samples. Nevertheless, even in the case of nanocomposites, the molecular weight reduction was significant, indicating that the composting process is favorable to the chain scission of PLA in studied materials. In the analysis performed by the bioassay using A. cepa as test organism, it was found that after degradation of the PLA and its nanocomposites the aqueous extract of compost samples induced a decreasing in the mitotic index and an increasing in the induction of chromosomal abnormalities. These results were statistically significant in relation to the negative control (distilled water). By comparing the results obtained for the nanocomposites in relative to pure polymer, there were no statistically significant differences. The types of the observed chromosomal aberrations indicated a possible genotoxic effect of the materials, which may be related to an aneugenic action of PLA degradation products.     

Synthesis,Characterization and Application of Biodegradable Crosslinked Carboxymethyl Chitosan/Poly(Ethylene Glycol) Clay Nanocomposites

Crosslinked carboxymethyl chitosan (CMCh)/poly(ethylene glycol) (PEG) nanocomposites were synthesized using terephthaloyl diisothiocyanate as a crosslinking agent, in presence of montmorillonite (MMT), in different weight ratios of the two matrices. Characterization of nanocomposites was performed using different analyses. Swelling behavior was studied in different buffered solutions. It was found that formation of crosslinked CMCh/PEG nanocomposites increased the swell ability. Metal ions adsorption had also been investigated. The results indicated that crosslinked CMCh adsorbs various metal ions much more than non-crosslinked CMCh. Antimicrobial activity was examined against Gram-positive bacteria (S. aureus (RCMB 010027) and S. Pyogens (RCMB 010015), Gram-negative bacteria (E. coli (RCMB 010056), and also against fungi (A. fumigates (RCMBA 02564, G. candidum (RCMB 05096) and C. albicans (RCMB 05035). Data indicated that most of these nanocomposites exhibited good antimicrobial potency. Degradation studies were carried out in simulated body fluid for different time periods in order to find out the degradation index. Results showed that weight loss (%) of most of the nanocomposites increased as a function of incubation time.     

Comparative Sustainability Assessment of Starch Nanocrystals

Fossil energy depletion and growing environmental concerns have brought up increasing interest in bio-based eco-efficient and high technology materials. Among them, starch nanocrystals (SNC) consist of crystalline nano-platelets produced from the hydrolysis of starch and mainly used as nano-fillers in polymeric matrix. New applications have brought up the need for scaling-up the SNC preparation process. However, for this new bio-based nano-material to be sustainable, its preparation and processing should have limited impacts on the environment. Thus, together with analyzing and making recommendations for the scaling-up of SNC production process, it is worth identifying “environmentally sensitive” steps using life cycle analysis (LCA). To that purpose, different scenarios have been proposed and compared according to different environmental impacts. Also, a comparison to its main competitor, i.e. organically modified nanoclay (OMMT), is proposed. From a LCA point of view, SNC preparation requires less energy than OMMT extraction, but global warming and acidification indicators were higher than for OMMT. However, SNC have the added advantages to be renewable and biodegradable contrary to OMMT which contribute to non-renewable energy and mineral depletion. Thus, used as filler, SNC have a positive impact on the end of life of the filled material. From these observations, recommendations for the scaling-up of the SNC preparation process are made and deal mainly with the use of land and water.     

Aging of Toughened Polylactic Acid Nanocomposites: Water Absorption,Hygrothermal Degradation and Soil Burial Analysis

The environmental aging behaviour of montmorillonite (MMT) filled polylactic acid (PLA) nanocomposites (PLA/MMT) and linear low density polyethylene (LLDPE)-toughened PLA (PLA/LLDPE ratio = 90/10) nanocomposites (PLA/LLDPE/MMT) were investigated in this study. The nanocomposites were subjected to water absorption, hygrothermal degradation and soil burial analysis. Both PLA/MMT and PLA/LLDPE/MMT nanocomposites were immersed in distilled water at three different temperatures (room temperature, 60, and 90 °C) and the weight difference before and after immersion was calculated. The kinetics of water absorption for both nanocomposites followed the Fick’s second law of diffusion, where a linear relationship exists between the initial moisture absorption at any time t and t ^1/2 (the square root of time), followed by a horizontal plateau (saturation). The equilibrium moisture content (M _m ) and diffusion coefficient (D) of PLA nanocomposites increased with the addition of MMT (2 phr) and LLDPE. However, the D values of both nanocomposites decreased by increasing MMT (4 phr). The M _m for PLA/MMT and PLA/LLDPE/MMT nanocomposites increased by increasing immersion temperature (60 °C) and prolonged immersion resulted in hygrothermal degradation of both nanocomposites. The hygrothermal degradation studies showed that PLA degrades much faster at 90 °C as compared to 60 °C in both the nanocomposites. The addition of MMT and LLDPE improved the hygrothermal stability of PLA in both nanocomposites. Soil burial test revealed deterioration of impact strength in all samples while the rate of biodegradation was retarded in the presence of MMT and LLDPE.     

