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.     

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.     

Enhancement of Tensile Strength and Flexibility of Polycaprolactone/Tapioca Starch Blends by Octadecylamine Modified Clay

Polycaprolactone/tapioca starch/octadecylamine modified clay (OMMT) nanocomposites were successfully prepared by melt blending. X-ray diffraction and transmission electron microscopy (TEM) of the products showed that they are nanocomposites of a mixture intercalated and exfoliated types. In addition, the TEM also revealed that the OMMT layers are homogeneously distributed in the polymer matrix. The presence of 1 php of OMMT improved the compatibility of the polymers in the blends which consequently increased the tensile strength of the blend of more than 60% and elongation at break of more than 1,000%.     

Preparation and Properties of Thermoplastic Starch/Montmorillonite Nanocomposite Using N-(2-Hydroxyethyl)formamide as a New Additive

N-(2-Hydroxyethyl)formamide (HF) was synthesized efficiently and used as a new additive to prepare thermoplastic starch/montmorillonite nanocomposite (TPS/MMT). Here, HF acted as both plasticizer for TPS and swelling agent for MMT. The hydrogen bond interaction among HF, starch and MMT was proven by Fourier-transform infrared (FT-IR) spectroscopy. By scanning electron microscope (SEM), starch granules were completely disrupted. Atomic force microscopy demonstrated that partially exfoliated TPS/MMT nanocomposite was formed. The crystallinity of corn starch, MMT, HF-plasticized TPS (HTPS) and TPS/MMT nanocomposite was characterized by X-ray diffraction (XRD). Thermal stability of HTPS and TPS/MMT was determined by thermogravimetric analysis (TGA). The water resistance of TPS/MMT nanocomposite increased compared with that of pure HTPS. Tensile strengths of TPS/MMT nanocomposites were higher than those of HTPS, but just the reverse for elongations at break.     

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

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

Effect of Cotton Fiber Contents and Lengths on Properties of Thermoplastic Starch Composites Prepared from Rice and Waxy Rice Starches

Biodegradable polymer was prepared as thermoplastic starch (TPS) using rice and waxy rice starches. In order to increase mechanical properties and reduce water absorption of the TPS, cotton fiber was incorporated as the fiber reinforcement into the TPS matrix. The effect of cotton fiber contents and lengths on properties of the TPS was examined. Internal mixer and compression molding machine were used to mix and shape the samples. It was found that the thermoplastic rice starch (TPRS) showed higher stress at maximum load and Young’s modulus but lower strain at maximum load than the thermoplastic waxy rice starch (TPWRS). In addition, stress at maximum load and Young’s modulus of both TPRS and TPWRS increased significantly with the addition of the cotton fiber. Cotton fiber contents and lengths also affected mechanical properties of the TPRS and TPWRS composites. Moreover, water absorption of the TPRS and TPWRS composites decreased by the use of the cotton fibers. FT-IR and XRD techniques were used to study a change in functional group and crystallinity of the thermoplastic starch composites. Morphological, thermal and biodegradable properties of different thermoplastic starch composites were also investigated.     

Processing and mechanical properties of biodegradable Poly(hydroxybutyrate-co-valerate)-starch compositions

Poly(hydroxybutyrate-co-valerate) (PHBV) is a completely biodegradable thermoplastic polyester produced by microbial fermentation. The current market price of PHBV is significantly higher than that of commodity plastics such as polyethylene and polystyrene. It is therefore desirable to develop low-cost PHBV based materials to improve market opportunities for PHBV. We have produced low-cost environmentally compatible materials by blending PHBV with granular starch and environmentally benign CaCO₃. Such materials can be used for specific applications where product biodegradability is a key factor and where certain mechanical properties can be compromised at the expense of lower cost. The inclusion of granular starch (25 wt%) and CaCO₃ (10 wt%) in a PHBV matrix (8% HV, 5% plasticizer) reduces the cost by approximately 40% and has a tensile strength of 16 MPa and flexural modulus of 2.0 Gpa, while the unfilled PHBV/plasticizer matrix has a tensile strength of 27 MPa and a flexural modulus of 1.6 GPa.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.     

