Preparation and Characterization of Polyhydroxyalkanoate Bioplastic-Based Green Renewable Composites from Rice Husk

The biodegradability, morphology, and mechanical properties of composite materials consisting of acrylic acid-grafted poly(hydroxyalkanoate) (PHA-g-AA) and rice husk (RH) were evaluated. Composites containing PHA-g-AA (PHA-g-AA/RH) exhibited noticeably superior mechanical properties compared with those of PHA/RH because of greater compatibility with RH. The dispersion of RH in the PHA-g-AA matrix was homogeneous because of ester formation and the consequent creation of branched and crosslinked macromolecules, between the carboxyl groups of PHA-g-AA and hydroxyl groups in RH. The water resistance of PHA-g-AA/RH was higher than that of PHA/RH, although the weight loss of composites buried in soil compost indicated that both were biodegradable, especially at high levels of RH substitution. After 60 days, the weight loss of the PHA-g-AA/RH (40 wt%) composite was greater than 90 %. PHA/RH exhibited a weight loss of approximately 4–8 wt% more than PHA-g-AA/RH. The PHA/RH and PHA-g-AA/RH composites were more biodegradable than pure PHA, which implies a strong connection between RH content and biodegradability.     

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.     

Biodegradable Polyester-Based Blend Reinforced with Curauá Fiber: Thermal,Mechanical and Biodegradation Behaviour

Biodegradable composites can be produced by the combination of biodegradable polymers (BP) as matrix and vegetal fibers as reinforcement. Composites of a commercial biodegradable polymer blend and curauá fibers (loaded at 5, 15 and 20 wt%) were prepared by melt mixing in a twin-screw extruder. Chemical treatments such as alkali treatment of the fiber and addition of maleic anhydride grafted polypropylene (MA-g-PP) as coupling agent were performed to promote polymer/fiber interfacial adhesion so that mechanical performance can be improved. The resulting composites were evaluated through hardness, melt flow index and tensile, flexural and impact strengths as well as water absorption. Thermal analysis and Fourier transform infrared spectroscopy were also employed to characterize the composites. The polymer/fiber interface was investigated through scanning electron microscopy analysis. The biodegradability of composites was evaluated by compost-soil burial test. The addition of curauá fiber promoted an increase in the mechanical strengths and composites treated with 2 wt% MA-g-PP with 20 wt% curauá fiber showed an increase of nearly 75% in tensile and 56% in flexural strengths besides an improvement in impact strength with respect to neat polymer blend. Nevertheless, treated composites showed an increase in water absorption and biodegradation tests showed that the addition of fiber retards degradation time. The retained mass of BP/20 wt% fiber composite with MA-g-PP and neat BP was 68 and 26%, respectively, after 210 days of degradation test.     

Compatibilization Improves Performance of Biodegradable Biopolymer Composites Without Affecting UV Weathering Characteristics

With growing interest in the use of eco-friendly composite materials, biodegradable polymers and composites from renewable resources are gaining popularity for use in commercial applications. However, the long-term performance of these composites and the effect of compatibilization on their weathering characteristics are unknown. In this study, five types of biodegradable biopolymer/wood fiber (WF) composites were compatibilized with maleic anhydride (MA), and the effect of accelerated UV weathering on their performance was evaluated against composites without MA and neat biopolymers. The composite samples were prepared with 30 wt% wood fiber and one of the five biodegradable biobased polymer: poly(lactic) acid (PLA), polyhydroxybutyrate (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), Bioflex (PLA blend), or Solanyl (starch based). Neat and composite samples were UV weathered for 2000 h (hours), and characterized for morphological, physical, thermal, and mechanical properties before and after weathering. Compared to composites without MA, composites containing MA grafted polymers exhibited improved properties due to increased interfacial adhesion between the fiber and matrix. Upon accelerated weathering, thermal and mechanical properties of 70% of the samples substantially decreased. Surfaces of all the samples were roughened, and drastic color changes were observed. Water absorption of all the samples increased after weathering exposure. Even though the compatibilization is shown to improve composite properties before weathering, it did not affect weathering of samples, as there were no considerable differences in properties exhibited by the composites with MA and without MA after weathering. The results suggest that compatibilization improves properties of biodegradable biobased composites without affecting its UV degradation properties.     

