Preparation and Properties of Green Composites Based on Tapioca Starch and Differently Recycled Paper Cellulose Fibers

Green composites obtained from biodegradable renewable resources have gained much attention due to environmental problems resulting from conventionally synthetic plastics and a global increasing demand for alternatives to fossil resources. In this work we used different cellulose fibers from used office paper and newspaper as reinforcement for thermoplastic starch (TPS) in order to improve their poor mechanical, thermal and water resistance properties. These composites were prepared by using tapioca starch plasticized by glycerol (30 % wt/wt of glycerol to starch) as matrix reinforced by the extracted cellulose fibers with the contents ranging from 0 to 8 % (wt/wt of fibers to matrix). Properties of composites were determined by mechanical tensile tests, differential scanning calorimetry, thermogravimetric analysis, water absorption measurements, scanning electron microscopy, and soil burial tests. The results showed that the introduction of either office paper or newspaper cellulose fibers caused the improvement of tensile strength and elastic modulus, thermal stability, and water resistance for composites when compared to the non-reinforced TPS. Scanning electron microscopy showed a good adhesion between matrix and fibers. Moreover, the composites biological degraded completely after 8 weeks but required a longer time compared to the non-reinforced TPS. The results indicated that these green composites could be utilized as commodity plastics being strong, inexpensive, plentiful and recyclable.     

New Multi-Scale Hybrid System Based on Maple Wood Flour and Nano Crystalline Cellulose: Morphological,Mechanical and Physical Study

In the first part of this work, composites based on polypropylene (PP) and maple wood flour (MF) were prepared by melt compounding using twin-screw extrusion followed by compression molding. The morphological and mechanical properties of the composites were analyzed for three samples: PP, MF/PP and MF/PP containing maleic anhydride grafted polypropylene (MAPP) as coupling agent. The results showed that MF/PP composites have improved mechanical properties, especially tensile modulus (+33 %), with only 8 % increase in density. The addition of MAPP further improved the mechanical properties, in particular tensile modulus (up to 51 %), which could be related to better fiber/matrix adhesion. In the second step, nano crystalline cellulose (NCC) was added to all samples to produce NCC-MF/PP hybrid composites. From the mechanical analysis performed, the hybrid composites with MAPP have improved properties, especially tensile (+53 %) and flexural (+40 %) moduli. These results confirmed that multi-scale hybrid NCC-MF composites can substantially improve the mechanical properties of polyolefins with limited increase in density (14 %) leading to high specific properties.     

Extraction and Characterization of Nanocrystalline Cellulose from Doum (<Emphasis Type="Italic">Chamaerops humilis</Emphasis>) Leaves: A Potential Reinforcing Biomaterial

The aim of this investigation was to extract nanocrystalline cellulose (NCC) from Moroccan Doum fibers (Chamaerops humilis) by chemical treatment to examine their potential for use as reinforcement fibers in bionanocomposite applications. The chemical composition, morphological and structural properties of the Doum fibers was determined at different stages of chemical treatment. Morphological (transmission electron microscopy and scanning electron microscopy), structural characterization (X-ray diffraction, Fourier transformed infrared), thermal characterization (thermogravimetric analysis). The suspension electrostatic stabilization (zeta potential) of NCCs was also carried out. The results of these characterization analysis found that average size of the NCC is 220 nm in length and 11 nm in diameter, with high crystallinity index (93 %), a thermal stability comparable to that of untreated Doum fibers (degradation temperature 340 °C), which is reasonably promising for the use of these nanofibers in reinforced-polymer manufacturing, and a good stability in water suspension that it allows their utilization such as reinforcement of the water-soluble polymers to prepare the bio-nanocomposite.     

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.     

