Thermal and biodegradation properties of poly(lactic acid)/fertilizer/oil palm fibers blends biocomposites

Poly(lactic acid) (PLA) and NPK fertilizer with empty fruit bunch (EFB) fibers were blends to produced bioplastic fertlizer (BpF) composites for slow release fertilizer. Thermal properties of BpF composites were investigated by thermogavimteric analysis (TGA), differential scanning calorimetry (DSC), and morphological and degradation properties were anlayzed by scanning electron microscopy (SEM), soil burial test, respectively. TGA themogram display that neat PLA, PLA/NPK, and BpF composites degradate at different temperatures. DSC curves of PLA and other composites exhibited same glass transition temperature (T_g) value indicating that both major blend components are miscible. The T_g, crystallization temperature (T_c), melting temperature (T_m) values also decreased with increased amount of fertilizer and fibers. The T_m of BpF composites did not change with an increase in fertilizer content because thermal stability of PLA and PLA/NPK composites was not affected. Soil burial and fungal degradation test of PLA, PLA/NPK, and BpF composites were also carried out. Soil burial studies indicated that BpF composites display better biodegradation as compared with neat NPK. Fungal degradation study indicated that fungi exposure times of BpF composites show higher value of degradation as compared with PLA/NPK. We attribute that developed BpF composites will help oil palm plantation industry to use it as slow release fertilizer. POLYM. COMPOS. 36:576–583, 2015. © 2014 Society of Plastics Engineers     

Enhanced biodegradation and processability of biodegradable package from poly(lactic acid)/poly(butylene succinate)/rice-husk green composites

This work aims to study the possibility to process PLA/PBS/RH green composites into hexagonal plant-pots employing a large-scale industrial operation using injection molding. Green composites based on poly(lactic acid) (PLA), poly(butylene succinate) (PBS), and rice husk (RH) with various RH contents (10–30%wt.) were produced successfully using a twin-screw extruder. The compatibility of RH-matrix was improved by chemical surface modifications using a coupling agent. RH was analyzed as an effective filler for PLA to develop green composites with low cost, high biodegradability, improved processability, and comparable mechanical properties as unfilled PLA. With increasing RH content, tensile modulus of the composites increased gradually. The addition of PBS, at PLA/PBS ratio of 60/40, improved the elongation at break and impact strength of PLARH30 by 55% and 7.1%, respectively. The suitable processing temperatures for PLA decreased from 220–230°C to 170–180°C when 30%wt. RH was composited into PLA matrix and were further reduced when PBS was applied. After biodegradation via either enzymatic degradation or hydrolysis, surface erosion with a large number of voids, mass loss, and the substantial decrease in tensile strength of all the composites were observed. In addition, the biodegradation of the composites has been improved by the addition of either RH or PBS.     

Biodegradable poly(lactic acid)/poly(butylene succinate)/wood flour composites: Physical and morphological properties

This work sought to improve the toughness and thermal stability of poly(lactic acid) (PLA) by incorporating poly(butylene succinate) (PBS) and wood flour (WF). The PLA/PBS blends showed a PBS‐dose‐dependent increase in the impact strength, elongation at break, degree of crystallinity, and thermal stability compared to the PLA, but the tensile strength, Young's modulus, and flexural strength were all decreased with increasing PBS content. Based on the optimum impact strength and elongation at break, the 70/30 (w/w) PLA/PBS blend was selected for preparing composites with five loadings of WF (5–30 phr). The impact strength, tensile strength, flexural strength, and thermal stability of the PLA/PBS/WF composites decreased with increasing WF content, and the degree of crystallinity was slightly increased compared to the 70/30 (w/w) PLA/PBS blend. Based on differential scanning calorimetry, the inclusion of PBS and WF into PLA did not significantly change the glass transition and melting temperatures of PLA in the PLA/PBS blends and PLA/PBS/WF composites. From the observed cold crystallization temperature of PLA in the samples, it was evident that the degree of crystallinity of PLA in all the blends and composites was higher than that of PLA. The PLA/PBS blend and PLA/PBS/WF composite degraded faster than PLA during three months in natural soil, which was due to the fast degradation rate of PBS. POLYM. COMPOS., 38:2841–2851, 2017. © 2016 Society of Plastics Engineers     

