Tensile Strength, Elongation, Hardness, and Tensile and Flexural Moduli of PLA Filled with Glycerol-Plasticized DDGS

Rapid growth of the biofuel industry is generating large amounts of coproducts such as distillers dried grains with solubles (DDGS) from ethanol production and glycerol from biodiesel. Currently these coproducts are undervalued, but they have application in the plastics industry as property modifiers. The objective of this research effort is to quantify the effects on mechanical properties of adding DDGS and glycerol to polylactic acid (PLA). The methodology was to physically mix DDGS, as filler, with PLA pellets and injection mold the blends into test bars using glycerol as a plasticizer. The bars were subject to mechanical testing procedures to obtain tensile strength, tensile and flexural moduli, elongation to break, and surface hardness of blends from 0 to 90?%, by weight, of plasticized filler. Blends were typically relatively brittle with little or no yielding prior to fracture, and the addition of glycerol enabled molding of blends with high levels of DDGS but did not increase strength. Any presence of filler decreased the tensile strength of the PLA, and 20?C30?% filler reduced strength by 60?%. The 35?C50?% filled PLA had about one-fifth the value for pure PLA; at 60?C65?% filler level, about 10?% tensile strength remained; and over 80?% filler, 95?% of the strength was lost. Over 20?% filler, the tensile modulus decreased. The 35?% plasticized, filled blend yielded about one-half the stiffness as the pure PLA case; flexural modulus trended in the same manner but demonstrated a greater loss of stiffness. Most blends had less than 3?% elongation to break while surface hardness measurements indicated that up to 60?% filler reduced Shore D hardness by less than 20?%. The tensile strength and modulus data are consistent with the findings of other researchers and indicate that the type of filler and amount and sequence of plasticization are secondary effects, and the total PLA displaced is the dominant factor in determining the mechanical strength of the PLA and DDGS blends. Up to 65?% plasticized DDGS filler can be injection molded, and sufficient mechanical strength exists to create a variety of products. Such a novel material provides higher-value utilization of the biofuel coproducts of glycerol and DDGS and maintains the biodegradable and biocompatible nature of PLA.     

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%.     

The Properties of PLA/Oxidized Soybean Oil Polymer Blends

Novel polymer blends based on completely renewable polymers were reported. Polymer blends based on polylactic acid (PLA) and oxidized and hydroxylated soya bean oil polymers were prepared. Plasticization and mechanical strength effect of the soya bean oil polymers on the PLA were observed. Fracture surface analysis of the polymer blends was carried out by using scanning electron microscopy. The PLA blends showed more amorphous morphologies compared to pure PLA. The blends had better elongation at break in view of the stress–strain measurement. Blend of PLA with the hydroxylated polymeric soya bean oil indicated the slightly antibacterial properties.     

Fabrication of Admicelled Natural Rubber by Polycaprolactone for Toughening Poly(lactic acid)

Natural rubber (NR) with polycaprolactone (PCL) core–shell (NR-ad-PCL), synthesized by admicellar polymerization, was acted as an impact modifier for poly(lactic acid) (PLA). PLA and NR-ad-PCL were melt-blended using a co-rotating twin screw extruder. The morphology of PLA/NR-ad-PCL blends showed good adhesion as smooth boundary around rubber particles and PLA matrix. Only 5 wt% of rubber phase, NR-ad-PCL was more effective than NR to enhance toughness and mechanical properties of PLA. The contents of the NR-ad-PCL were varied from 5, 10, 15 and 20 wt%. From thermal results, the incorporation of the NR-ad-PCL decreased the glass transition temperature and slightly increased degree of crystallinity of PLA. Mechanical properties of the PLA/NR-ad-PCL blends were investigated by dynamic mechanical analyser, pendulum impact tester and universal testing machine for tension and flexural properties. The increasing NR-ad-PCL contents led to decreasing Young’s and storage moduli but increasing loss modulus. Impact strength and elongation at break of the PLA/NR-ad-PCL blends increased with increasing NR-ad-PCL content up to 15 wt% where the maximum impact strength was about three times higher than that of pure PLA and the elongation at break increased to 79%.     