Synthesis,Characterization and Nanocomposite Formation of Poly(glycerol succinate-co-maleate) with Nanocrystalline Cellulose

A novel biodegradable polymer based on glycerol, succinic anhydride and maleic anhydride, poly(glycerol succinate-co-maleate), poly(GlySAMA), was synthesized by melt polycondensation and tested as a matrix for composites with nanocrystalline cellulose. This glycerol-based polymer is thermally stable as a consequence of its targeted cross-linked structure. To broaden its range of properties, it was specifically formulated with nanocrystalline cellulose (NCC) at concentrations of 1, 2 and 4 wt%, and showed improved mechanical properties with NCC. Specifically, the effect of reinforcement on mechanical properties, thermal stability, structure, and biodegradability was evaluated, respectively, by tensile tests and thermogravimetric analyses, X-ray diffraction and respirometry. The neat poly(GlySAMA) polymer proved flexible, exhibiting an elongation-to-break of 8.8 % while the addition of nanowhiskers (at 4 wt%) caused tensile strength and Young’s modulus to increase, 20 and 40 %, respectively. Stiffness improved without significantly decreasing thermal stability as measured by thermogravimetric analysis. Biodegradation tests indicated that all samples were degradable but NCC reduced the rate of biodegradation.     

Process,Characterization and Biodegradability of Aliphatic Aromatic Polyester/Sisal Fiber Composites

The biodegradability, morphology, and mechanical properties of composite materials made of Poly(butylene adipate-co-terephthalate) (PBAT) and sisal fiber (SF) were evaluated. Composites containing acrylic acid-grafted PBAT (PBAT-g-AA/SF) exhibited noticeably superior mechanical properties due to greater compatibility between the two components. The dispersion of SF in the PBAT-g-AA matrix was highly homogeneous as a result of ester formation between the carboxyl groups of PBAT-g-AA and hydroxyl groups in SF and the consequent creation of branched and cross-linked macromolecules. Each composite was subjected to biodegradation tests in Rhizopus oryzae compost. Morphological observations indicated severe disruption of film structure after 60 days of incubation, and both the PBAT and the PBAT-g-AA/SF composite films were eventually completely degraded. Water resistance of PBAT-g-AA/SF was higher than that of PBAT/SF, although weight loss of composites buried in Rhizopus oryzae compost indicated that both were biodegradable, even at high levels of SF substitution. The PBAT-g-AA/SF films were more biodegradable than those made of PBAT, implying a strong connection between these characteristics and biodegradability.     

Grafting of Glycidyl Methacrylate onto Poly(lactide) and Properties of PLA/Starch Blends Compatibilized by the Grafted Copolymer

Poly(lactide)-graft-glycidyl methacrylate (PLA-g-GMA) copolymer was prepared by grafting GMA onto PLA in a batch mixer using benzoyl peroxide as an initiator. The graft content was determined with the ¹H-NMR spectroscopy by calculating the relative area of the characteristic peaks of PLA and GMA. The result shows that the graft content increases from 1.8 to 11.0 wt% as the GMA concentration in the feed varies from 5 to 20 wt%. The PLA/starch blends were prepared by the PLA-g-GMA copolymer as a compatibilizer, and the structure and properties of PLA/starch blends with or without the PLA-g-GMA copolymer were characterized by SEM, DSC, tensile test and medium resistance test. The result shows that the PLA/starch blends without the PLA-g-GMA copolymer show a poor interfacial adhesion and the starch granules are clearly observed, nevertheless the starch granules are better dispersed and covered by PLA when the PLA-g-GMA copolymer as a compatibilizer. The mechanical properties of the PLA/starch blends with the PLA-g-GMA copolymer are obviously improved, such as tensile strength at break increasing from 18.6 ± 3.8 MPa to 29.3 ± 5.8 MPa, tensile modulus from 510 ± 62 MPa to 901 ± 62 MPa and elongation at break from 1.8 ± 0.4 % to 3.4 ± 0.6 %, respectively, for without the PLA-g-GMA copolymer. In addition, the medium resistance of PLA/starch blends with the PLA-g-GMA copolymer was much better than PLA/starch blends.     

Tensile and Combustion Properties of PP/IFR/POE/nano-CaCO<Subscript>3</Subscript> Composites

The tensile and combustion properties of polypropylene/polyolyaltha olefin composites filled with intumescent flame retardant (IFR) and nanometer calcium carbonate (nano-CaCO₃) were measured. It was found that the values of the Young’s modulus of the composites increased almost linearly, while the values of the tensile yield strength and tensile fracture strength of the composites decreased with increasing the IFR weight fraction; the values of the elongation at break of the composites decreased quickly when the IFR weight fraction was lower than 10 wt%, and then varied slightly when the IFR weight fraction was higher than 10 wt%. Moreover, the morphology of the specimens after combustion was observed and the frame retardant mechanisms of the composites were discussed.     

