Tensile Properties of Polylactide/Poly(ethylene glycol) Blends

The blends of polylactide (PLA) and poly(ethylene glycol) (PEG) with different contents (0, 5, 10, 15, and 20 wt%) and molecular weights (\( \overline{M}_{w} \) 6000, 10,000 and 20,000, called respectively as PEG 6000, PEG 10,000, and PEG 20,000) were prepared by means of melt blending method. The effects of tensile speed, content and molecular weight of the PEG on the tensile properties of the PLA/PEG blends were investigated using a universal testing machine at 24 °C. With increasing tensile speed, the tensile modulus, strength and stress at break of the PLA/PEG blends marginally increased, while the tensile modulus and stress at break declined non-linearly, and the tensile strength dropped nearly linearly with increasing PEG 10,000 content. When the PEG 10,000 content was 5–15 wt%, the tensile strain at break of the PLA/PEG 10,000 blend markedly increased, and then decreased as the PEG 10,000 content exceeded 15 wt%. With increasing the molecular weight of PEG, tensile modulus and strength increased, whereas the tensile strain at break decreased. This showed that the application of right amount of lower molecular weight PEG was more conducive to improving the tensile toughness of the PLA/PEG blends, which was attributed to its better miscibility with PLA and increased mobility of PLA molecular chains.     

Soybean-Oil-Based Polyisocyanurate Rigid Foams

Polyisocyanurate foams were prepared from polymeric 4,4-diphenylmethane diisocyanate (MDI), soy polyol and polypropylene oxide polyol by varying isocyanate index from 110 to 350. The higher isocyanate index produced polyisocyanurate foams with higher thermal stability, improved flame resistance, tensile strength, higher modulus, and higher glass transition. Soy-based foams displayed better thermal stability, lower flammability, higher rigidity (modulus) and higher compression strength than those based on the propylene oxide polyols of the same molecular weight and functionality.     

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.     

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.     

Thermo-Chemical Decomposition Study of Polyurethane Elastomer Through Glycerolysis Route with Using Crude and Refined Glycerine as a Transesterification Agent

Due to the increasing amount of polyurethane waste, chemical recycling of these materials is a topic of growing interest for many researchers. The primary purpose of polyurethane feedstock recycling is to recover the starting polyol. In this study glycerolysis using glycerine from two sources and two purity grades is proposed as a method of chemical recycling. The main effort of this paper focuses on the employment of commercial glycerine of analytical grade and waste glycerine without purification derived from the biodiesel production, as a decomposing agent for polyurethane recycling. In this study, the influence of polyurethane to glycerine mass ratio (PU/GL) and the type of decomposing agent on the chemical structure by FTIR, ¹H NMR and GPC was examined. FTIR analysis of the glycerolysates showed absorption peaks similar to the virgin polyol. Those results are in compliance with GPC chromatograms, which showed for all samples, well-defined peak at ca. 13 min of retention time. The molecular weight of glycerolysates was ranging from 800 to 1300 g mol^?1 depending on PU/GL mass ratio. The novel decomposition agent, namely waste glycerine derived from biodiesel production was successfully used in glycerolysis process.     

Mechanical Properties and Morphology of Polypropylene/Poly(ethylene-co-octene) Blends

The polypropylene (PP)/poly(ethylene-co-octene) (POE) blends was prepared by means of a twin screw extruder in a range of temperature from 185 to 195 °C. The mechanical properties including tensile, flexural and impact of the PP/POE blends were measured at room temperature to identify the effect of the POE content on the mechanical properties. It was found that the Young’s modulus, tensile strength and tensile elongation at break decreased nonlinearly with increasing the POE weight fraction. While the V-notched and unnotched impact fracture strength increased nonlinearly with an increase of the POE weight fraction. The flexural modulus and strength decreased roughly linearly with increasing the POE weight fraction. Furthermore, the impact fracture surface of the blends was observed by using a scanning electronic microscope and the toughening mechanisms were discussed.     

Tensile Strength, Elongation, Hardness, and Tensile and Flexural Moduli of Injection-Molded TPS Filled with Glycerol-Plasticized DDGS

Continuing growth of biofuel industries 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. This research effort has quantified the effects on mechanical properties of adding DDGS and glycerol to a commercial thermoplastic starch (TPS). The methodology was to physically mix DDGS, as filler, with the TPS pellets and injection mold the blends into test bars using glycerol as a processing aid. The bars were then mechanically tested with blends from 0 to 65 %, by weight, of plasticized filler. The test bars were typically relatively brittle with little yielding prior to fracture with elongation between 1 and 3 %. 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 starch, and up to 30 % filler, the tensile strength drops about 15 %. The 20 and 50 % blends (without glycerol) have slightly greater stiffness than pure starch. With some other blends, the presence of plasticized filler degrades the tensile modulus with 35 % filler yielding about 1/3 the stiffness. Changes in the flexural modulus are much more pronounced as 20–25 % filled TPS has a 30 % increase in flexural stiffness. In terms of surface hardness, blends up to 60 % filler are within 20 % of the TPS baseline.     