Resistance of poly(lactic acid)/starch composites to weathering effects

In order to produce a completely bio-based and cost-effective filled polymer, PLA and native potato starch as a filler were compounded by twin screw extrusion. Subsequently injection molded test specimens were manufactured and subjected to artificial weathering as well as different storages (high temperature, high humidity, freeze, water) for 504 h with a view to long-term resistance. Depending on the starch content a significant reduction of up to 100% in tensile strength can be seen, as the starch accelerates or inhibits the triggered aging effects. As a result of the influence of humidity and water as well as artificial weathering, stress cracks are formed in starch-containing samples. Storage at an elevated temperature (70°C, 50% RH) leads to polymer degradation of the PLA. This degradation can be inhibited by the addition of starch. Freezing storage has no significant influence on the mechanical and structural properties of the PLA starch composites.     

Preparation and properties of poly(lactic acid)/lignin-modified polyvinyl acetate composites

Poly(lactic acid)(PLA) has good application in the field of packaging because of its good biodegradability, tensile strength, and film-forming properties. However, the disadvantages of high brittleness and high cost limit the wider application of PLA. PLA/lignin-modified polyvinyl acetate (L-PVAc) composites with excellent toughness were prepared by melt blending PLA with modifier L-PVAc. The mechanical properties, thermal properties and morphology of the composites were characterized to evaluate the effect of L-PVAc content on the properties of the composites. The results showed that the introduction of L-PVAc could increase the impact strength, elongation at break, glass transition temperature, melting temperature and the degree of crystallinity of PLA/L-PVAc composites. When the L-PVAc content reached up to 20.0 wt%, the impact strength, elongation at break, glass transition temperature, melting temperature and the degree of crystallinity of the composites were increased by 298.2%, 167.5%, 3.8%, 1.8%, and 78.8%, respectively compared to pure PLA due to the good toughness of PVAc and heterogeneous nucleation of lignin. This research can promote the high-value utilization of lignin and the application of PLA in the fields of clothing, agriculture, medical and hygiene.     

Preparation of poly(lactic acid) and modified starch composites

In this article, the pretreatment before extrusion between the PLA and the modified starch was researched. The research on the composites of PLA and the modified starch focused on improving its compatibility and mechanical properties. The pretreatment samples were characterized by solid ¹³C-NMR and the chemical titration of the carboxyl end (–COOH) groups in PLA. The results illuminated that the pretreatment reaction was successful and the –COOH in PLA had reacted with the –OH in modified starch. The compatibility of the composites was determined by differential scanning calorimetry and scanning electron microscopy. The results showed that pretreatment could improve the compatibility of the composites. The mechanical properties of the composites were also enhanced. This approach is identified as a reasonable method to produce commercial PLA/modified starch composites with economical feasibility.     

Mechanical and thermal properties of wood fibers reinforced poly(lactic acid)/thermoplasticized starch composites

Thermoplasticized starch (TPS) filled poly(lactic acid) (PLA) blends are usually found to have low mechanical properties due to poor properties of TPS and inadequate adhesion between the TPS and PLA. The purpose of this study was to investigate the reinforcing effect of wood fibers (WF) on the mechanical properties of TPS/PLA blends. In order to improve the compatibility of wood with TPS/PLA blends, maleic anhydride grafted PLA (MA‐g‐PLA) copolymer was synthesized and used. TPS, TPS/PLA blends, and WF reinforced TPS/PLA composites were prepared by twin‐screw extrusion and injection molded. Scanning electron microscope and crystallinity studies indicated thermoplasticity in starch. WF at two different weight proportions, that is, 20% and 40% with respect to TPS content were taken and MA‐g‐PLA at 10% to the total weight was chosen to study the effect on mechanical properties. At 20% WF and 10% MA‐g‐PLA, the tensile strength exhibited 86% improvement and flexural strength exhibited about 106% improvement over TPS/PLA blends. Increasing WF content to 40% further enhanced tensile strength by 128% and flexural strength by 180% with respect to TPS/PLA blends. Thermal behavior of blends and composites was analyzed using dynamic mechanical analysis and thermogravimetric analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46118.     