The Effects of Additives on the Biodegradation of Polycaprolactone Composites

Because environmental pollution caused by plastic waste is a major problem investigations concerning biodegradable packaging are important and required. In this study, the biodegradation of PCL composite films with organic (glycerol monooleate and oleic acid) and inorganic additives (organo nano clay) was investigated to understand which additive and the amount of additive was more effective for biodegradation. The relationship between the degree of crystallinity and the effect of additives on the biodegradability of polycaprolactone (PCL) was examined. PCL composite films were prepared using organo nano clay (0.1–0.4–1–3 wt%) and oleic acid (1–3–5 wt%) or GMO (1–3–5 wt%). The 35 films prepared with PCL (P), clay (C), oleic acid (O), or glycerol monooleate (G) are coded as P_C#wt%_O (or G)#wt%. The composite films, P_C0.4_O5 contains 0.4 wt% clay and 5 wt% oleic acid and the P_C3_G1 contains 3 wt% clay and 1 wt% glycerol monooleate. The biodegradation of PCL films in simulated soil was studied for 36 months. The films were periodically removed from the simulated soil and film thicknesses, weight losses, visual changes, crystal structures, and a functional group analyses were performed. PCL composite films are separated into three groups, depending on degradation time, (1) films that degraded before 8 months (fast degradation), (2) films that degraded around 24 months (similar to neat PCL), and (3) films that take longer to degrade (slow degradation). The films in the first group are PCL films with 1 and 3 wt% clay additive and they begin to biodegrade at the 5th month. However, a composite film of PCL with only 0.4 wt% clay and 5 wt% GMO addition has the shortest degradation time and degraded in 5 months. The films in the last group are; P_G3, P_G5, P_C0.1, P_C0.1_O1, and P_C0.1_O5 and they took around 30 months for biodegradation. It was observed that increasing the organo nanoclay additive increases the biodegradability by disrupting the crystal structure and causing a defective crystal formation. The addition of GMO with organo nano clay also accelerates biodegradation. The addition of organo nano clay in an amount as small as 0.1 wt% acts as the nucleating agent, increases the degree of crystallinity of the PCL composites, and slows the biodegradation period by increasing the time.     

The Relationship Between the Chemical Structure of Poly(alkylene glycol)s and Their Aerobic Biodegradability in an Aqueous Environment

The relationship between the chemical structure of poly(alkylene glycol)s (PAGs) and their biodegradability was studied using a set of polymeric fluids that included poly(ethylene glycol), poly(propylene glycol) (PPG), random copolymers of ethylene oxide (EO) and propylene oxide (PO) differing in the EO/PO ratio as well as PAGs capped with ether or acyl moieties. The PAGs that were tested had an average molecular weight (MW) in the range of 350–3,600 Da and differed in their polymer backbones by either linear (diol type) or branched (triol type) molecules. The ultimate biodegradability of the PAGs was determined according to ISO 14593 (CO₂ headspace test) with a non-pre-exposed (as in OECD 310 test) and pre-exposed (adapted) inoculum. PAGs with the structure of PPG and copolymers of EO/PO of diol or triol structures with average molecular weights lower than 1,000 Da can be considered as readily biodegradable. Their ultimate biodegradation exceeds the limit of 60 % (according to the criteria of the OECD 310 test). PAGs with a copolymer structure and MW values ranging between 1,000 and 3,600 Da are not readily biodegradable, but they can be considered as those of inherent ultimate biodegradability. The increased EO content in PAG structures and the acylation of the terminal hydroxyl groups with carboxylic acids favourably influenced their biodegradability. Capped PAGs containing terminal ether groups appeared to be resistant to biodegradation.     

The Influence of Artificial Photodegradation on Properties of Poly(3-hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-3-hydroxyvalerate)(PHBV)/Graphite Nanosheets (GNS) Nanocomposites

The potential use of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/graphite nanosheets (GNS) as a biodegradable nanocomposite has been explored. PHBV/GNS nanocomposites films were prepared by solution casting at various concentrations of GNS—0.25, 0.50 and 1.00 wt% GNS. The films were exposed to artificial ultraviolet radiation (UV) during 52 h. The effect of GNS on PHBV photodegradation was investigated and compared to neat PHBV film. The artificial photodegradation induced changes in physical (weight loss), chemical carbonyl index by Fourier transform infrared spectroscopy, thermal degree of crystallinity and melting temperature by differential scanning calorimetry and morphological scanning electron microscopy characteristics. Based on the results obtained from aforementioned analyzes it was verified that GNS inhibits the oxidative degradation of PHBV matrix.     