Synthesis and Characterization of Polyols and Polyurethane Foams from PET Waste and Crude Glycerol

In this study, polyethylene terephthalate (PET) waste from post-consumer soft-drink bottles and crude glycerol from the biodiesel industry were used for the preparation of polyols and polyurethane foams. PET waste was firstly depolymerized by the glycolysis of diethylene glycol. The glycolyzed PET oligomers were then reacted with crude glycerol at different weight ratios to produce polyols via a series of reactions, such as esterification, transesterification, condensation, and polycondensation. The polyols were characterized by titration, viscometry, gel permeation chromatography (GPC), and differential scanning calorimetry. Subsequently, polyurethane (PU) foams were made via the reaction between the produced polyols and polymeric methylene-4,4′-diphenyl diisocyanate and were characterized by mechanical testing, scanning electron microscopy, and thermogravimetric analysis. Polyols from crude glycerol and their PU foams were also prepared to compare properties with those of polyols and PU foams from PET and crude glycerol. The influence of aromatic segments existing in glycolyzed PET and glycerol content on the properties of the polyols and PU foams was investigated. It was found that aromatic segments of polyols from glycolyzed PET helped increase their molecular weights and improve thermal stability of PU foams, while high glycerol content in polyols increased the hydroxyl number of polyols and the density and compressive strength of PU foams.     

Synthesis and Properties of Polyesters from Waste Grapeseed Oil: Comparison with Soybean and Rapeseed Oils

The aim of this study was to investigate the application of grapeseed oil, a waste product from the wine industry, as a renewable feedstock to make polyesters and to compare the properties of these materials with those derived from soybean and rapeseed oils. All three oils were epoxidized to give renewable epoxy monomers containing between 3.8 and 4.7 epoxides per molecule. Polymerisation was achieved with cyclic anhydrides catalysed by 4-methyl imidazole at 170 and 210 °C. Polymers produced from methyl tetrahydrophthalic anhydride (Aradur917^®) had greater tensile strength and Young’s Modulus (tensile strength = 12.8 MPa, Young’s Modulus = 1005 MPa for grapeseed) than methyl nadic anhydride (MNA) derived materials (5.6 and 468 MPa for grapeseed) due to increased volume of MNA decreasing crosslink density. Soybean and grapeseed oils produced materials with higher tensile strength (5.6–29.3 MPa) than rapeseed derived polyesters (2.5–3.9 MPa) due to a higher epoxide functionality increasing crosslinking. T _g’s of the polyesters ranged from ?36 to 62 °C and mirrored the trend in epoxide functionality with grapeseed producing higher T _g polymers (?17 to 17 °C) than soybean (?25 to 6 °C) and rapeseed (?36 to ?27 °C). Grapeseed oil showed similar properties to soybean oil in terms of T _g, thermal degradation and Young’s Modulus but produced polymers of lower tensile strength. Therefore grapeseed oil would only be a viable substitute for soybean for low stress applications or where thermal properties are more important.     

Instrumental Physical Analysis of Microwaved Glycerol Citrate Foams

Solid glycerol citrate polyester polymeric foams generated by microwave heating were further cured in a conventional oven at 100?°C for 0, 6, 24, 48, or 72?h and their physical properties were tested. Curing glycerol citrate polyesters resulted in decreased moisture content (MC), altered color, increased hydrated polymer weight loss (HWL), and increased polymer oven weight loss (OWL). Polyester polymer samples were evaluated for firmness and springiness employing a texture analyzer (Model TA/TX2i). Oven curing increased polymer firmness and springiness. For example, firmness and springiness in 48?h cured samples increased 202 and 143%, respectively, when compared to uncured controls. High correlations were found comparing OWL, MC, HWL, firmness, and springiness. Compression molded samples obtained from ground cured and non-cured polymers were evaluated for tensile strength, elongation and Young??s modulus using the Instron universal test machine (Model 4201). Curing promoted higher tensile strengths and elongation but did not affect Young??s modulus values. High correlations were found between springiness, firmness, tensile strength, and elongation. The texture analyzer was shown to have merit in the preliminary evaluation of the glycerol citrate polyester polymers.     