Biodegradable poly(L‐lactic acid)/TiO2 nanocomposites: Thermal properties and degradation

Poly(L ‐lactic acid)‐titanium dioxide nanocomposites (with various loadings of TiO₂: 0.5, 1, 2, 5, and 10 wt %) were produced by solution casting method. The influence of TiO₂ on thermal properties and crystallinity of PLA was investigated by DSC and FTIR spectroscopy. The TiO₂ nano filler has no significant influence on the characteristic temperatures (T_g, T_c, and T_m), but has high impact on the crystallinity of these systems. The degree of crystallinity X_c significantly increases for PLA nanocomposites loaded with up to 5 wt % of TiO₂, while for 10 wt % load of TiO₂ it drops below X_c of the pure resin. The degradation of the prepared composites was evaluated hydrolytically in 1N NaOH, enzymatically in α‐amylase solutions, and under UV irradiation. The catalytic effect of TiO₂ nano particles on the degradation processes under UV light exposure (λ = 365 nm) and hydrolytic degradation was confirmed with the increase of the filler content. The opposite effect was identified in enzymatic degradation experiments. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal,mechanical and rheological properties of poly (lactic acid)/epoxidized soybean oil blends

Summary  Poly(lactic acid) (PLA) was melt blended with epoxidized soybean oil (ESO) in an internal mixer and thermal, mechanical and rheological properties of the blends were investigated by means of differential scanning calorimetry, dynamic mechanical analysis, tensile test and small amplitude oscillatory shear rheometry. ESO lowered glass transition temperature and increased the ability of PLA to cold crystallization. The blend exhibited improved elongation-at-break along with a plastic deformation. The plasticization effect by ESO was also manifested by the lowering of dynamic storage modulus and viscosity in the melt state of the blends compared with neat PLA.     

Thermal degradation and biodegradability of poly (lactic acid)/corn starch biocomposites

Thermal degradation and biodegradability of poly (lactic acid) (PLA) and poly (lactic acid)/corn starch (PLA/CS) composites with and without lysine diisocyanate (LDI) were evaluated by thermogravimetric analysis measurement and enzymatic degradation using Proteinase K and burial tests, respectively. Thermal stability was decreased by addition of CS and the composites with LDI showed higher thermal degradation temperature than those without LDI. In enzymatic biodegradation, the weight remaining of all samples decreased almost linearly with time. The addition of CS resulted in a faster rate of degradation and the composites with LDI were more difficult to degrade than those without it. In the composite without LDI, the degradation was faster at the interface between PLA and CS, showing deep and wide clearance, but degradation starting at the interface was not clearly observed in the composite with LDI. There was no considerable difference in molecular weight and distribution of the samples after enzymatic degradation. The lactic acid content of the water‐soluble product obtained after enzymatic degradation increased with degradation time. In burial tests, pure PLA was little degraded but the composites gradually degraded. The degradation of the composite without LDI was faster than that of the composite with LDI. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3009–3017, 2006     

聚乙二醇改性淀粉/聚乳酸薄膜的结构与性质研究

将热塑性淀粉(TPS)与聚乙二醇(PEG)、聚乳酸(PLA)共混后,采用溶剂蒸发法制备出完全生物降解的聚乙二醇改性淀粉/聚乳酸薄膜(SPLA)。研究了SPLA膜的力学性能、耐水性,并对薄膜的结构进行了研究,结果表明聚乳酸可以明显改善淀粉基薄膜的耐水性与力学强度;当w(PLA)≤20%时,共混物各组分间有较好的相容性。SPLA膜的玻璃化转变温度低于淀粉和聚乳酸,XRD显示共混膜中淀粉和聚乳酸的颗粒结晶结构均受到破坏。     

Effects of treated waste silicon rubber on properties of poly(lactic acid)/ammonium polyphosphate composites

Considering the massive waste silicone rubber composites (WSiRC) in electrical and electronic engineering industries every year, the utilization of WSiRC is a meaningful and urgent task. In this study, WSiRC was utilized after a simple treatment in the flame retardant polylactic acid (PLA). The TG data in N₂ indicated that the char residues at 700 °C of the PLA/ammonium polyphosphate(APP)/WSiRC samples are improved with the loading of WSiRC, which means that WSiRC could act as the carbonization promoter for the PLA blends. Moreover, it is found in LOI, UL94, and cone tests that WSiRC can only improve the flame retardancy of PLA in an appropriate loading range since the crosslink structure formed by WSiRC may interact with that formed by APP and jointly improve the char‐formation ability of PLA. However, too much WSiRC deteriorated the flame retardancy of PLA because of the effect of WSiRC cluster at its higher loading. The photographs of the char residue after the cone tests also manifested that. The cone data showed that WSiRC could suppress the production of smoke as well. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45231.     