Study of Thermo-Mechanical and Morphological Behaviour of Biodegradable PLA/PBAT/Layered Silicate Blend Nanocomposites

Poly (lactic acid) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT) blend nanocomposites were prepared using melt blending technique followed by compression moulding. The blend nanocomposites were prepared with a variation of PBAT loading along with maleic anhydride and benzoyl peroxide ranging from 5 to 20 wt% along with two different commercially available nanoclays cloisite 93A and cloisite 30B (C30B) at 3 wt% loading. The maleic anhydride and benzoyl peroxide were used during the melt blending of the blend nanocomposites as a compatibilizer and as an accelerator respectively. Maleic anhydride used to enhance the compatibility of the PLA/PBAT blend and as well as the uniform adhesion of the nanoclays with them. The properties and characterizations of PLA matrix and the PLA/PBAT blend nanocomposites have been studied. The tensile strength, % elongation and impact strength increased with the preparation of PLA/PBAT blend nanocomposites as compared with PLA matrix. PLA/PBAT/C30B blend nanocomposites exhibited optimum tensile strength at 15 wt% of PBAT loading. Differential scanning calorimetry and thermogravimetric analysis also showed improved thermal properties as compared with virgin PLA. The wide angle X-ray diffraction studies indicated an increase in d-spacing in PLA/PBAT/C30B blend nanocomposite thus revealing intercalated morphology.     

Assessment of Ball Milling as a Compounding Technique to Develop Nanocomposites of Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate) and Bacterial Cellulose Nanowhiskers

The aim of this study was the assessment of high energy ball milling technique to develop poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanocomposites containing bacterial cellulose nanowhiskers (BCNW). Crystallization behaviour of PHBV/BCNW nanocomposites was studied under non-isothermal and isothermal conditions using differential scanning calorimetry. The changes in PHBV crystalline structure were also studied using X-ray diffraction. The results confirmed that BCNW acted as nucleating agents and, hence, favored the crystallization of the PHBV. The oxygen permeability of the nanocomposites was reduced by ~22 % when compared to that of the neat PHBV. This work provides a new insight into the development of polyhydroxyalkanoate composites by means of the high energy ball milling technique.     

A Comparison of Modified and Unmodified Cellulose Nanofiber Reinforced Polylactic Acid (PLA) Prepared by Twin Screw Extrusion

The goal of this work was to evaluate the effect of chemical modification of cellulose nanofibers (CNF) on the properties of polylactic acid (PLA) nanocomposites. Acetylated nanofibers (ACNF), with degree of substitution 1.07, were isolated from acetylated kenaf fibers by mechanical treatments. Acetylated nanofibers showed more hydrophobic properties compared to non-acetylated ones. The results showed that both crystallinity and thermal stability of acetylated nanofibers were lower than non-acetylated ones. The nanocomposites were prepared by premixing two PLA master batches, one with a high concentration of ACNF and the second with CNF. These were diluted to final concentrations (5?wt%) during the extrusion. The morphology studies of PLA and its nanocomposites showed nanofiber aggregates in both materials. The results showed that the tensile and dynamic mechanical properties were enhanced for both acetylated and non-acetylated nanocomposites compared to the neat PLA matrix while no significant improvement was observed for the acetylated nanocomposites compared to non-acetylated ones. However, the storage modulus increased slightly for acetylated nanocomposites compared to non-acetylated ones.     

Fabrication and Characterization of PLA/PHBV-Chitin Nanocomposites and Their Foams

This paper examines the effect of biobased chitin nanowhisker fillers on the thermal, rheological, physical, mechanical and morphological properties of biobased polylactic acid (PLA) and PLA/polyhydroxybutyrate-co-valerate (PHBV) blended nanocomposites as well as the physical, mechanical and morphological properties of porous PLA and PLA/PHBV nanocomposite foams. Solid nanocomposites of PLA, PLA/PHBV and chitin nanowhiskers were manufactured through melt blending while porous nanocomposites foams were fabricated through a batch foaming process with the aid of CO₂ as blowing agent. It was found that by incorporating small quantities of chitin nanowhiskers (<2 wt%) the mechanical properties of solid specimens are improved while strength and expandability of the foam can be significantly improved, yielding a homogenously distributed cell morphology with average cell size of 1.5 μm.     

Preparation of Lignin Sulfonate Based/Organo-Montmorillonite Composite Hydrogel for Adsorbing Methylene Blue from Aqueous Solution

Journal of Polymers and the Environment - In this study, an environmentally friendly lignin-based hybrid hydrogel (LS/OMMT) was prepared by grafting of acrylamide (AM) and acrylic acid (AA) onto...