Effect of Poly(Vinyl Acetate) on Mechanical Properties and Characteristics of Poly(Lactic Acid)/Natural Rubber Blends

Natural rubber grafted with poly(vinyl acetate) copolymer (NR-g-PVAc) was synthesized by emulsion polymerization. Three graft copolymers were prepared with different PVAc contents: 1 % (G1), 5 % (G5) and 12 % (G12). Poly(lactic acid) (PLA) was melt blended with natural rubber (NR) and/or NR-g-PVAc in a twin screw extruder. The blends contained 10–20 wt% rubber. The notched Izod impact strength and tensile properties were determined from the compression molded specimens. The effect of NR mastication on the mechanical properties of the PLA/NR/NR-g-PVAc blend was evaluated. Characterization by DMTA and DSC showed an enhancement in miscibility of the PLA/NR-g-PVAc blend. The temperature of the maximum tan δ of the PLA decreased with increasing PVAc content in the graft copolymer, i.e., from 71 °C (pure PLA) to 63 °C (the blend containing 10 % G12). The increase in miscibility brought about a reduction in the rubber particle diameter. These changes were attributed to the enhancement of toughness and ductility of PLA after blending with NR-g-PVAc. Therefore, NR-g-PVAc could be used as a toughening agent of PLA and as a compatibilizer of the PLA/NR blend. NR mastication was an efficient method for increasing the toughness and ductility of the blends which depended on the blend composition and the number of mastications.     

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.     

Novel Environmentally Friendly Copolymers Carboxymethyl Starch Grafted Poly(Lactic Acid)

Modified natural polymers have been gaining increasing scientific interest for many years. In this study carboxymethyl starch (CMS) was grafted with L(+)-lactic acid (LA) in different molar ratios CMS/LA (1/36, 1/22 and 1/12), resulting carboxymethyl starch-g-poly(lactic acid) (CMS-g-PLA) copolymers. The grafting reaction was carried out by solution polycondensation procedure in toluene and stannous 2-ethyl hexanoate Sn(Oct)₂ as catalyst was utilized. Poly(lactic acid) (PLA) was synthesized in the same conditions with the copolymers for comparative analyses of the physico-chemical and thermal properties. The copolymers and PLA were structurally and morphologically characterized by FT-IR, ¹H-NMR spectroscopy, WAXD and SEM analyses, taking CMS as reference. The molecular weight of the copolymers, CMS and PLA were determined, using a dynamic light scattering technique. The thermal behavior of the products was studied by DSC and TG-DTG analyses. The CMS-g-PLA graft copolymers exhibited lower Tg and thermal stability than pure CMS.     

Poly(Lactic Acid) Blended with Cellulolytic Enzyme Lignin: Mechanical and Thermal Properties and Morphology Evaluation

“Green”/bio-based blends of poly(lactic acid) (PLA) and cellulolytic enzyme lignin (CEL) were prepared by twin-screw extrusion blending. The mechanical and thermal properties and the morphology of the blends were investigated. It was found that the Young’s modulus of the PLA/CEL blends is significantly higher than that of the neat PLA and the Shore hardness is also somewhat improved. However, the tensile strength, the elongation at break, and the impact strength are slightly decreased. Thermogravimetric analysis (TGA) shows that the thermal stability of the PLA is not significantly affected by the incorporation of the CEL, even with 40 wt% CEL. The results of FT-IR and SEM reveal that the CEL and the PLA are miscible and there are efficient interactions at the interfaces between them. These findings show that the CEL is a kind of feasible filler for the PLA-based blends.     