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.     

Preparation and Characterization of Clay Nanocomposites of Plasticized Starch and Polypropylene Polymer Blends

Plasticized starch (PLS) is a renewable, degradable, and inexpensive polymer, but it suffers from poor mechanical properties. The mechanical properties can be improved by blending PLS with polyolefins, nonetheless, at high PLS content, the mechanical properties remain poor. Here we show that addition of clay can greatly improve the mechanical properties of PLS/polypropylene blends at high starch content. Unmodified and organically modified montmorillonite clays, MMT and Cloisite 30B respectively, were added to blends of glycerol-plasticized starch and polypropylene, compatibilized using maleated polypropylene. TEM indicates that MMT is well dispersed in the PLS phase of the blends, while Cloisite 30B is located both within the PLS phase as well as at the interface between PLS and PP. At high PLS content, the addition of clay increased the tensile strength and tensile modulus by an order of magnitude, while reducing the ultimate elongation only slightly. Such improvements are attributable to both the addition of clay as a reinforcing component, as well as to the change in the two phase morphology due to addition of clay.     

The Effect of Polymeric Chain Extenders on Physical Properties of Thermoplastic Starch and Polylactic Acid Blends

The effects of a polymeric chain extender on the properties of bioplastic film made from blends of plasticized polylactic acid (p-PLA) and thermoplastic starch (TPS) were studied. Joncryl^? ADR 4370S, a polymeric chain extender, was blended with TPS and p-PLA at a level of 1% (w/w). A co-rotating twin-screw extrusion process was used to prepare films with various ratios of TPS and p-PLA. Mechanical and physical properties of films, including film tensile properties, surface energy, moisture content, hydrophilicity, moisture sorption behaviour and thermal mechanical properties were determined. During extrusion, films enhanced by 1% Joncryl addition demonstrated more desirable and consistent qualities, such as smoother film edge and surface. Addition of Joncryl significantly improved film tensile strength, 0.2% offset yield strength, and elongation, especially evident with the 250% elongation of 70/30 (TPS/p-PLA) film. Total surface energy of films was not significantly influenced by addition of Joncryl. However, the polar contribution to the total surface energy of 70/30 (TPS/p-PLA) film increased after the addition of Joncryl. The study showed that blending TPS with p-PLA transformed TPS film from being highly hydrophilic to highly hydrophobic. On the other hand, addition of Joncryl had limited effects on moisture content, water solubility, glass transition temperature and moisture sorption behaviour of TPS/p-PLA blend films.     

Application of Cellulose Microfibrils in Polymer Nanocomposites

Cellulose microfibrils obtained by the acid hydrolysis of cellulose fibers were added at low concentrations (2–10% w/w) to polymer gels and films as reinforcing agents. Significant changes in mechanical properties, especially maximum load and tensile strength, were obtained for fibrils derived from several cellulosic sources, including cotton, softwood, and bacterial cellulose. For extruded starch plastics, the addition of cotton-derived microfibrils at 10.3% (w/w) concentration increased Young’s modulus by 5-fold relative to a control sample with no cellulose reinforcement. Preliminary data suggests that shear alignment significantly improves tensile strength. Addition of microfibrils does not always change mechanical properties in a predictable direction. Whereas tensile strength and modulus were shown to increase during addition of microfibrils to an extruded starch thermoplastic and a cast latex film, these parameters decreased when microfibrils were added to a starch–pectin blend, implying that complex interactions are involved in the application of these reinforcing agents.     

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.     

