Preparation and properties of thermoplastic starch/montmorillonite nanocomposites using N,N‐bis(2‐hydroxyethyl)formamide as a new additive

N,N‐Bis(2‐hydroxyethyl)formamide (BHF) was synthesized efficiently and used as a new additive to prepare thermoplastic starch/montmorillonite (TPS/MMT) nanocomposites. Here, BHF acted as both plasticizer for TPS and swelling agent for MMT. The hydrogen bond interaction among BHF, starch, and MMT was proven by Fourier transform infrared (FTIR) spectroscopy. By scanning electron microscope (SEM), starch granules were completely disrupted. Atomic force microscopy demonstrated that partially exfoliated TPS/MMT nanocomposites were formed. The crystallinity of corn starch, MMT, BHF‐plasticized TPS (BTPS), and TPS/MMT nanocomposites was characterized by X‐ray diffraction (XRD), XRD demonstrated that partially intercalated TPS/MMT nanocomposites were formed. The water resistance of TPS/MMT nanocomposites increased compared with that of pure BTPS. Mechanical properties of BTPS and TPS/MMT nanocomposites were examined. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

N-(2-Hydroxyethyl)formamide as a new plasticizer for thermoplastic starch

N-(2-Hydroxyethyl)formamide (HF) was synthesized efficiently and used as a new plasticizer for corn starch to prepare thermoplastic starch (TPS). The hydrogen bond interaction between HF and starch was proved by Fourier-transform infrared (FT-IR) spectroscopy. Scanning electron microscope (SEM) revealed that starch granules were completely disrupted and a continuous phase was obtained. The crystallinity of corn starch and HF-plasticized TPS (HTPS) were characterized by X-ray diffraction (XRD). The glass transitions of glycerol-plasticized TPS (GTPS) and HTPS were investigated by differential scanning calorimetry (DSC). The water resistance of GTPS was better than that of HTPS. In addition, the flexibility of HTPS was better than that of GTPS at low relative humidity.     

Urea and formamide as a mixed plasticizer for thermoplastic starch

Mixtures of urea and formamide were tested as plasticizers for thermoplastic starch (TPS). The hydrogen bonding interactions between urea/formamide and starch were investigated by using Fourier‐transform infrared spectroscopy (FT‐IR). The thermal stability, mechanical properties and starch retrogradation behavior were also studied by thermogravimetric analysis (TGA), tensile testing and X‐ray diffraction (XRD), respectively. TPS plasticized by urea (20 wt%) and formamide (10 wt%) showed better thermal stability and water resistance than conventional TPS plasticized by glycerol. Moreover, the tensile stress, strain and energy at break, respectively, reached 4.83 MPa, 104.6 % and 2.17 N m after storing in an atmosphere of relative humidity (RH) of 33 % for one week. At the same time, this mixed plasticizer could effectively restrain the retrogradation of starch. Copyright © 2004 Society of Chemical Industry     

Formamide as the plasticizer for thermoplastic starch

As a novel plasticizer, formamide was tested in thermoplastic starch (TPS), in which native cornstarch granules were proved to transfer to a continuous phase by scanning electron microscope (SEM) and the hydrogen bond interaction between plasticizer and starch was proved by Fourier transform infrared (FTIR) spectroscopy. Mechanical tests showed that tensile strength and Young's modulus of formamide‐plasticized TPS (FPTPS) were lower than glycerol‐plasticized TPS (GPTPS) and elongation at break and energy break were higher. The effect of formamide and glycerol on the retrogradation of TPS was studied using X‐ray diffractometry. Formamide could effectively restrain the starch retrogradation at three different relative humidity (RH) environments, because it could form the more stable hydrogen bonds with the starch hydroxy group than glycerol. From these results, we found that the elongation at break, energy break, and the retrogradation of TPS were ameliorated by formamide. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1769–1773, 2004     

Microstructural characterization of corn starch‐based porous thermoplastic composites filled with multiwalled carbon nanotubes

Microstructural characterization of corn starch‐based porous thermoplastic (TPS) composites containing various contents (0.1, 0.5, and 1 wt %) of multiwalled carbon nanotubes (MWCNTs) was performed. Corn starch was plasticized with a proper combination of glycerol and stearic acid. TPS composites with MWCNT were prepared conducting melt extrusion followed by injection molding. TPS containing 1 wt % of MWCNTs exhibited higher tensile strength and elastic modulus values than neat TPS. Moreover, TPS electrical conductivity was determined to increase with increasing content of MWCNTs. X‐ray diffraction measurements revealed that incorporation of MWCNTs increased the degree of TPS crsystallinity to some extent. Scanning electron microscopy examination revealed that MWCNT altered TPS surface morphology and tensile failure modes, significantly. Transmission electron microscopy investigation showed that dispersion characteristics of MWCNTs within TPS were in the form of tiny clusters around micro pores of TPS, which is considered influential on electrical conductivity of the resulting composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Comparison of sorbitol and glycerol as plasticizers for thermoplastic starch in TPS/PLA blends