Biodegradable Poly(lactic acid) Blends with Chemically Modified Polyhydroxyoctanoate Through Chain Extension

Poly(lactic acid) (PLA) was blended with chemically modified Polyhydroxyoctanoate (mPHO) using a Haake twin-screw mixer. Due to the melt viscosity disparity between the two components, PHO was reacted with Hexamethylene diisocyanate (HDI) used as a chain extender to produce high molecular weight for improving compatibility and processability with PLA. The number average and weight average molecular weight of the PHO, reacted with 0.55 wt% HDI, were increased 314 and 275%, respectively, compared with those of the unmodified PHO. The blends were characterized for rheological, thermal, and mechanical properties. Infrared spectra confirmed the formation of the urethane linkages in mPHO. The shear viscosity, as a function of shear rate or shear stress, decreased with an increase in mPHO content, indicating that the PLA/mPHO blends show shear-thinning behavior along with the power-law model. DSC thermograms showed that the two components in the blends were found with two crystalline phases and two amorphous phases confirming the coexistence of two immiscible components. Tensile results indicated that tensile strength for blends decreased with increasing mPHO content up to 80%. A decrease in elastic modulus, as well as an increase in elongation at break, was seen as a function of mPHO content. Results of aging tests showed that the mechanical properties of the blends also dropped more at a higher PLA level when compared with those of the unaged samples.     

Environmental Impact Assessment of Polylactide(PLA)/Chicken Feathers Biocomposite Materials

The aim of this study is to analyse the environmental impacts (EIs) of the process of preparation of new biocomposite materials obtained from polylactide (PLA) and chicken feathers (CFs). Two CFs stabilization methods and different percentages of CFs have been studied. The EIs of these new composites were compared to the impact of virgin PLA. Cradle-to-gate life cycle inventories were assessed for 0–35% v/v of CFs in a CFs/PLA biocomposite. Two CFs stabilization processes, autoclave and surfactant, were tested and compared with the aim to prioritize one of them from the environmental point of view. A composite plate of 184?×?184?×?2.2 mm³ was defined as the functional unit. Autoclave stabilization process exhibited lower environmental impact compared with surfactant stabilization process mainly due to both the lower requirements of electricity and water and the reduced pollution loads of the generated wastewater. Thus, the autoclave process was selected as the standard method when comparing the EIs of the proposed CFs/PLA biocomposites. In this sense, the addition of CFs to PLA matrix proportionally reduces all the EIs compared to pure PLA due to the replacement of PLA with CFs. This behaviour can be explained because the PLA production accounts for the 99% of the impact of the biocomposite. Consequently, CFs conveniently stabilized might be an alternative raw material to prepare CFs/PLA biocomposites with less environmental impact compared to pure PLA.     

Biodegradable Blends with Potential Use in Packaging: A Comparison of PLA/Chitosan and PLA/Cellulose Acetate Films

Poly(lactic acid) (PLA) is a biodegradable polymer that exhibits high elastic modulus, high mechanical strength, and feasible processability. However, high cost and fragility hinder the application of PLA in food packaging. Therefore, this study aimed to develop flexible PLA/acetate and PLA/chitosan films with improved thermal and mechanical properties without the addition of a plasticizer and additive to yield extruder compositions with melt temperatures above those of acetate and chitosan. PLA blends with 10, 20, and 30 wt% of chitosan or cellulose acetate were processed in a twin-screw extruder, and grain pellets were then pressed to form films. PLA/acetate films showed an increase of 30 °C in initial degradation temperature and an increase of 3.9 % in elongation at break. On the other hand, PLA/chitosan films showed improvements in mechanical properties as an increase of 4.7 % in elongation at break. PLA/chitosan film which presented the greatest increase in elongation at break proved to be the best candidate for application in packaging.     

Reactive Blending of Biodegradable Polymers: PLA and Starch

Poly(lactic acid) (PLA) and starch are important biodegradable polymers. Mechanical properties of blends of PLA and starch using conventional processes were very poor because of incompatibility. In this study, PLA and starch were blended with a reactive agent during the extrusion process. The affects of the reactive blending were investigated and significant improvements were confirmed by measuring the tensile strength and elongation at break, IR spectra, and DSC.     