Poly(ethylene oxide)-coated granular starch-poly(hydroxybutyrate-co-hydroxyvalerate) composite materials

Granular cornstarch was coated with several biodegradable polymers in an effort to improve the mechanical properties of starch-poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) composites. Only samples containing poly(ethylene oxide) (PEO)-coated granular starch showed a large improvement in tensile properties over uncoated starch. For example, a 50/50 blend of PEO-coated starch and PHBV had a tensile strength of 19 MPa and an ultimate elongation of 23%, compared to 10 MPa and 11% for a similar blend containing uncoated starch. PEO may act as an adhesive between the starch and the PHBV and/or increase the toughness and resistance to crack growth of PHBV around the starch granules.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product and the use of the name by the USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Biodegradable corn starch loose- fill. I. The effect of the extrusion temperature on the physical properties of loose-fill

Extrusion with an intermeshing corotating twin-screw extruder with a limited amount of water caused structural changes in corn starch. The structural changes resulted in a transformation-from a semicrystalline to an amorphous state and the development of orientation of molecular chains in the amorphous region during extrusion. These structural changes, in turn, caused an increase in theT _g, tensile strength, and resilience of the extruded corn starch. Our experimental results showed that the tensile properties and resilience of the expanded corn starch extruded at 240‡C were the best: tensile strength, 1.7 kPa; tensile modulus, 40.4 kPa; and resilience, 57.2%. Extrusion produced an expanded corn starch suitable for protective loose-fill.     

A Biobased Blend of Cellulose Diacetate with Starch

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

Preparation and Characterization of Gamma Irradiated Sugar Containing Starch/Poly (Vinyl Alcohol)-Based Blend Films

Blends based on different ratios of starch (35–20%) and plasticizer (sugar; 0–15%) keeping the amount of poly(vinyl alcohol) (PVA) constant, were prepared in the form of thin films by casting solutions. The effects of gamma-irradiation on thermal, mechanical, and morphological properties were investigated. The studies of mechanical properties showed improved tensile strength (TS) (9.61 MPa) and elongation at break (EB) (409%) of the starch-PVA-sugar blend film containing 10% sugar. The mechanical testing of the irradiated film (irradiated at 200 Krad radiation dose) showed higher TS but lower EB than that of the non-radiated film. FTIR spectroscopy studies supported the molecular interactions among starch, PVA, and sugar in the blend films, that was improved by irradiation. Thermal properties of the film were also improved due to irradiation and confirmed by thermo-mechanical analysis (TMA), differential thermo-gravimetric analysis (DTG), differential thermal analysis (DTA), and thermo-gravimetric analysis (TGA). Surface of the films were examined by scanning electron microscope (SEM) image that supported the evidence of crosslinking obtained after gamma irradiation on the film. The water up-take and degradation test in soil of the film were also evaluated. In this study, sugar acted as a good plasticizing agent in starch/PVA blend films, which was significantly improved by gamma radiation and the prepared starch-PVA-sugar blend film could be used as biodegradable packaging materials.     

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.     

A Processing,Characterization and Marine Biodegradation Study of Melt-Extruded Polyhydroxyalkanoate (PHA) Films