Novel Renewable Polyols Based on Limonene for Rigid Polyurethane Foams

Novel renewable polyols based on limonene were synthesized using thiol-ene “click” chemistry. These limonene based polyols were structurally characterized using wet methods (hydroxyl number, acid value and viscosity), gel permeation chromatography and spectroscopic methods. The results indicated that high yield of polyols from limonene based materials can be obtained using thiol-ene reaction. These limonene based polyols were used successfully for preparation of rigid polyurethane foams. These foams had regular shape cells and uniform cell size distribution. Thermal studies on these foams indicated that foams were thermally stable up to 250 °C. The glass transition temperature of the foams was higher than 200 °C. These rigid polyurethane foams had high compressive strength and the highest compressive strength of 195 kPa was observed. These foams have good physical–mechanical characteristics and could be suitable for all the applications of rigid polyurethane foams such as thermal insulation of freezers, storage tanks for the chemical and food industries, and packing materials for food industries.     

Aliphatic Polyester-Based Green Renewable Eco-composites from Agricultural Residues: Characterization and Assessment of Mechanical Properties

The biodegradability, morphology, and mechanical properties of composite materials consisting of maleic anhydride-grafted poly(butylene succinate adipate) (PBSA-g-MA) and agricultural residues (wheat bran, WB) were evaluated. Composites containing maleic anhydride-grafted PBSA (PBSA-g-MA/WB) exhibited noticeably superior mechanical properties compared with those of PBSA/WB because of greater compatibility with WB. PBSA/WB exhibited a tensile strength at break of approximately 2–15 MPa more than PBSA-g-MA/WB. The dispersion of WB in the PBSA-g-MA matrix was highly homogeneous as a result of ester formation and the subsequent creation of branched and cross-linked macromolecules between the anhydride carboxyl groups of PBSA-g-MA and hydroxyl groups in WB. Additionally, the PBSA-g-MA/WB composites were more easily processed due to their lower melt viscosity. Water resistance of PBSA-g-MA/WB was higher than that of PBSA/WB, although weight loss of composites buried in Azospirillum brasilense BCRC 12270 liquid culture medium compost indicated that both were biodegradable, especially at high levels of WB substitution. After 60 days, the weight loss of the PBSA-g-MA/WB (40 wt%) composite was greater than 90 %. PBSA/WB exhibited a weight loss of approximately 4–8 wt% more than PBSA-g-MA/WB. The PBSA/WB and PBSA-g-MA/WB composites were more biodegradable than pure PBSA, which implies a strong connection between WB content and biodegradability.     

Mechanical Properties of Microcrystalline Cellulose (MCC) Filled Engineering Thermoplastic Composites

In this study, engineering thermoplastic composites were prepared from microcrystalline cellulose (MCC)-filled nylon 6. MCC were added to nylon 6 using melt mixing to produce compounded pellets. The MCC-filled nylon 6 composites with varying concentrations of MCC (from 2.5 to 30 wt%) were prepared by injection molding. The tensile and flexural properties of the nylon 6 composites were increased significantly with the addition of MCC. The maximum strength and modulus of elasticity for the nylon 6 composites were achieved at a MCC weight fraction of 20 %. The Izod impact strength of composites decreased with the incorporation of MCC without any surface treatments and coupling agent. This observation is quite expected for filled polymer systems and has been commonly observed. There was a strong correlation between density and tensile (r = 0.94) and flexural modulus of elasticity (r = 0.9). MCC filled composites manufactured by injection method had highly uniform density distribution through their thickness. The higher mechanical results with lower density demonstrate that MCC can be used as a sufficient reinforcing material for low cost, eco-friendly composites in the automotive industry especially for under-the-hood applications (engine covers, intake manifolds and radiator end tanks) as well as in other applications such as the building and construction industries, packaging, consumer products etc.     