New Non-food-Based Composites of Acorn Nutlet and Polycaprolactone: Preparation and Characterization Evaluation

Two dissimilar renewable resource-based thermoplastic acorn nutlet (TPAN) materials were prepared via twin-screw extrusion with the aid of glycerol or monoethanolamine as plasticizers, and then two TPAN/polycaprolactone (PCL) composites with different plasticized systems were prepared. Mechanical test showed that glycerol-based composites had excellent tensile properties, and at a PCL content of 50 wt%, their tensile strength and elongation at break reached 14.4 MPa and 1,361 %, respectively. The micro-morphologic investigation of liquid-nitrogen brittle fracture surface indicated certain interface adhesion between glycerol-based thermoplastic acorn nutlet (GTPAN) and PCL. Dynamic mechanical thermal analysis , differential scanning calorimetry and thermogravimetric analysis demonstrated that the weight ratios of TPAN in composites significantly affected the crystallinity, glass transition temperature (T_g), melting temperature (T_m) and thermal stability of composites. Soil burial degradation analysis displayed that all composites had excellent biodegradability. These results demonstrated that GTPAN/PCL composites had superior mechanical and biodegradable properties, enough to partially replace the conventional thermoplastic plastics.     

A Biobased Blend of Cellulose Diacetate with Starch

Two bio-based polymers, cellulose diacetate (CDA) and starch, were used to prepare blends with reasonable properties and low cost. Due to the poor processing properties, starch was modified in the presence of glycerol and epoxidized soybean oil (ESO), and CDA was plasticized by triacetin (TA) and ESO, respectively. The morphologies of the blends with different amounts of modified starch (MST) were studied by scanning electron microscope (SEM), and the physical properties of the blends, including thermal stability, mechanical property, water and moisture resistance, were investigated. The equilibrium moisture absorption rates of the blends containing 30 and 50 wt% MST at 100 % of relative humidity(RH) were 9.4 and 15.0 %, respectively. SEM and DMA results demonstrated that CDA and MST had a certain extent of compatibility. Due to the partial plasticization of starch, the tensile strength of the blends was nearly not affected by the amount of MST. Even if 50 wt% MST was added, the tensile strength of the blend was as high as 24.7 MPa. The obtained blend containing 30 wt% MST can keep good mechanical properties at 50 % RH, and its tensile strength and elongation at break are 30.2 MPa and 3.6 %, respectively. All the results show that the CDA/MST blends have a potential as an environmental friendly material.     

Effect of Gamma Radiation on the Properties of Crosslinked Chitosan Nano-composite Film

Chitosan nano-composite film crosslinked by citric acid and with glycerol as plasticizer and MgO as antibacterial agent was prepared by casting method. MgO nanoparticles were synthesized via calcination method in furnace at 500 °C for 4 h and characterized by X-ray diffraction and transmission electron microscope. The chitosan nano-composite film with composition chitosan/citric/glycerol/magnesium oxide (1 wt%:1 wt%:75 vol%:10 wt%) has high mechanical properties than other films. The effects of different irradiation doses on the mechanical, thermal and antibacterial activity were investigated. The tensile strength enhanced by increasing irradiation dose up to 10 kGy and the elongation negligible changed as irradiation dose increased. The thermal stability slightly increased up to dose 2.5 kGy then decreased with dose increment. The antimicrobial activity film was studied against white mulberry-borne bacterial pathogens either Gram positive or Gram negative bacteria and has positive impact of gamma irradiation on the antimicrobial activity. The use of the selected chitosan nano-composite film which irradiated by dose of 2.5 kGy and has magnesium oxide of average particle size 54.3 nm as new packaging materials found to improve storage quality and shelf-life of mulberry fruit.     

Behavior of Cellulose Reinforced Cross-Linked Starch Composite Films Made with Tartaric Acid Modified Starch Microparticles

Tartaric acid modified starch microparticles (TA-SM) previously obtained using the dry preparation technique were introduced as filler within glycerol plasticized-corn starch (GCS), the composites being prepared by casting process. The effects of cellulose addition within the TA-SM-GCS matrix on the structure, surface properties and water sorption, as well as mechanical and thermal properties of starch-based composite films were investigated. The water resistance and thermal stability were slightly improved through addition of high content of cellulose due to the inter-component H-bonding between components. The evaluation of mechanical properties evidenced a significant increase of the tensile strength of the composites with increasing the content level of cellulose.     

