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     

Properties of fatty-acid esters of starch and their blends with LDPE

In the present study, starch octanoates OCST1.8 and OCST2.7 with degrees of substitution (d.s.) of 1.8 and 2.7, respectively, and dodecanoate DODST2.7 (d.s. = 2.7), were prepared by esterification of native starch with fatty acid chlorides. Our analyses, including elemental analysis, FTIR, contact angle, DSC, and TGA measurements confirmed the esterification reaction of starch and the degree of substitution. The ester group was found to act like an internal plasticizer, with an increase in the number and the size of fatty acyl chains grafted onto starch. These starch esters were mixed with low density polyethylene (LDPE) at various proportions in a Haake Rheomixer. Water and moisture absorption, thermal and mechanical properties, and biodegradation were investigated as a function of blend composition. The DODST2.7/LDPE blends showed, in general, better thermal stability and higher elongation, but lower tensile strength and water absorption, than did corresponding OCST/LDPE blends. The addition of starch esters to LDPE led to a very slow rate of biodegradation of these blends. © 1997 John Wiley & Sons, Inc. J Appl Polym 65: 705–721, 1997     

Radiation‐assisted morphology modification of LDPE/TPS blends: A study on starch degradation‐processing‐morphology correlation

Potato starch was radiolytically degraded to different extents by irradiating with Co‐60 gamma radiation in wide dose range. The degraded starch was plasticized using glycerol and water to obtain radiation processed thermoplastic starch (RTPS). Blends of different RTPS and low density polyethylene (LDPE) were prepared by internal melt mixing. Characterization of blends using differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction, Fourier transformed infrared spectroscopy, scanning electron microscope, melt flow, contact angle, and soil burial studies indicated changes in the blend morphology and biodegradation behavior with the increase in the dose imparted to the starch fraction. Molecular weight of starch decreased substantially in the dose range of the study. The melt viscosity of LDPE/RTPS blend decreased whereas crystallinity of LDPE phase increased with the incorporation of RTPS. No significant change in the carbonyl index and thermal stability of the blends was observed in the dose range studied; therefore, the observed changes in the physical and thermal properties of the blends were attributed primarily to the kinetic factors affecting crystallization and time‐dependent phase separation process. Biodegradability of blends varied with the radiation dose imparted to starch component of blend, suggesting better encapsulation of RTPS by LDPE chains. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effects of glycerol and PE‐g‐MA on morphology,thermal and tensile properties of LDPE and rice starch blends

The effects of glycerol and polyethylene‐grafted maleic anhydride (PE‐g‐MA) on the morphology, thermal properties, and tensile properties of low‐density polyethylene (LDPE) and rice starch blends were studied by scanning electron microscopy (SEM), differential scanning calorimetry, and the Instron Universal Testing Machine, respectively. Blends of LDPE/rice starch, LDPE/rice starch/glycerol, and LDPE/rice starch/glycerol/PE‐g‐MA with different starch contents were prepared by using a laboratory scale twin‐screw extruder. The distribution of rice starch in LDPE matrix became homogenous after the addition of glycerol. The interfacial adhesion between rice starch and LDPE was improved by the addition of PE‐g‐MA as demonstrated by SEM. The crystallization temperatures of LDPE/rice starch/glycerol blends and LDPE/rice starch/glycerol/PE‐g‐MA blends were similar to that of pure LDPE but higher than that of LDPE/rice starch blends. Both the tensile strength and the elongation at break followed the order of rice starch/LDPE/glycerol/PE‐g‐MA blends > rice starch/LDPE/glycerol > LDPE/rice starch blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 344–350, 2004     

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.     

Mechanical properties and biodegradability of LDPE blends with fatty‐acid esters of amylose and starch

In the present article a series of low‐density polyethylene (LDPE) blends with different amounts of fatty esters of amylose and starch, were prepared in a Haake‐Buchler Reomixer. The tensile as well as the dynamic thermomechanical (DMTA) properties of the blends were measured. It was found that as the amount of the esters increases in the blends, the tensile strength and especially the elongation at break decrease nonlinearly. Scanning electron microscopy (SEM) was used to assess the interfacial adhesion between LDPE and the corresponding esters. The incompatibility of the blends was also verified with DMTA and differential scanning calorimetry (DSC). From the biodegradation studies of the blends during exposure in activated sludge, it was found that all esters are biodegradable, although to a much lesser degree compared to pure strach. The biodegradation rate of the composites is relatively small due to the low biodegradation rate of the pure esters. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1089–1100, 1999     