This article investigates the structure and properties of thermoplastic starch/PLA blends where the TPS phase is plasticized by sorbitol, glycerol, and glycerol/sorbitol mixtures. The blends were prepared using a twin‐screw extruder where starch gelatinization, water removal, and dispersion of TPS into a PLA matrix were carried out sequentially. The plasticizers were added to starch in the first stage of the extruder to allow complete starch gelatinization. The PLA was added at mid‐extruder and thoroughly mixed with the TPS. The plasticizer concentration was varied from 30 to 42% and the TPS content was varied from 27 to 60% on a weight basis. In all investigated blends, the PLA formed the continuous phase and the TPS was the dispersed phase. The viscosity, blend morphology, tensile mechanical properties as well as the thermal properties of the materials were measured. It was found that the glycerol/sorbitol ratio has an important effect on the blend properties. Finer blend morphologies, higher tensile strength and modulus but lower crystallization rate were found for the sorbitol plasticized blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Poly(lactic acid) formulations with improved toughness by physical blending with thermoplastic starch

This work focuses on poly(lactic acid) (PLA) formulations with improved toughness by physical blending with thermoplastic maize starch (TPS) plasticized with aliphatic–aromatic copolyester up to 30 wt %. A noticeable increase in toughness is observed, due to the finely dispersed spherical TPS domains in the PLA matrix. It is worth to note the remarkable increase in the elongation at break that changes from 7% (neat PLA) up to 21.5% for PLA with 30 wt % TPS. The impact‐absorbed energy is markedly improved from the relatively low values of neat PLA (1.6 J m^?2) up to more than three times. Although TPS is less thermally stable than PLA due to its plasticizer content, in general, PLA/TPS blends offer good balanced thermal stability. The morphology reveals high immiscibility in PLA/TPS blends, with TPS‐rich domains with an average size of 1 μm, finely dispersed which, in turn, is responsible for the improved toughness. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45751.     

Poly(3‐hydroxybutyrate)–thermoplastic starch–organoclay bionanocomposites: Surface properties

Bionanocomposites based on poly(3‐hydroxybutyrate) (PHB) and starch plasticized with glycerol and water [thermoplastic starch (TPS)] with organically modified montmorillonite clay as a nanofiller were obtained by melt‐blending. The influence of the clay and TPS on the thermal and mechanical properties of the resultant bionanocomposite was investigated by various techniques, such as X‐ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM), thermogravimetric analysis, differential scanning calorimetry, and nanoindentation. The results obtained by AFM showed that bionanocomposites have a surface roughness of 30.88 nm, compared to 14.53 nm for processed PHB. This result is obtained due to the migration of clay layers to the surface. From XRD and TEM it was determined that the clay layers of the bionanocomposites are completely separated. The hardness and elastic moduli of bionanocomposites have values similar to those of PHB, improving the drawbacks of the PHB–TPS blends (65:35 weight ratio). The thermal properties do not present significant changes, and only the degree of crystallinity decreased with increasing clay content. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45217.     

High performance modified thermoplastic starch/linear low‐density polyethylene blends in one‐step extrusion

In this study, the morphology and the mechanical properties of thermoplastic starch (TPS)/linear low‐density polyethylene (LLDPE) blends prepared by one‐step and two‐step extrusion processing conditions were contrasted. In the presence of citric acid (CA), the compatibility of TPS/PE blends were proved to transfer to a high continuous dispersion in one‐step extrusion process by scanning electron microscopy analysis. By increasing the interaction between two phases, the mechanical properties of the blends were markedly improved, even reached the levels of the conventional plastics. The rheological study proved that the viscosity (η) of TPS and TPS/PE blends were both decreasing with increase in the content of CA at the same temperature, which ascribed to the acidity of CA was propitious to fragmentation and dissolution of cornstarch granules, deteriorated the chain entanglement in starch, and weakened the interaction of starch molecules. Both FTIR spectroscopy and thermal properties analysis of TPSs and TPS/PE blends showed that the interactions between starch and plasticizer became stronger in the presence of CA. POLYM. COMPOS. 28:89–97, 2007. © 2007 Society of Plastics Engineers     