Biodegradation of Polylactide and Gelatinized Starch Blend Films Under Controlled Soil Burial Conditions

The biodegradability of polylactide (PLA) and gelatinized starches (GS) blend films in the presence of compatibilizer was investigated under controlled soil burial conditions. Various contents (0–40 wt%) of corn and tapioca starches were added as fillers; whereas, different amounts of methylenediphenyl diisocyanate (MDI) (0–2.5 wt%) and 10 wt% based on PLA content of polyethylene glycol 400 (PEG400) were used as a compatibilizer and a plasticizer, respectively. The biodegradation process was followed by measuring changes in the physical appearance, weight loss, morphological studies, and tensile properties of the blend films. The results showed that the presence of small amount of MDI significantly increased the tensile properties of the blends compared with the uncompatibilized blends. This is attributed to an improvement of the interfacial interaction between PLA and GS phases, as evidenced by the morphological results. For soil burial testing, PLA/GS films with lower levels (1.25 wt%) of MDI had less degradation; in contrast, at high level of MDI, their changes of physical appearance and weight loss tended to increase. These effects are in agreement with their water absorption results. Furthermore, biodegradation rates of the films were enhanced with increasing starch contents, while mechanical performances were decreased.     

Stiff Biodegradable Polylactide Composites with Ultrafine Cellulose Filler

Polylactide (PLA) composites with 10–30 wt% of commercial fine grain filler of native cellulose were prepared by melt-mixing, and examined. The composite films had esthetic appearance, glossy surface, creamy color and density close to that of neat PLA. Good dispersion of the filler in PLA matrix was achieved. The composites were stiffer than neat PLA; in the glassy region the storage modulus increased by approx. 30 %. The tensile strength of the composite materials in the temperature range from 25 to 45 °C was similar to that of neat PLA. No marked decrease in molar mass of PLA in the composites occurred during processing in comparison to neat PLA. Moreover, thermogravimetry experiments demonstrated good thermal stability of the composites; 5 % weight loss occurred well above 300 °C.     

Water Absorption Kinetics and Hygrothermal Aging of Poly(lactic acid) Containing Halloysite Nanoclay and Maleated Rubber

Poly(lactic acid)/halloysite nanoclay composites (PLA/HNC) containing maleic anhydride grafted styrene-ethylene/butylene-styrene (SEBS-g-MAH) were produced using melt compounding followed by compression molding. The effects of hygrothermal aging on the thermal properties and functional groups changes of the HNC reinforced PLA (with and without SEBS-g-MAH) at three different temperatures (i.e., 30, 40 and 50 °C) were analyzed using differential scanning calorimetry and Fourier transform infrared spectroscopy techniques. The diffusion coefficient (D) of PLA was decreased by the incorporation of HNC and SEBS-g-MAH. The activation energy of water diffusion (E _a ) of PLA/HNC/SEBS-g-MAH nanocomposites was higher than that of pure PLA. The glass transition temperature (T _g ), cold-crystallization temperature (T _cc ) and melting temperature (T _m ) of the PLA sample were shifted to lower temperature and the effect was more pronounced at 50 °C. The carbonyl index values of all PLA samples increased after immersed in 40 and 50 °C, which is due to the formation of higher amount of carboxyl groups during the hydrolysis process.     

Mechanical Properties of Poly (Lactic Acid)/Hemp Fiber Composites Prepared with a Novel Method

This research dealt with a novel method of fabricating green composites with biodegradable poly (lactic acid) (PLA) and natural hemp fiber. The new preparation method was that hemp fibers were firstly blending-spun with a small amount of PLA fibers to form compound fiber pellets, and then the traditional twin-screw extruding and injection-molding method were applied for preparing the composites containing 10–40 wt% hemp fibers with PLA pellets and compound fiber pellets. This method was very effective to control the feeding and dispersing of fibers uniformly in the matrix thus much powerful for improving the mechanical properties. The tensile strength and modulus were improved by 39 and 92 %, respectively without a significant decrease in elongation at break, and the corresponding flexural strength and modulus of composites were also improved by 62 and 90 %, respectively, when the hemp fiber content was 40 wt%. The impact strength of composite with 20 wt% hemp fiber was improved nearly 68 % compared with the neat PLA. The application of the silane coupling agent promoted further the mechanical properties of composites attributed to the improvement of interaction between fiber and resin matrix.     