Thermal properties and non‐isothermal crystallization behavior of poly(trimethylene terephthalate)/poly(lactic acid) blends

Thermal properties and non‐isothermal melt‐crystallization behavior of poly(trimethylene terephthalate) (PTT)/poly(lactic acid) (PLA) blends were investigated using differential scanning calorimetry and thermogravimetric analysis. The blends exhibit single and composition‐dependent glass transition temperature, cold crystallization temperature (T_cc) and melt crystallization peak temperature (T_mc) over the entire composition range, implying miscibility between the PLA and PTT components. The T_cc values of PTT/PLA blends increase, while the T_mc values decrease with increasing PLA content, suggesting that the cold crystallization and melt crystallization of PTT are retarded by the addition of PLA. The modified Avrami model is satisfactory in describing the non‐isothermal melt crystallization of the blends, whereas the Ozawa method is not applicable to the blends. The estimated Avrami exponent of the PTT/PLA blends ranges from 3.25 to 4.11, implying that the non‐isothermal crystallization follows a spherulitic‐like crystal growth combined with a complicated growth form. The PTT/PLA blends generally exhibit inferior crystallization rate and superior activation energy compared to pure PTT at the same cooling rate. The greater the PLA content in the PTT/PLA blends, the lower the crystallization rate and the higher the activation energy. Moreover, the introduction of PTT into PLA leads to an increase in the thermal stability behavior of the resulting PTT/PLA blends. Copyright © 2011 Society of Chemical Industry     

Study on the mechanical and thermal properties of poly(lactic acid)/office waste paper fiber composites

Environment friendly composites with favorable mechanical properties and low water absorption performance were successfully produced from poly(lactic acid) (PLA), office waste paper fiber (OWF), and coupling agents. The perfect sample was easily manufactured by melting–blending and injection molding. The PLA/OWF composites were comparable with other PLA/plant fiber composites, and the results indicated that the PLA/OWF composites show better performance than PLA/wheat straw fiber composites and PLA/bamboo fiber composites. On this basis, influence of modification of OWF on the properties of composites was investigated. The infrared results show that the OWF modification by different coupling agents was successful, and the scanning electron microscopy indicates that prepared composites exhibit good interfacial compatibility due to preferable binding force between fiber and matrix. With addition of 2 wt% γ-(2,3-propylene oxides)propyl trimethylsilane, the composite exhibits high tensile strength of 58.96 MPa, reflecting increase of 14% than the pure PLA. According to the crystallization and melting performance table, OWF can act as nucleating agent to promote the crystallization properties on composites, while the coupling agents have little effect on thermal stability. This article confirmed that the OWF has appropriate properties and is suitable for preparing composite materials and this work provides a novel idea for the utilization of office waste paper.     

Non-isothermal crystallization kinetics of poly (lactic acid)/modified carbon black composite

A novel method was employed to modify the surface of carbon black (CB) by an organic small molecule in a Haake Rheomix mixer. Jeziorny equation, the Ozawa model and Mo equation were employed to describe the non-isothermal crystallization process of poly (lactic acid) (PLA), PLA/CB and PLA/modified carbon black (MCB) composites. It is found that the Ozawa model fail to describe the non-isothermal crystallization process for PLA and its composites, while Jeziorny equation and Mo’s theory provide a good fitting. The comparison of crystallization kinetics between PLA/MCB and PLA through Lauritzen–Hoffman model indicates that there appears a transition from regimes II to III in PLA and PLA/MCB. The fold surface free energy σ _e of PLA/MCB composite is higher than that of neat PLA, implying that the existence of nucleating agent is unfavorable for the regular folding of the molecule chain.     

Thermal oxidative degradation kinetics and thermal properties of poly(ethylene terephthalate) modified with poly(lactic acid)

The thermal oxidative degradation kinetics of poly(ethylene terephthalate) (PET) copolymers modified with poly(lactic acid) (PLA) were investigated with thermogravimetric analyzer (TGA). The thermal properties of the modified products were also determined by differential scanning calorimeter (DSC) technique. Waste PET (P100) obtained from postconsumer water bottles was modified with a low‐molecular‐weight PLA. The PET/PLA weight ratio was 90/10 (P90) and 50/50 (P50) in the modified samples. The thermal oxidative degradation kinetics of the modified samples was compared with those of PET (P100). The segmented block and/or random copolymer structure of the modified samples formed by a transesterification reaction between the PLA and PET units in solution and the length of the aliphatic and aromatic blocks were found to have a great effect on the degradation behavior. On the basis of the results of the degradation kinetics determined by Kissinger method, the degradation rate of the samples decreased in the order of P50 > P90 > P100, depending on the amount of PLA in the copolymer structure. However, the degradation activation energies (E_A) of the samples decreased in the order of P100 > P90 > P50. It was concluded that the degradation rate and mechanism were affected significantly by the incorporation of PLA into the copolymer structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal properties of extruded/injection‐molded poly(lactic acid) and biobased composites