Polyhydroxybutyrate-Based Nanocomposites with Cellulose Nanocrystals and Bacterial Cellulose

Polyhydroxybutyrate (PHB) films nanoreinforced with hydrolyzed cellulose nanocrystals (CNC) and bacterial cellulose (BC) were prepared by solvent casting. The influence of different cellulose nanoparticles content (2, 4 and 6 wt% of CNC and 2 wt% of BC) on the PHB properties was studied. CNC nanocomposites presented good dispersion of the nanocrystals, improving transparency, mechanical and barrier properties of the PHB films. On the other hand, reduced thermal stability and mechanical properties were yielded by BC addition due to the intrinsic lower degradation temperature and higher length of the BC nanofibrils compared to CNC. Nanocomposites performance variation is mainly caused by the marked difference in nanoparticles structure. It was demonstrated that PHB–CNC films exhibited higher performance enhancement without detrimental effect of the pristine PHB properties.     

Performance of Cow Dung Reinforced Biodegradable Poly(Lactic Acid) Biocomposites for Structural Applications

In this work, performance of cow dung (CD) reinforced poly(lactic acid) (PLA) biocomposites was investigated for the potential use in load bearing application. CD of average 4 mm size was blended with PLA at different CD ratios (0–50 wt%) and their effects on the biocomposite properties were studied. The results showed an improvement in the flexural properties, while the tensile and impact strength dropped by 20 and 28% with the addition of 50% CD. The decline in the tensile and impact strength was due to micro-cracking and voids formation at higher CD content. Also, the incorporation of CD slightly decreased the thermal stability of the biocomposite. However, dynamic mechanical properties of the biocomposites generally improved. SEM analysis of tensile and impact fractured surfaces indicated that the CD had a reasonable adhesion with matrix. Moreover, the SEM micrographs of soil burial studies showed an accelerated degradation of higher CD wt% biocomposites.     

Preparation and Properties of Propylene Glycol Plasticized Wheat Protein Isolate Novel Green Films

Novel bio-based green films were prepared using wheat protein isolate (WPI) by solution casting method using Propylene Glycol as a plasticizer for packaging applications. The effect of the plasticizer content (10, 15, 20 and 25 wt%) on mechanical properties (tensile strength, young’s modulus and  % of elongation) was investigated. A thermal degradation and phase transition of the prepared WPI was assessed by means of TGA and DSC analysis. The results showed that the tensile strength and young’s modulus decreased and  % of elongation increased with increasing PG content. The ATR-FTIR and SEM were used for structural characterization and morphology of the films, respectively. FTIR studies reveals that the intensity of the bands corresponding to the amide groups increases with increasing PG content tending to increase protein–PG interactions. Further, the glass transition temperature was decreased and the thermal stability of the WPI was found to be increased by plasticization. The overall thermal stability of the films was improved and is attributed to the increase in mobility of the polymer chains.     

Experimental Investigation of Cellulose/Silver Nanocomposites Using In Situ Generation Method

Cellulose gel films were prepared by regeneration process using pre-cooled aq.(8 wt% LiOH + 15 wt% urea) mixture as solvent and ethyl alcohol as non solvent. The Terminus cattapa leaf extract diffused wet cellulose films were then dipped in 1–5 mM aq.AgNO₃ solutions to allow in situ generation of silver nanoparticles (AgNPs). Besides the in situ generation, some AgNPs were also formed outside the wet films in the solution. The AgNPs formed outside the films were observed under transmission electron microscope and scanning electron microscope. The nanocomposite films were also characterized by Fourier transform infrared spectroscopy, X-ray diffraction and thermogravimetric analysis and tensile test. The thermal stability of the composite films was lower than that of the matrix up to a temperature of ~300 °C and afterwards showed a reverse trend. The tensile strength of the nanocomposite films was found to be higher than the matrix but decreased with increasing concentration of aq.AgNO₃. The cellulose/AgNPs composite films showed good antibacterial activity against E. coli (gram positive) and Bacillus sp. (gram negative). Based on the aforementioned properties, the cellulose/AgNPs composite films can be considered for antibacterial packaging and medical applications.     