Starch‐based biodegradable blends: morphology and interface properties

In order to improve the properties of plasticized wheat starch (PWS) and to conserve its final biodegradability, PWS can be blended with biodegradable polyesters [polyesteramide, poly(ε‐caprolactone), poly(lactic acid), poly(butylene succinate adipate) and poly(butylene adipate terephthalate)] which exhibit variable polar characteristics. This paper is focused on the analysis of the compatibility of these blends which vary according to their formulation. To understand the lack of affinity between the different phases, interface adhesion has been investigated by contact angle measurements to obtain the work of adhesion. From these determinations a forecast approach has been developed to predict blend compatibility. Blend structures were obtained by scanning electron microscopy observations. Blends show either a dispersed structure or a co‐continuous morphology. Percolation thresholds (co‐continuity) and full continuity regions were determined thanks to a method based on solvent extraction. Finally, rheological investigations have been carried out on the different biodegradable polymers to understand better the blend structure formation during the process. Copyright © 2004 Society of Chemical Industry     

Tensile properties,morphology, and biodegradability of blends of starch with various thermoplastics

In the present study, blends of starch with different thermoplastics were prepared by a melt blending technique. The tensile properties and morphology of the blends were measured. It was found that with increasing starch content in starch/ionomer blends, the tensile strength and modulus increase. But for starch/low‐density polyethylene (LDPE) and starch/aliphatic polyester (APES) blends, tensile strength and modulus decrease with increasing the starch loading. Elongation at break values of all the blend systems decrease with increasing starch loading. The scanning electron micrographs (SEM) support the findings of tensile properties. Better homogeneity is observed in starch/ionomer systems compared with that in starch/APES and starch/LDPE systems. Up to 50% starch content, the starch/ionomer blends appear as a single phase. The extent of phase interactions of starch/APES system lies in between the starch/LDPE and starch/ionomer systems. From the biodegradability studies of the blends it was found that, although the pure LDPE and ionomer are not biodegradable, the starch/LDPE and starch/ionomer blends are biodegradable with an appreciable rate. The rate of biodegradation of the starch/APES is very high as both the components are biodegradable. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2907–2915, 2002     

Influence of the porous morphology on the in vitro degradation and mechanical properties of poly(L‐lactide) disks

Poly(L ‐lactide) (PLLA) materials having an interconnected porosity are proposed as an alternative to nonporous biomaterials. Such materials allow for the potential of modulating the degradation behavior and the mechanical properties. In this article, the preparation of porous PLLA disks or cylinders with 50 and 65% void volume is presented. It is demonstrated that both a symmetric and asymmetric porosity can be generated within the disk itself. In addition, open‐ and closed‐cell structures can also be prepared. The accelerated in vitro degradation on symmetric open‐cell porous PLLA disks and on the nonporous control indicate a similar behavior in terms of melting temperature and inherent viscosity of the remaining pieces of the specimens, but the crystallinity and the mass of the remaining fragments are much smaller for the porous specimens. The mechanical properties under compression are determined for open and closed‐cell porous cylinders, porous tubes, and for the nonporous PLLA. The results highlight the excellent mechanical integrity of the prepared porous structures and demonstrate that such materials could have potential for use as biomedical implants. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1039–1047, 2006     

Rheological,mechanical, thermal,and morphological properties of blends poly(butylene adipate-co-terephthalate), thermoplastic starch,and cellulose nanoparticles

The objective of the present study was the preparation and characterization of poly(butylene adipate-co-terephthalate) (PBAT) and thermoplastic starch (TPS) blends reinforced with cellulose nanoparticles (CNCs) by extrusion. The work was conducted in four steps. Initially, the CNCs were prepared from eucalyptus cellulose pulp by acid hydrolysis. The second step was the preparation of the nanocomposite (TPS-CNC), composed of cassava starch, CNC, glycerol, and citric and stearic acids, by double screw extrusion. The third step was the preparation of PBAT/TPS-CNC blends in twin-screw extruders. In the fourth step, the films were produced by flat extrusion. Blends exhibited similar rheological behavior, increasing the CNC concentration in blends increased the viscosity as a function of the shear rate, and altered the behavior of the shear storage (G′) and shear loss (G″) curves as a function of the oscillation frequency (ω). The presence of CNC in blend provided improvements significant in mechanical properties, with 120% increase in Young's modulus, and 46% increase in maximum tensile. Thermal behavior (thermogravimetric analysis and differential scanning calorimetry) was altered with the incorporation of the CNC, showing a single melt peak (T_m) and a slight increase in T_g, indicating good dispersion between the phases of the blends, corroborating with the fracture surface microscopy of films.     