To determine the degree of compatibility between poly(lactic acid) and different biomaterials (fibers), poly(lactic acid) was compounded with sugar beet pulp and apple fibers. The fibers were added in 85 : 15 and 70 : 30 poly(lactic acid)/fiber ratios. The composites were blended by extrusion followed by injection molding. Differential scanning calorimetry and thermogravimetric analysis were used to analyze the extruded and extruded/injection‐molded composites. After melting in sealed differential scanning calorimetry pans, the composites were cooled through immersion in liquid nitrogen and aged (stored) at room temperature for 0, 7, 15, and 30 days. After storage, the samples were heated from 25 to 180°C at 10°C/min. The neat poly(lactic acid) showed a glass‐transition transition at 59°C with a change in heat capacity (ΔC_p) value of 0.464. The glass transition was followed by crystallization and melting transitions. The enthalpic relaxation of the poly(lactic acid) and composites steadily increased as a function of the storage time. Although the presence of fibers had little effect on the enthalpic relaxation, injection molding reduced the enthalpic relaxation. The crystallinity percentage of the unprocessed neat poly(lactic acid) dropped by 95% after extrusion and by 80% for the extruded/injection‐molded composites. The degradation was performed in air and nitrogen environments. The degradation activation energy of neat poly(lactic acid) exhibited a significant drop in the nitrogen environment, although it increased in air. This meant that the poly(lactic acid) was more resistant to degradation in the presence of oxygen. Overall, injection molding appeared to reduce the activation energy for all the composites. Sugar beet pulp significantly reduced the activation energy in a nitrogen environment. In an air environment, both sugar beet pulp and apple fibers increased the activation energy. The enzymatic degradation of the composites showed a higher degradation rate for the extruded samples versus the extruded/injection‐molded composites, whereas the apple composites exhibited higher weight loss. The thermogravimetric analysis data showed that the degradation of unprocessed and extruded neat poly(lactic acid) followed a one‐step mechanism, whereas extruded/injection‐molded composites showed two‐step degradation. A higher fiber content resulted in up to three‐step degradation mechanisms. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Thermal and mechanical properties of poly(lactic acid)/starch/methylenediphenyl diisocyanate blending with triethyl citrate

Triethyl citrate (TC) was added as a plasticizer to a blend of poly(lactic acid) (PLA) and starch in the presence of methylenediphenyl diisocyanate (MDI). As expected, TC improved the elongation at break and toughness and, at the same time, decreased the tensile strength and modulus. However, TC did not significantly affect the coupling effects of MDI on starch and PLA. The tensile strength of the blend with MDI was much greater than the tensile strength without MDI at the same TC level. The tensile properties of the blend changed dramatically as the TC concentration increased from 5 to 12.5%. At a TC concentration of 7.5%, the blend produced desirable elongation and toughness with fairly good tensile strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2947–2955, 2003     

Rheological and mechanical properties of poly(lactic acid)/polystyrene polymer blend

Properties modification by blending polymers has been an area of immense interest. In this work, rheological and mechanical properties of poly(lactic acid)/polystyrene (PLA/PS) blends were investigated. PLA/PS blends in different ratios were prepared using a laboratory scale single screw extruder to obtain (3 mm) granules. Rheological properties were studied using a capillary rheometer and the Bagley’s correction was performed. True shear rate (γ _r ), true shear stress (τ _r ), and true viscosity (η _r ) were determined, the relationship between true viscosity and (1/T) was studied for PLA70 blend and the flow activation energy at a constant shear stress (E _τ ) and a constant shear rate (E _γ ) was determined. The mechanical property measurements were performed at room temperature. Stress at break and strain at break were determined. The results showed that PLA/PS blend exhibited a typical shear-thinning behavior over the range of the studied shear rates, and the viscosity of the blend decreased with increasing PLA content. Also it was found that no equal-viscosity temperature exists between PLA and PS. The mechanical results showed immiscibility between PLA and PS in the blend.