Glycerol and esterified products of palmitic acid as a mixed plasticizer for thermoplastic tapioca starch

In this work, a mixture of glycerol (Gly) and derivatives of pentaerythritol or α,α′‐diglycerol is used as a plasticizer for preparing a thermoplastic starch (TPS). A coplasticizer containing both hydroxyl group and a long aliphatic chain was synthesized by esterification reaction between pentaerythritol or α,α′‐diglycerol and palmitoyl chloride in two different molar ratios, that is, 1:1 (PT1 and DG1), 1:2 (PT2 and DG2). The esterification products were characterized using Fourier transform infrared spectroscopy, ¹H, and ¹³C nuclear magnetic resonance spectroscopy. The starch and the mixed plasticizer were blended in an internal mixer. The morphology and miscibility of the blends were investigated by scanning electron microscope. The mechanical properties, moisture adsorption, and retrogradation phenomenon of the TPS specimens were studied. The results indicated that the TPS specimen containing a mixed plasticizer in a weight ratio of 80% Gly: 20% PT1 showed the highest values of Young's modulus and tensile strength, because this mixed plasticizer system could form stronger hydrogen bonds with starch molecules. Moreover, thermoplastic starch with higher content of pentaerythritol or α,α′‐diglycerol derivatives as a coplasticizer showed lower moisture adsorption, because its long aliphatic chain (hydrophobic part) of pentaerythritol derivatives may prevent starch molecules to reform hydrogen bonding and to recrystallize. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Optimizing the mechanical and physical properties of thermoplastic starch via tuning the molecular microstructure through co‐plasticization by sorbitol and glycerol

Nowadays, environmental hazards caused by plastic wastes are a major concern in academia and industry. Utilization of biodegradable polymers derived from renewable sources for replacing common petroleum‐based plastics is a potential solution for reducing the problem. In this regard, starch has become one of the most promising alternatives to non‐biodegradable polymers for depleting plastic waste thanks to its low expense, abundance, renewability and biodegradability. However, the main drawbacks of starch are its poor processability, weak mechanical properties and severe hydrophilicity. In this work, thermoplastic starch (TPS) samples have been prepared using glycerol and sorbitol as co‐plasticizers in a laboratory co‐rotating twin screw extruder. Based on the mechanical test results, glycerol caused higher elongation to break but had lower tensile strength and elastic modulus compared to sorbitol plasticized starch. Fourier transform infrared spectroscopy and DSC results indicated that the hydrogen bond interaction between starch chains and plasticizers could be improved by replacing glycerol by sorbitol, which resulted in higher resistance against retrogradation proved by XRD results. TGA illustrated that the higher the sorbitol to glycerol ratio was, the more stable was the TPS. Using a proper amount of plasticizers (42 wt% total plasticizer, sorbitol to glycerol ratio 2:1) led to the preparation of a TPS sample with optimized properties including enhanced mechanical properties, high thermal stability, strong hydrogen bond formation and high resistance against retrogradation. © 2017 Society of Chemical Industry     

Characterization of extruded film based on thermoplastic potato flour

Potato flour is abundant and less expensive than starch, though its major component is starch. It would therefore seem to be an attractive and viable source of biomass for biodegradable thermoplastic products. This study prepared thermoplastic potato flour (TPF) and thermoplastic potato starch (TPS) films by extrusion and investigated their properties. A mixture of glycerol and triethyl citrate (25−35% of total weight) was chosen for the plasticizer. Properties of the TPF film, such as mechanical properties, surface hydrophilicity, surface energy, moisture sorption isotherm, and glass transition temperature (T_g), were characterized and compared with TPS film. The results showed that TPF film was comparable to TPS film in many properties. The mechanical properties of the TPF film, including tensile strength, elongation at break, and tensile modulus, were similar in magnitude to TPS film. In addition, TPF film showed lower T_g and surface hydrophilicity, but higher surface wetting capacity than TPS film. Components other than starch in potato flour were believed to have had a plasticization effect on TPF properties. Overall, potato flour demonstrated a comparable capacity for manufacturing thermoplastic film similar to the more expensive starch feedstock. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The properties of blends of maleic‐anhydride‐grafted polyethylene and thermoplastic starch using hyperbranched polyester polyol as a plasticizer