Effect of Varying Filler Concentration on Zinc Oxide Nanoparticle Embedded Chitosan Films as Potential Food Packaging Material

Prevailing scenario of non-biodegradable food packaging materials worldwide was the motivation for this research. More than half of the packaging materials used today are non-biodegradable and lack one or the other feature that keeps it from being an ideal food packaging material. Based on the current need of food grade packaging materials, the present study illustrates the amelioration of the properties of biodegradable chitosan films with the incorporation of zinc oxide (ZnO) nanoparticles in varying concentration. The ZnO nanoparticles (ZnONPs) used as fillers in the chitosan films were synthesized by supersaturation method. They were characterized using UV–visible spectrophotometry, X-ray diffraction and field emission scanning electron microscopy (FE-SEM). The particles were observed to be around 100–200 nm in size. The chitosan films with varying concentration of ZnONPs were synthesized and characterized using Fourier transform infrared spectroscopy and FE-SEM. The films were studied for their thermal stability, water vapor transmission rate (WVTR) and mechanical properties. The thermal stability, as determined by Thermo Gravimetric Analysis and Differential Scanning Calorimetry increased slightly with increasing percentage of embedded ZnONPs while a substantial decrease in WVTR was observed. Mechanical properties also showed improvements with 77% increment in tensile modulus and 67% increment in tensile strength. The antimicrobial activity of the films was also studied on gram positive bacterium Bacillus subtilis (B. subtilis) and gram negative bacterium Escherichia coli (E. coli) by serial dilution method. A twofold and 1.5-fold increment in the antimicrobial activity was observed for B. subtilis and E. coli, respectively, with increased ZnONPs concentration in the films from 0(w/w) to 2%(w/w). Films thus prepared can prove to be of immense potential in the near future for antimicrobial food packaging applications.     

Characterization of Extruded Thermoplastic Starch Reinforced by Montmorillonite Nanoclay

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

Aliphatic–Aromatic Polyols by Thiol–Ene Reactions

Aliphatic–aromatic polyols were synthesized by thiol–ene reactions (photochemical or thermal) using mercaptanized starting materials from bio-based compounds: limonene dimercaptan, thioglycerol, mercaptanized castor oil and isosorbide (3-mercaptopropyl) ether. Aromatic starting materials were phenols containing double bonds; ortho-allyl phenol (OAP, petrochemical-based) and eugenol (EUG, bio-based). The phenolic hydroxyl groups were blocked by alkoxylation with propylene oxide (PO) or glycidol (GLY) prior to use in thiol–ene reaction. The aromatic rings were attached to the mercaptans by reacting thiol groups with the double bonds of alkoxylated OAP (OAP–PO and OAP–GLY) and alkoxylated EUG (EUG–PO and EUG–GLY). These synthesized aliphatic–aromatic polyols were utilized for preparation of rigid polyurethane foams whose physical–mechanical properties were superior to those made only from bio-based aliphatic polyols. These rigid PU foams can be used in a wide range of applications; such as thermal insulation of freezers, buildings, pipes and storage tanks for food and chemical industries, as wood substitute, packaging materials and flotation materials.     

Possible use of sludge ash as filler in natural rubber

Potential use of sludge ash as a filler in NR was studied. In this study, two grades of sludge ash namely SA-300 and SA-700 were prepared by sintering sludge waste obtained from concentrated natural rubber (NR) latex production at 300 and 700 °C, respectively. Properties of NR filled with various contents of SA-300 and SA-700 were then investigated and compared with those of NR filled with precipitated calcium carbonate (CaCO₃). The results reveal that, regardless of the filler type, both scorch time (t _s1) and optimum cure time (t _c90) decrease whereas hardness and modulus increase with increasing filler loading. At a given loading, both SA-300 and SA-700 give shorter scorch time and cure time with higher hardness and modulus than CaCO₃. Due to their higher specific surface area and greater cure activation efficiency, SA-300 and SA-700 provide better reinforcement, i.e., greater tensile strength; tear strength and abrasion resistance than CaCO₃. Taken as a whole, it could be said that the two grades of sludge ash could be utilized as rubber fillers with economic advantage.     

Biodegradability of Epoxidized Soybean Oil Based Thermosets in Compost Soil Environment

In this study, bio-thermoset from epoxidized soybean oil (ESO) was prepared in the presence of methylhexahydrophthalic anhydride curing agent and 2-ethyl-4-methylimidazole catalyst. The crosslink densities of the synthesized ESO are ranged from 0.109 × 10^?3 to 0.308 × 10^?3 mol/cm³. The ESO bio-thermosets were exposed to the soil-burial test for 8 months. Weight change and morphology of the degraded ESO specimens were assessed. It was found that the weight loss of ESO was governed by the materials compositions, crosslink density and the soil-burial exposure time. The 3 mm thickness ESO bio-thermosets with crosslink density of 0.109 × 10^?3 mol/cm³ had fully biodegraded after soil-burial for 6 months. In addition, 16S rDNA sequencing was carried out to identify the soil microorganisms. It was suggested that Comamonas sp., Bacillus sp., Streptomyces sp. and Acinetobacter sp. are the possible soil microbes that degrade the ESO bio-thermosets in the compost soil environment.     

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.     

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.