Investigation on the Influence of EVA Content on the Mechanical and Thermal Characteristics of Poly(lactic acid) Blends

Poly(lactic acid) (PLA) has gained considerable attention nowadays as a biocompatible polymer owing to its advantage of being prepared from renewable resources. PLA exhibits excellent tensile strength, fabricability, thermal plasticity and biocompatibility properties comparable to many petroleum based plastics. However, low heat distortion temperature, brittleness and slow crystallization rate limit the practical applications of PLA. In order to address these limitations, an attempt has been made in the current work to prepare binary blends of PLA with ethylene vinyl acetate (EVA) at different compositions via melt mixing technique. Systematic investigation on the mechanical properties, thermal degradation and crystallization behavior for PLA-EVA blends was carried out. The impact strength of binary blends of PLA–EVA was found to increase significantly by 176% for 15 wt% of EVA compared to virgin PLA. This is due to the strong interfacial adhesion among PLA and EVA resulting in brittle to ductile transition. Scanning electron microscopy analysis for impact fractured surfaces of binary blends of PLA implied the toughening effect of PLA by EVA. Thermogravimetry analysis results revealed that the activation energy of PLA–EVA blends decreased with increase in EVA content in the PLA matrix. While, differential scanning calorimetry results obtained for PLA–EVA blends revealed the improvement in crystallinity when compared with neat PLA. The effect of EVA on non-isothermal melt crystallization kinetics of PLA was also examined via DSC at various heating rates. Decreasing trend in the t_1/2 values indicated the faster rate of crystallization mechanism after addition of EVA in the PLA matrix.     

Poly(Ethylene Glycol) as a Compatibilizer for Poly(Lactic Acid)/Thermoplastic Starch Blends

A new route to prepare poly(lactic acid) (PLA)/thermoplastic starch (TPS) blends is described in this work using poly(ethylene glycol) (PEG), a non-toxic polymer, as a compatibilizer. The influence of PEG on the morphology and properties of PLA/TPS blends was studied. The blends were processed using a twin-screw micro-compounder and a micro-injector. The morphologies were analyzed by scanning and transmission electron microscopies and the material properties were evaluated by dynamic-mechanical, differential scanning calorimetry, thermogravimetric analysis and mechanical tests. PLA/TPS blends presented large TPS phase size distribution and low adhesion between phases which was responsible for the lower elastic modulus of this blend when compared to pure PLA. The addition of PEG resulted in the increase of PLA crystallization, due to its plasticizing effect, and improvement of the interfacial interaction between TPS and PLA matrix. Results show that incorporation of PEG increased the impact strength of the ternary blend and that the elastic modulus remained similar to the PLA/TPS blend.     

Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), ¹H and ¹³C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, ¹³C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.     

Characterization of EVA/PLA Blends When Exposed to Different Environments

EVA/PLA blends compatibilized with EVA-g-PLA grafted copolymers synthesized by reactive extrusion, through transesterification reaction between ethylene-vinyl-acetate (EVA) and polylactide (PLA) using titanium propoxide (Ti(OPr)₄) as catalyst, were characterized when exposed to different environments. Stability to UV radiation was assessed exposing the samples to a Xenon lamp, which simulates the sun UV spectrum and the biodegradability was evaluated by biochemical oxygen demand (BOD) in a closed respirometer. Exposed samples were removed periodically and analyzed by several analytical techniques, such as, FTIR, DSC, rheology and tensile tests. The results obtained evidenced that UV radiation induces structural modifications, which affect substantially rheological and mechanical properties. Moreover, the blend with higher amount of copolymer exhibits lower photo durability and greater biodegradability. From the environmental point of view, these new materials are very promising for application with short lifetime, like packaging.     