The morphology,rheological, and mechanical properties of wood flour/starch/poly(lactic acid) blends

An entirely biosourced blend composed of poly(lactic acid) (PLA), starch, and wood flour (WF) was prepared by a co‐extruder with glycerol as a plasticizer. The morphology, rheological properties, and mechanical properties of the WF/starch/PLA blends were comprehensively analyzed. The results showed that with the decrease of the starch/WF ratio, the morphology experienced a large transformation, and the compatibility of the blends was found to be superior to other blends, with a starch/wood flour ratio of 7/3. The dynamic mechanical thermal analysis (DMA) results demonstrated the incompatibility of the components in WF/starch/PLA blends. Following the decrease of the starch/WF ratio, the storage modulus (G″) and the complex viscosity (η*) of the blends increased. The mechanical strength first increased, and then decreased with the increase of the WF concentration. The water absorption results showed that the water resistance of the blends was reduced with the lower starch/WF ratio. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44743.     

Effect of propylation of starch with different degrees of substitution on the properties and characteristics of starch‐low density polyethylene blend films

Corn starch was modified by propylation and degree of substitution (DS) of four starch modifications were 0.61, 1.56, 2.27, and 2.51. Different films were prepared by blending native and propylated starch with low‐density polyethylene (LDPE). The mechanical properties, thermal properties, water absorption capacity, and biodegradability of the blend films varied with the quantity of starch as well as DS. Tensile strength, elongation, and melt flow index of propylated starch blend films were higher compared to the corresponding native starch blend film. These properties improved with increase in DS from 1.56 to 2.51. Propylated starch blend films were found thermally stable than native starch blend films. There was a decrease in water absorption capacity for the films containing propylated starch at high DS. Enzymatic and soil burial degradation results showed that biodegradability of starch‐LDPE films increased with the increase in the starch concentration but it decreased with increase in the DS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Low‐density polyethylene/plasticized tapioca starch blends with the low‐density polyethylene functionalized with maleate ester: Mechanical and thermal properties

In this study, the mechanical and thermal properties of low‐density polyethylene (LDPE)/thermoplastic tapioca starch blends were determined with LDPE‐g‐dibutyl maleate as the compatibilizer. Mechanical testing for the evaluation of the impact strength and tensile properties was carried our as per standard ASTM methods. Thermogravimetric analysis and differential scanning calorimetry were also used to assess the thermal degradation of the blends. Scanning electron micrographs were used to analyze fracture and blend morphologies. The results show significant improvement in the mechanical properties due to the addition of the compatibilizer, which effectively linked the two immiscible blend components. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1109–1120, 2006     

Biodegradation of low‐density polyethylene/thermoplastic starch foams before and after electron beam irradiation

Foamy low‐density polyethylene/plasticized starch (LDPE/PLST) blends at different compositions were produced in the presence of azodicarbonamide (ACA) compound as foaming agent. The LDPE/PLST blends before and after electron beam irradiation were investigated in terms of mechanical properties, bulk density, and structure morphology. Moreover, the biodegradability of these materials was evaluated by the soil burial test for 2 months, in which the buried sheets were also examined by scanning electron microscopy (SEM). The results showed that the increase of PLST content from 24 to 30% was accompanied by a decrease in the yield and break stresses of 10 and 20% for the unirradiated blends without the foaming agent, respectively. Further decrease in these mechanical parameters was observed after the foaming process. The bulk density, void fraction, cell size measurements as well as the examination by SEM illustrate clearly the cell growth of the foam structure. The soil burial test and SEM micrographs indicate the growth of microorganisms overall the blend sheets and that the blend was completely damaged after two months of burying. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Gelatinized starch/biodegradable polyester blends: Processing,morphology, and properties

Blends of polycaprolactone (PCL)/gelatinized starch and polybutylene succinate adipate/gelatinized starch have been prepared in various ratios and their phase morphology and thermal/mechanical properties have been analyzed. For both the PCL/plasticized starch and polybutylene succinate adipate/plasticized starch blends the resistance to impact increased with increasing polyester content, and the tensile modulus reached a maximum at around 80 wt % polyester content. In blends containing up to 70 wt % polyester (as observed by scanning electron microscopy) a hierarchical dispersion of the gelatinized starch phase was observed (distinct domain sizes of those less than 5 μm and those greater than 15 μm) and in the blends containing 70–90 wt % polyester a more singular dispersed phase of gelatinized starch was observed within the polyester matrix. Dynamical mechanical analysis results showed some phase mixing was present in the PCL/gelatinized starch blends noted by the appearance of an additional tan δ peak located between the glass transition temperatures of the respective components and broadening of the low temperature transition corresponding to the T_g of the polyester (possibly the result of a starch‐rich polyester phase) with some overlap with the low temperature β transition of the gelatinized starch itself. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 802–811, 2007     

Processing and properties of thermoplastic starch and its blends with sodium alginate