Environmentally Friendly Oil-Modified Polyesters as Polymeric Plasticizers for Poly(vinyl chloride)

Oil-modified polyesters were synthesized to serve as polymeric plasticizers for PVC. A total of four polymeric plasticizers with different average molecular weights were prepared. Characterizations were done using Fourier-transformed infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and gel permeation chromatography. Some of the tests conducted on PVC films include thermal stability test using thermogravimetric analyser, determination of glass transition temperature (T_g), plasticizer migration and leaching resistance test, morphology study of plasticized PVC films using field emission scanning microscope, toxicity test, and tensile test. Owing to the plasticizing effect of the palm oil-based compound, T_g of the plasticized PVC has decreased to an average of 65 °C at 20 wt% loading. The polymeric plasticizer is also able to contribute positively to the thermal stability and mechanical properties of the PVC films. Some of the advantages of incorporating polymeric plasticizer with high molecular weight includes lower rate of leaching from plastic, and improved tensile strength and elongation at break. Besides, thermal stability of the plastic studied using Kissinger’s and Flynn–Wall–Ozawa’s approaches shows that PVC blended with high molecular weight oil-modified polyester is more thermally stable, evidenced by the increase in the activation energy of decomposition, E_d. Toxicity test using brine shrimp egg shows encouraging results, where the oil-based plasticizer is considerably less toxic compared to some of the commercial plasticizers.     

Phosphogypsum Waste Used as Reinforcing Fillers in Polypropylene Based Composites: Structural,Mechanical and Thermal Properties

The industrial production of wet phosphoric acid in Morocco led to controversial stockpiling of waste phosphogypsum by-products resulting in the release of significant amounts of toxic impurities in salt marshes. In the framework of fighting against global climate change and efforts to reduce toxic industrial wastes (phosphate industry), this work presents a new polymer composite based on phosphogypsum (PhG) and polypropylene (PP).The compounds were produced by twin-screw extrusion and injection molding. The morphological results show that good affinity between PhG and PP led to good particle dispersion/distribution in the polymer matrix. Thermal characterizations showed that PhG particles improved the thermal stability of PP with a 50 °C increase at 40 wt%. The optimum tensile modulus was also obtained at 40 wt% with a 74 % increase over neat PP. Dynamical mechanical analysis showed that PhG addition can improve the viscoelastic properties of PP for potential applications under dynamic stress. Overall, it can be concluded that PhG is potential reinforcing filler for the production of PP composites and represents a promising avenue for the valorization of this waste as a new raw material while resolving some environmental issues.     

Melt Compounded Blends of Short and Medium Chain-Length Poly-3-hydroxyalkanoates

Blends of poly-3-hydroxybutyrate with an elastomeric medium-chain-length poly-3-hydroxyalkanoate (MCL-PHA), containing 98 mol% 3-hydroxyoctanoate and 2 mol% 3-hydroxyhexanoate (referred to as PHO), were prepared by melt compounding. Coarsening of the droplet-matrix morphology of the blends was noted as the PHO content increased beyond 5 wt%; this was attributed to the significant viscosity mismatch between the components. Addition of PHO improved the thermal stability of the blends, reduced their crystallinity and resulted in shifts in their melting and crystallization temperatures. The blends had improved tensile strain at break. The unnotched impact strength showed a threefold increase at 30 wt% PHO content. Cross-linking of PHO using a peroxide initiator increased its viscosity, thus improving the morphology and mechanical properties of the blends.     

Poly(lactic acid)-Based Composites Containing Natural Fillers: Thermal,Mechanical and Barrier Properties

Natural filler/poly(lactic acid)-Based composites have been prepared by melt blending in order to investigate the resulting thermal, mechanical, and oxygen permeability properties. To this aim, several wastes or by-products (namely, cellulose fibers, wood sawdust, hazelnut shells, flax fibers, corn cob and starch) have been used, ranging from 10 to 30 wt%. The presence of these fillers is responsible of a slight reduction of the polymer degradation temperature in nitrogen as well as of a significant increase of the storage modulus as a function of the filler content. The experimental data obtained by dynamic mechanical analysis have been mathematically fitted, employing three micromechanical models (namely, Voigt, Reuss and Halpin–Tsai). Furthermore, the presence of cellulose or starch has turned out to significantly reduce the polymer oxygen permeability. Finally, in order to fully assess the feasibility of such materials, an economic analysis has been carried out and discussed.     