The first aim of this study was to prepare thermoplastic starch (TPS), namely blends of tapioca starch and hyperbranched polyester polyol and to evaluate the hyperbranched polyester polyol (HBP) as a plasticizing agent for tapioca starch. The second aim was to prepare blends of maleic‐anhydride‐grafted low‐density polyethylene (LDPE‐g‐MA) and TPS, and to evaluate the effect of the mass ratio LDPE‐g‐MA/TPS on the structural, thermal, rheological, morphological, and mechanical properties of the blends. The melting and crystallization temperatures of the LDPE‐g‐MA/TPS blends did not correlate well with the ratio of LDPE‐g‐MA/TPS. The blends exhibited a reduction in the A‐type crystallinity and a pseudoplastic rheological behavior. V‐type crystallinity was not observed for neither TPS nor LDPE‐g‐MA/TPS blends. Scanning electronic microscophy provided an evidence for the presence of starch granules in all the blends and for low interaction degree between LDPE‐g‐MA and TPS. Young's modulus and tensile strength of the LDPE‐g‐MA/TPS blends decreased with the decreasing LDPE‐g‐MA/TPS ratio. POLYM. ENG. SCI., 55:2526–2533, 2015. © 2015 Society of Plastics Engineers     

Morphology and rheological properties of compatibilized low‐density polyethylene/linear low‐density polyethylene/thermoplastic starch blends

Morphology and rheological properties of low‐density polyethylene/linear low‐density polyethylene/thermoplastic starch (LDPE/LLDPE/TPS) blends are experimentally investigated and theoretically analyzed using rheological models. Blending of LDPE/LLDPE (70/30 wt/wt) with 5–20 wt % of TPS and 3 wt % of PE‐grafted maleic anhydride (PE‐g‐MA) as a compatibilizer is performed in a twin‐screw extruder. Scanning electron micrographs show a fairly good dispersion of TPS in PE matrices in the presence of PE‐g‐MA. However, as the TPS content increases, the starch particle size increases. X‐ray diffraction patterns exhibit that with increase in TPS content, the intensity of the crystallization peaks slightly decreases and consequently crystal sizes of the blends decrease. The rheological analyses indicate that TPS can increase the elasticity and viscosity of the blends. With increasing the amount of TPS, starch particles interactions intensify and as a result the blend interface become weaker which are confirmed by relaxation time spectra and the prediction results of emulsion Palierne and Gramespacher‐Meissner models. It is demonstrated that there is a better agreement between experimental rheological data and Coran model than the emulsion models. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44719.     

Preparation and studying properties of polybutene‐1/thermoplastic starch blends

Starch as an inexpensive and renewable source has been used as a filler for environmental friendly plastics for about two decades. In this study, glycerol was used as a plasticizer for starch to enhance the dispersion and the interfacial affinity in thermoplastic starch (TPS)/polybutene‐1(PB‐1) blend. PB‐1 was melt blended with TPS using a single screw extrusion process and molded using injection molding process to investigate the rheological and mechanical properties of these blends. Rheological properties were studied using a capillary rheometer, and the Bagley's correction was performed. Mechanical analysis (stress–strain curves) was performed using Testometric M350‐10 kN. The rheological properties showed that the melt viscosity of the blend is less than that of PB‐1, and the flow activation energy at a constant shear stress of the blend increases with increasing glycerol content in the blend. The mechanical experiments showed that both stress and strain at break of the blends are less than that of PB‐1, whereas the Young's modulus of the most blends is higher than that of PB‐1 which confirms the filling role of TPS in the blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Malic acid: A novel processing aid for thermoplastic starch/poly(butylene adipate‐co‐terephthalate) compounding and blown film extrusion

The processing of polysaccharide‐based polymer compounds represents a major challenge because these materials behave considerably different compared to their petro‐based counterparts. Especially in the manufacture of thermoplastic starch (TPS)–polyester films by means of blown film extrusion, an increase in the natural material proportion generally leads to processing difficulties. In addition, higher TPS contents adversely affect mechanical material characteristics. The present study focuses on the effect of malic acid (MA) on processing parameters and on the quality of TPS/poly(butylene adipate‐co‐terephthalate) films. The MA enantiomers d (+) and l (–) as well as the racemate were applied at various concentrations (0.2, 0.4, and 0.8 wt %). Results indicate that the addition of racemic MA at concentrations of 0.2% and 0.4% significantly improved the processibility of TPS. Simultaneously, positive effects such as improved ductility and water sorption characteristics were found. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45539.     