Viscosity measurements were carried out on corn starch (CS) and CS–sodium alginate (SA) suspensions at low levels of SA [1 to 10% (w/w)], as a function of temperature. The addition of SA caused the granular CS gelatinization process to occur at a lower onset temperature. CS and CS–SA mixtures were extruded in single‐ and twin‐screw extruders, with 15% glycerol and different water contents. Processing of plasticized CS–SA mixtures required lower temperatures, which is consistent with the viscosity results. Homogeneous and flexible extrudates were obtained by processing in a twin‐screw extruder. Samples in the composition range between 0 and 10% (w/w) SA were examined using tensile tests as a function of water content. Mechanical properties were dependent on the water content and on the SA composition. A significant increase in the Young's modulus value was observed for the blend containing 1% SA. Dynamic mechanical analysis was carried out for CS and CS–SA blends. Two transitions were detected in the temperature range –80 to 150°C. Scanning electron microscopy was used to examine the morphology of the extruded samples. The surfaces of the films were homogeneous, which demonstrated that the CS granules in all samples were characteristically destructured under the conditions used in processing. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 412–420, 2001     

Curing and combustion properties of a PU‐coating system with UV‐reactive phosphazene

A UV‐curable polyurethane (PU)‐coating system containing phosphorus is formulated by the combination of photoinitiator, PU acrylate oligomer, and UV‐reactive phosphazene monomer. PU acrylate oligomer is prepared by the addition of 2‐hydroxyethylmethacrylate (HEMA) to NCO‐terminated PU prepolymer. UV‐reactive phosphazene monomer is derived from the HEMA substitution reaction to hexachlorocyclotriphosphazene (NPCl₂)₃. The curing reaction of this PU‐coating system is carried out by UV irradiation. The resultant UV‐cured PU‐coated films demonstrated better performance properties than those of original UV‐cured PU acrylate (UV‐PU) without UV‐reactive phosphazene monomer. Furthermore, their thermal properties are investigated by a thermogravimetric analyzer and a dynamic mechanical thermal analyzer, respectively. The combustion behaviors of these UV‐cured PU‐coated films are evaluated by the measurements of a limiting oxygen index and a cone calorimeter. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1980–1991, 2002     

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     

Interfacially compatibilized LDPE/POE blends reinforced with nanoclay: investigation of morphology,rheology and dynamic mechanical properties

Morphological, melt rheological and dynamic mechanical properties of low-density polyethylene (LDPE)/ethylene–octene copolymer (POE)/organo-montmorillonite (OMMT) nanocomposites, prepared via melt compounding were studied. The XRD traces indicated different levels of intercalated structures for the nanocomposites. Addition of a compatibilizer (PE-g-MA) improved the intercalation process. TEM results revealed existence of clay layers in both phases but they were mainly localized in the elastomeric POE phase. Addition of 5 wt% OMMT to the LDPE/POE blend led to reduction in the size of the elastomer particles confirmed by AFM. The complex viscosity and storage modulus showed little effect of the presence of the clay when no compatibilizer was added. As the extent of exfoliation increased with addition of compatibilizer, the linear viscoelastic behavior of the composites gradually changed specially at low-frequency regions. The interfacially compatibilized nanocomposites with 5 wt% OMMT had the highest melt viscosity and modulus among all the studied nanocomposites and blends. Also, this particular composition showed the best improvement in dynamic storage modulus. The results indicated that clay dispersion and interfacial adhesion, and consequently different properties of LDPE/POE/clay nanocomposites, are greatly affected by addition of compatibilizer.     

Development of nanofibrous morphology in LDPE/LLDPE/PP blends and its effect on mechanical properties of blend films

Nanofibrous morphology has been observed in ternary blends of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and isotactic polypropylene (PP) when these were melt‐extruded via slit die followed by hot stretching. The morphology was dependent on the concentration of the component polymers in ternary blend LDPE/LLDPE/PP. The films were characterized by wide angle X‐ray diffraction (XRD), scanning electron microscopy (SEM), and testing of mechanical properties. The XRD patterns reveal that the β phase of PP is obtained in the as‐stretched nanofibrillar composites, whose concentration decreases with the increase of LLDPE concentration. The presence of PP nanofibrils shows significant nucleation ability for crystallization of LDPE/LLDPE blend. The SEM observations of etched samples show an isotropic blend of LDPE and LLDPE reinforced with more or less randomly distributed and well‐defined nanofibrils of PP, which were generated in situ. The tensile modulus and strength of LDPE/LLDPE/PP blends were significantly enhanced in the machine direction than in the transverse direction with increasing LLDPE concentration. The ultimate elongation increased with increasing LLDPE concentration, and there was a critical LLDPE concentration above which it increased considerably. There was a dramatic increase in the falling dart impact strength for films obtained by blow extrusion of these blends. These impressive mechanical properties of extruded samples can be explained on the basis of the formation of PP nanofibrils with high aspect ratio (at least 10), which imparted reinforcement to the LDPE/LLDPE blend. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008