Preparation and Characterization of Biodegradable Blend Membranes of PBS/CA

Asymmetric membranes of cellulose acetate/poly (butylene succinate) were prepared using immersion precipitation technique. The blended membranes were characterized by contact angle, scanning electron microscopy, thermogravimetric analysis, degradation test in compost and dynamic test of raisin wastewater treatment. Results demonstrated that hydrophilicity of cellulose acetate was enhanced by addition of poly (butylene succinate) up to 50 %. Furthermore, polymeric composition affects cross sectional structure of the membranes by controlling formation of macrovoids. Addition of poly (butylene succinate) improved the membranes thermal stability and obviously their degradation in compost. The prepared membranes were able to reject the wastewater pollutants properly.     

Utilization of Sunflower Stalk in Manufacture of Thermoplastic Composite

Dimensional stability and mechanical performance of polypropylene thermoplastic composites filled with sunflower stalk (SS) flour at 30, 40, 50, and 60 wt% contents of the SS flour were investigated. The thickness swelling and water absorption of the specimens increased with increasing SS flour content. The modulus in the flexural and tensile improved with increasing SS flour content while the tensile and flexural strengths of the specimens decreased. The use of maleic anhydride polypropylene (3 wt%) had a positive effect on the dimensional stability and mechanical properties of the polypropylene thermoplastic composites filled with SS flour. The melting temperature of polypropylene decreased with increasing content of the SS flour. The degree of crystallinity of filled polypropylene composites between fibre loading of 0–30 % by weight was higher than that of unfilled polypropylene composites. However, further increment in the filler content decreased the degree of crystallinity. The obtained results showed that SS flour could be potentially suitable raw material in the manufacture of polypropylene composites.     

Effect of Glycerol on the Properties of 100 % Biodegradable Thermoplastic Based on Wheat Flour

This paper reports the effect of glycerol on thermal, mechanical and morphology of the wheat-flour based thermoplastic sheets (<3 mm) fabricated using single screw extrusion followed by compression molding. The amount of glycerol (plasticizer) added during the formulation varies from 20 to 35 % w/w (20, 23, 25, 30 and 35 % w/w). Results indicate that increase in the amount of glycerol in the starch based thermoplastic sheets, lowers its hardness and tensile properties while an increase in the melt flow index. Variation in the glycerol content from 20 to 25 % w/w increases the impact strength of the thermoplastic sheets beyond this limit it decreases. The contact angle analysis shows that glycerol has effect on the surface energy and work of adhesion of the thermoplastic sheets. However, the presence of glycerol has no significant influence on the thermal stability of thermoplastic sheets above 200 °C.     

Study on the Effect of Dicumyl Peroxide on Structure and Properties of Poly(Lactic Acid)/Natural Rubber Blend

In attempt to enhance the compatibility of NR in PLA matrix, and furthermore to enhance mechanical properties of PLA, PLA/NR blends with strong interaction were prepared in Haake internal mixer, using dicumyl peroxide (DCP) as cross-linker. The effects of dicumyl peroxide on morphology, thermal properties, mechanical properties and rheological properties of PLA and PLA/NR blends were studied. The results indicated that dicumyl peroxide could increase the compatibility of poly(lactic acid) and natural rubber. With small amount of dicumyl peroxide, the effect on NR toughening PLA was enhanced and the tensile toughness of PLA/NR blends was improved. When the DCP content was up to 0.2 wt%, the PLA/NR blend reached the maximum elongation at break (26.21 %) which was 2.5 times of that of neat PLA (the elongation at break of neat PLA was 10.7 %). Meanwhile, with introducing 2 wt% DCP into PLA/NR blend, the maximum Charpy impact strength (7.36 kJ/m²) could be achieved which was 1.8 times of that of neat PLA (4.18 kJ/m²). Moreover, adding adequate amount of DCP could improve the processing properties of blends: the viscosity of PLA/NR blend decreased significantly and the lowest viscosity of the blends could be achieved when the DCP content was 0.5 wt%.