Mechanical Properties and Isothermal Crystallization Behaviour of Poly(lactide)/Poly(methyl methacrylate)/α-Cellulose Composites

Polylactide (PLA)/polymethylmethacrylate (PMMA)/α-cellulose composites were fabricated using a twin-screw extruder. During fabrication, α-cellulose short fibres were incorporated for improving the toughness of the brittle PLA and a chain extender was used for reducing PLA hydrolysis. Highly transparent PLA and PMMA were blended to obtain miscible and transparent blends. For evaluating the performance of the PLA/PMMA/α-cellulose composites, a series of measurements, including tensile and Izod impact tests, light transmission and haze measurements, thermomechanical analysis, and determination of isothermal crystallisation behaviour, was conducted. Adding the chain extender considerably reduced the occurrence of hydrolytic degradation. Both the chain extender and α-cellulose short fibres increased the elongation at break and Izod impact strength of the composites. Compared with the neat PLA, including 1.0 wt% α-cellulose short fibres increased the elongation at break and Izod impact strength of the composite PLA by approximately 211 and 219 %, respectively. According to the observed mechanical performance, the optimal blending ratios for PLA and PMMA were between 90:10 and 80:20. The total light transmittance of the composites was as high as 91 %, indicating that the PLA/PMMA blend was highly miscible. The haze value of the PLA/PMMA/α-cellulose composites was lower than 32 %. Incorporating cellulose short fibres increased the number of crystallisation sites and crystallinity of the PLA/PMMA/α-cellulose composites while reducing the spherulite dimensions.     

Effects of Compatibilizer and Thermoplastic Starch (TPS) Concentration on Morphological,Rheological, Tensile,Thermal and Moisture Sorption Properties of Plasticized Polylactic Acid/TPS Blends

The blends of polylactic acid plasticized with acetyl tributyl citrate (P-PLA) and thermoplastic wheat starch (TPS) were prepared by a co-rotating twin screw extruder and the effect of maleic anhydride grafted PLA (PLA-g-MA) content as reactive compatibilizer on blends compatibility through morphological, rheological and tensile properties of the blends was investigated. Considerable improvement in properties of P-PLA/TPS (70/30 w/w) blend with incorporating the optimum PLA-g-MA content of 4 phr was achieved as this blend exhibited better morphological and rheological properties with an increase by 158 and 276% in tensile strength and elongation at break, respectively, compared to the uncompatibilized blend. Also the thermal stability and moisture sorption properties of the blends as effected by TPS content were studied. Decreasing in thermal stability and increasing in equilibrium moisture content of the blends were observed with progressively increasing of TPS content. For prediction the moisture sorption behaviour of blends with various TPS contents at different relative humidity, the moisture sorption isotherm data were modeled by GAB (Guggenheim–Anderson–de Boer) model.     

Mechanical and Barrier Properties of Biodegradable Films Made from Chitosan and Poly (Lactic Acid) Blends

Biodegradable film blends of chitosan with poly(lactic acid) (PLA) were prepared by solution mixing and film casting. The main goal of these blends is to improve the water vapor barrier of chitosan by blending it with a hydrophobic biodegradable polymer from renewable resources. Mechanical properties of obtained films were assessed by tensile test. Thermal properties, water barrier properties, and water sensitivity were studied by differential scanning calorimeter analysis, water vapor permeability measurements, and surface-angle contact tests, respectively. The incorporation of PLA to chitosan improved the water barrier properties and decreased the water sensitivity of chitosan film. However, the tensile strength and elastic modulus of chitosan decreased with the addition of PLA. Mechanical and thermal properties revealed that chitosan and PLA blends are incompatible, consistent with the results of Fourier transform infrared (FTIR) analysis that showed the absence of specific interaction between chitosan and PLA.     

Biodegradability of Poly (lactic acid), Preparation and Characterization of PLA/Gum Arabic Blends

In this study, the biodegradation of PLA films using microorganisms from Lake Bogoria (Kenya) were investigated. The biodegradation tests done using certain strains of thermophilic bacteria showed faster biodegradation rates and demonstrated temperature dependency. The biodegradation of the PLA films was studied using Gel Permeation Chromatography (GPC) and light microscopy. The biodegradation of PLA was demonstrated by decrease in molecular weight. The preparation and characterization of PLA/Gum Arabic blends were also investigated using DSC, TGA, TMA and NMR. In summary, the results obtained in this research show that PLA films undergo fast biodegradation using thermophiles isolated from Lake Bogoria. The PLA/GA blends studies show it is possible to prepare films of varying hydrophobic–hydrophilic properties for various applications.