A series of polyhydroxyalkanoates (PHA), all containing 1% nucleating agent but varying in structure, were melt-processed into films through single screw extrusion techniques. This series consisted of three polyhydroxybutyrate (PHB) and three polyhydroxybutyrate-valerate (PHBV) resins with varying valerate content. Processing parameters of temperature in the barrel (165–173 °C) and chill rolls (60 °C) were optimized to obtain cast films. The gel-permeation chromatography (GPC) results showed a loss of 8–19% of the polymer’s initial molecular weight due to extrusion processing. Modulated differential scanning calorimetry (MDSC) displayed glass transition temperatures of the films ranging from −4.6 to 6.7 °C depending on the amount of crystallinity in the film. DSC data were also used to calculate the percent crystallinity of each sample and slightly higher crystallinity was observed in the PHBV series of samples. X-ray diffraction patterns did not vary significantly for any of the samples and crystallinity was confirmed with X-ray data. Dynamic mechanical analysis (DMA) verified the glass transition trends for the films from DSC while loss modulus (E′) reported at 20 °C showed that the PHBV (3,950–3,600 MPa) had the higher E′ values than the PHB (3,500–2,698 MPa) samples. The Young’s modulus values of the PHB and PHBV samples ranged from 700 to 900 MPa and 900 to 1,500 MPa, respectively. Polarized light microscopy images revealed gel particles in the films processed through single-screw extrusion, which may have caused diminished Young’s modulus and tensile strength of these films. The PHBV film samples exhibited the greatest barrier properties to oxygen and water vapor when compared to the PHB film samples. The average oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) for the PHBV samples was 247 (cc-mil/m²-day) and 118 (g-mil/m²-day), respectively; while the average OTR and WVTR for the PHB samples was 350 (cc-mil/m²-day) and 178 (g-mil/m²-day), respectively. Biodegradation data of the films in the marine environment demonstrated that all PHA film samples achieved a minimum of 70% mineralization in 40 days when run in accordance with ASTM 6691. For static and dynamic incubation experiments in seawater, microbial action resulting in weight loss as a function of time showed all samples to be highly biodegradable and correlated with the ASTM 6691 biodegradation data.     

Effect of Coconut, Sisal and Jute Fibers on the Properties of Starch/Gluten/Glycerol Matrix

Coconut, sisal and jute fibers were added as reinforcement materials in a biodegradable polymer matrix comprised of starch/gluten/glycerol. The content of fibers used in the composites varied from 5% to 30% by weight of the total polymers (starch and gluten). Materials were processed in a Haake torque rheometer (120 °C, 50 rpm) for 6 min. The mixtures obtained were molded by heat compression and further characterized. Addition of lignocellulosic fibers in the matrix decreased the water absorption at equilibrium. The diffusion coefficient decreased sharply around 5% fiber concentration, and further fiber additions caused only small variations. The thermogravimetric (TG) analysis revealed improved thermal stability of matrix upon addition of fibers. The Young’s modulus and ultimate tensile strength increased with fiber content in the matrix. The storage modulus increased with increasing fiber content, whereas tanδ curves decreased, confirming the reinforcing effect of the fibers. Morphology of the composites analyzed under the scanning electron microscope (SEM) exhibited good interfacial adhesion between the matrix and the added fibers. Matrix degraded rapidly in compost, and addition of increased amounts of coconut fiber in the matrix caused a slowdown the biodegradability of the matrix. Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may be suitable.     

Storage stability of injection-molded starch-zein plastics under dry and humid conditions

Corn starch and zein mixtures (4 : 1 dry weight) were extruded and injection-molded in the presence of plasticizers (glycerol and water). Tensile strength and percentage elongation of the molded plastics were measured before and after 1 week of storage under a dry or humid condition (11 or 93% RH). With 10–12% glycerol and 6–8% water, injection-molded plastics had relatively good tensile properties (20- to 25-MPa tensile strength and 3.5–4.7% elongation). But while exposed to dry conditions (11% RH), the molded plastics lost weight (0.5–1.5% in 7 days) and became very brittle, with significant decreases in tensile strength and elongation. Partial replacement (5–10%) of starch with a maltodextrin (average DE 5) reduced the glass transition and melting temperatures of the starch-zein mixture as well as the dry storage stability. Using potato starch instead of corn starch significantly improved the dry storage stability of the injection-molded starch-zein plastics (18- vs 11-MPa tensile strength). Anionic corn starches with a maleate or succinate group (DS<0.01) produced injection-molded plastics with improved tensile properties and storage stability. Plastics prepared from the starch maleate and zein mixture retained the strength during 1 week of dry storage without a significant change (26-MPa tensile strength and 3.7% elongation after 1 week of storage).Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.Journal paper No. J-15561 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa, Project No. 2863.