Evaluation of starch‐PE multilayers: Processing and properties

Adhesion tests performed on various plasticized starch‐polyethylene multi‐layer systems led to the selection of a suitable combination of polymers compatible with the starch‐based layer. The compatibility of starch and polyethylene was better achieved through maleic anhydride functionalized polyethylene (PEg) than chemically modifying starch. The PEg method proved efficient provided that the water content, and the plasticizer nature and contents of the starch layer were carefully chosen. Computed shear viscosity allowed us to select a suitable botanical origin of starch such that the interfacial instabilities of the coextrusion process were minimized. The use of a multilayer structure (PE/PEg/starch/PEg/PE) improved gas barrier properties at high relative humidity. The higher quantity of water sorbed by thermoplastic starch (as compared to EVOH) coupled with starch's specific water sorption isotherm lengthened the water equilibration time in the hydrophilic inner layer significantly. As a result the gas barrier properties of the starch based multiplayer systems were enhanced as compared to existing commercial multiplayer systems (PE/PEg/EVOH/PEg/PE). This specific “water‐buffering property” of the starch inner layer should prove useful in packaging applications of perishables with extended shelf life in environments of varying relative humidity. Polym. Eng. Sci. 45:217–224, 2005. © 2005 Society of Plastics Engineers.     

Preparation and characterization of maleated thermoplastic starch‐based nanocomposites

Biodegradable nanoscale‐reinforced starch‐based products were prepared from an in situ chemically modified thermoplastic starch and poly(butylene adipate‐co‐terephthalate) (PBAT) through reactive processing. Natural montmorillonite (hydrophilic Cloisite Na) and organophilic Cloisite 30B were studied. In situ chemically modified thermoplastic starch (MTPS) was first prepared starting from (nano)clay (previously swollen in glycerol as plasticizer), and maleic anhydride (MA) as an esterification agent. Then, these nanoscale‐reinforced MTPS was reactively melt‐blended with PBAT through transesterification reactions promoted by MA‐derived acidic moieties grafted onto the starch backbone. The tensile and barrier properties of resulting (nano)composites were studied. High‐performance formulations with superior tensile strength (>35 MPa as compared with 16 MPa for the PBAT‐g‐MTPS copolymer) and break elongation (>800%) were obtained, particularly with Cloisite30B. Better water vapor and oxygen barrier properties of nanoscale‐reinforced MTPS‐g‐PBAT were achieved rather than the PRECURSORS. Wide angle X‐ray diffraction and transmission electronic microscopy analyses show that partial exfoliation of the clay platelets was observed within the PBAT‐g‐MTPS graft copolymer‐Cloisite 30B nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electron‐beam processing of destructurized allylurea–starch blends: Immobilization of plasticizer by grafting

Allylurea (AU) was used as a reactive additive with poor aptitude to homopolymerization for obtaining grafted plasticized starch films with stabilized physical properties. Potato starch was mixed with AU (30–50 parts per hundred/pph) in a mixer operating at 125°C. Upon storage in well‐defined hygrothermal conditions, the resulting thermoplastic material shows strong plasticizer migration revealed by AU crystals blooming at the samples surface and exhibits strong opacity assigned to phase separation of the organic additive inside the material. Freshly prepared thermoplastic films of appropriate thickness were exposed to a 175‐kV electron beam (EB) radiation for inducing covalent grafting of AU by a free radical process. FTIR monitoring of the resulting chemical changes in thin films of AU–starch blends indicates unambiguously the transformation of AU allylic bond. High irradiation doses are required for achieving complete conversion of AU in the blend. However, no detectable AU migration was observed for intermediate AU conversion, probably as a consequence of higher plasticizer solubility in the grafted polysaccharide. Examination of the viscoelastic properties by dynamic mechanical thermal analysis shows that artificial aging by placing the films alternatively in high and low relative humidity (RH) atmosphere does not significantly alter the thermomechanical spectrum of the material reconditioned in a cell at 58% RH. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 409–417, 1999     

D‐isosorbide and 1,3‐propanediol as plasticizers for starch‐based films: Characterization and aging study

In the present work, D‐isosorbide and 1,3‐propanediol are proposed as alternative plasticizers obtained from renewable resources. Plasticized starch films were prepared by solvent casting method. The influence of using different “green” plasticizers in the final properties of starch‐based films was analyzed. Besides, the characterization of the films was also performed after storage time in order to evaluate the effect of the plasticizer on aging. UV‐spectrophotometry results showed better optical properties for both glycerol and D‐isosorbide films with higher transparency. The thermal and mechanical properties resulted influenced by the nature of the plasticizer. It was demonstrated that water vapor permeability was governed by the starch‐water interactions, whereas the oxygen permeability depended on the plasticizer's nature. The storage time affected the surface, mechanical, and thermal properties of the plasticized starch films. Atomic force microscopy results concluded that the topography of the films changed due to aging. The use of D‐isosorbide as plasticizer reduced the evolution of the mentioned properties and enhanced the reliability of the material. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44793.