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 Nano-SiO<Subscript>2</Subscript> and Bark Flour Content on the Physical and Mechanical Properties of Wood–Plastic Composites

The aim of this study is to evaluate the impact of nano-SiO₂ and bark flour (BF) on the natural fiber–plastic composites engineering properties made from high density polyethylene (HDPE) and beech wood flour (WF). For this purpose, WF and BF in 60 mesh size and weight ratio of (50, 0 %), (30, 20 %), (10, 40 %) and (0, 50 %) respectively were mixed with HDPE. In order to increase the interfacial adhesion between the filler and the matrix, the maleic anhydride grafted polyethylene was constantly used at 3 wt% for all formulations as a coupling agent. The nano-SiO₂ particles with weight ratio of 0, 1, 2, and 4 % were also utilized to enhance the composites properties. The materials were mixed in an internal mixer (HAAKE) and then the bark and/or wood–plastic composite samples were made utilizing an injection molding machine. The physical tests including water absorption and thickness swelling, and mechanical tests including bending characteristics and un-notched impact strength were carried out on the samples based on ASTM standard. The results indicated that as the BF content increased in the composite, mechanical and physical properties were reduced, but the given properties were increased with the addition of nano-SiO₂. The addition of nano-SiO₂ had a negative impact on the physical properties, but when it was up to 2 %, it increased the impact strength.     

Novel Biodegradable Thermoplastic Elastomer Based on Poly(butylene succinate) and Epoxidized Natural Rubber Simple Blends

Novel biodegradable thermoplastic elastomer based on epoxidized natural rubber (ENR) and poly(butylene succinate) (PBS) blend was prepared by a simple blend technique. Influence of blend ratios of ENR and PBS on morphological, mechanical, thermal and biodegradable properties were investigated. In addition, chemical interaction between ENR and PBS molecules was evaluated by means of the rheological properties and infrared spectroscopy. Furthermore, the phase inversion behavior of ENR/PBS blend was predicted by different empirical and semi-empirical models including Utracki, Paul and Barlow, Steinmann and Gergen models. It was found that the co-continuous phase morphology was observed in the blend with ENR/PBS about 58/42 wt% which is in good agreement with the model of Steinmann. This correlates well to morphological and mechanical properties together with degree of crystallinity of PBS in the blends. In addition, the biodegradability was characterized by soil burial test after 1, 3 and 9 months and found that the biodegradable ENR/PBS blends with optimum mechanical and biodegradability were successfully prepared.     

Mechanical, Thermal and Water Absorption Properties of Kenaf-Fiber-Based Polypropylene and Poly(Butylene Succinate) Composites

The use of composites made from non-biodegradable conventional plastic materials (e.g., polypropylene, PP) is creating global environmental concern. Biodegradable plastics such as poly(butylene succinate) (PBS) are sought after to reduce plastic waste accumulation. Unfortunately, these types of plastics are very costly; therefore, natural lignocellulosic fibers are incorporated to reduce the cost. Kenaf fibers are also incorporated into PP and PBS for reinforcing purposes and they have low densities, high specific properties and renewable sourcing. However without good compatibilization, the interfacial adhesion between the matrix and the fibers is poor due to differences in polarity between the two materials. Maleic anhydride-grafted compatibilizers may be introduced into the system to improve the matrix-fiber interactions. The overall mechanical, thermal and water absorption properties of PP and PBS composites prepared with 30 vol.% short kenaf fibers (KFs) using a twin-screw extruder were being investigated in this study. The flexural properties for both types of composites were enhanced by the addition of compatibilizer, with improvements of 56 and 16 % in flexural strength for the PP/KF and PBS/KF composites, respectively. Good matrix-fiber adhesion was also observed by scanning electron microscopy. However, the thermal stability of the PBS/KF composites was lower than that of the PP/KF composites. This result was confirmed by both DSC and TGA thermal analysis tests. The water absorption at equilibrium of a PBS composite filled with KFs is inherently lower than of a PP/KF composite because the water molecules more readily penetrate the PP composites through existing voids between the fibers and the matrix. Based on this research, it can be concluded that PBS/KF composites are good candidates for replacing PP/KF composites in applications whereby biodegradability is essential and no extreme thermal and moisture exposures are required.