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     

Diffusion of benzene vapor in blends of poly(vinyl acetate) and poly(methyl acrylate)

Sorption and diffusion of benzene in miscible blends of poly(vinyl-acetate), PVAc, and poly(methyl acrylate), PMA, have been studied. The polymer-polymer interaction parameter values calculated from equilibrium vapor sorption data were all negative, indicating favorable interaction between the two polymers. The sorption of benzene vapor into these blends was measured at a temperature above the T_g's of the pure polymers and found to obey Fickian kinetics. The mutual diffusion coefficients were estimated from the initial slopes of the sorption curves. The concentration dependent diffusion coefficients were fitted to the empirical relation D = D_o exp(αC) which satisfactorily correlated the data. Values of the constant D_o were found to vary continuously with blend composition, while the α values did not. These experimental data were analyzed employing Fujita's free volume theory. It was found that the data was consistent with this theory. If the f_o values for the blends are assumed to be the weighted average of the component polymers, then the β parameter values for the blends also obey the additivity rule.     

Effects of polyethylene‐grafted maleic anhydride (PE‐g‐MA) on thermal properties,morphology, and tensile properties of low‐density polyethylene (LDPE) and corn starch blends

The effects of polyethylene‐grafted maleic anhydride (PE‐g‐MA) on the thermal properties, morphology, and tensile properties of blends of low‐density polyethylene (LDPE) and corn starch were studied with a differential scanning calorimeter (DSC), scanning electron microscope (SEM), and Instron Universal Testing Machine, respectively. Corn starch–LDPE blends with different starch content and with or without the addition of PE‐g‐MA were prepared with a lab‐scale twin‐screw extruder. The crystallization temperature of LDPE–corn starch–PE‐g‐MA blends was similar to that of pure LDPE but higher than that of LDPE–corn starch blends. The interfacial properties between corn starch and LDPE were improved after PE‐g‐MA addition, as evidenced by the structure morphology revealed by SEM. The tensile strength and elongation at break of corn starch–LDPE–PE‐g‐MA blends were greater than those of LDPE–corn starch blends, and their differences became more pronounced at higher starch contents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2904–2911, 2003     

Rheological behavior of LDPE/CaCO3 blends containing EAA

Calcium carbonate (CaCO₃) filler particles were surface treated with organic titanate (TTS), a coupling agent. The composites were prepared by blending low‐density polyethylene (LDPE) with the surface‐modified fillers at various weight ratios. Ethylene‐acrylic acid copolymer (EAA) was added to improve the adhesion of LDPE to fillers. A capillary rheometer was used to evaluate rheological properties of the LDPE/CaCO₃/EAA blends. The blends were shown to be pseudoplastic with shear thinning behavior. When CaCO₃ was modified by TTS (<2 wt%), the viscosity of the blends decreased quickly, and, addition of a small amount of EAA (<6 wt%) could also decrease the viscosity of the blends. The thermal behavior of these materials is evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The addition of a small amount of EAA and TTS enhances the stabilization of the blends, which could be explained by the “ball belling” action. The effects of temperature, TTS content, CaCO₃ granule size, and content on the rheological property were also studied. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Moisture‐sorption characteristics of starch/low‐density polyethylene films

Moisture‐sorption characteristics of starch/low‐density polyethylene (LDPE) blends were carried out at 27°C for water activity (a_w) from 0.1 to 0.9. The sorption data were used to fit six different sorption isotherm models proposed in the literature. The model constants were determined by linear fitting of the sorption equations. The ranges of applicability of water activity for the isotherm models reported in the article lies between 0.1 and 0.4 (monomolecular layer) for the BET model and between 0.3 and 0.9 (multimolecular and capillary condensation layers) for other models. The value of the coefficient of determination (R² = 0.97 ± 0.02) confirms the linear fitting of the equations studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1193–1202, 2002; DOI 10.1002/app.10417     

Effect of Morphology on the Biodegradation of Thermoplastic Starch in LDPE/TPS Blends

In this study, thermoplastic starch (TPS) was mixed with low density polyethylene with different melt flow indexes in a one-step extrusion process to produce LDPE/TPS blends varied from 32% to 62% by weight of TPS. The influence of starch content and LDPE viscosity on morphology, biodegradation and tensile properties of LDPE/TPS blends were evaluated. Starch continuity and biodegradability were studied by hydrolytic, enzymatic and bacterial degradation. The LDPE viscosity had a considerable effect on the morphology and the connectivity of the starch particles. Evaluation of hydrolytic extraction showed that blends having TPS content above 50 wt% possessed a full connectivity. Studies of biodegradation indicated that the bacterial attack on starch resulted in weight loss of TPS of 92%, 39% and 22%, for PE1/TPS having 62% and 32% TPS, and PE2/TPS (31% TPS), respectively. Comparatively, the weight loss was more significant at 100%, 66% and 31% by hydrolytic extraction. Differences between these two techniques were discussed in terms of the accessibility of starch domains to microorganisms. Tensile properties (ε_b and E) decreased with increasing exposure time to activated sludge. Changes in tensile properties were highly dependent on the biodegradation rate. PE1/TPS blends having 32% starch remained ductile after 45 days of exposure to bacterial attack.     

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     

Relationship between segmental dynamics and tracer diffusion of low mass compounds in polyacrylates

We studied the relationship between segmental dynamics of matrix polymers and tracer diffusion of low mass compounds by the use of forced Rayleigh scattering and dielectric spectroscopy. Specifically poly(methyl acrylate), poly(ethyl acrylate) and poly(n-butyl acrylate) were used as the polymer matrices and six azobenzene derivatives with various substituents as the diffusant. The temperature dependence of the tracer diffusion coefficient D was measured on methylyellow (MY)/polyacrylate blends at the MY concentration of 1 wt%. The results indicate that the temperature dependence of D is weaker than the dielectric loss maximum frequencies f_m for the α processes of the matrices. The effect of volume of the dye molecules on D was also investigated at 305 K. Comparison of the tracer diffusion coefficients among various dye/polymer systems indicates that log D in the same matrix decreases linearly with the molar volume of the dyes.     

Gas permeation of polymer blends. IV. Poly(vinyl chloride) (PVC)/acrylonitrile–butadiene–styrene (ABS) terpolymer

The transport behavior of He, O₂, N₂, and CO₂ in membranes of poly(vinyl chloride) (PVC)/acrylonitrile–butadiene–styrene (ABS) blends has been studied at 25°C. The blends were further characterized by dynamic mechanical measurements, differential thermal analysis (DTA), density measurements, and x-ray diffraction. The equilibrium sorption of CO₂ and N₂ was measured directly at atmospheric pressure using an electromicrobalance and compared with sorption values obtained as P/D ratios from permeation measurements. The rates of permeation (P) and diffusion (D) increase with increasing ABS content in the blends. The P and D values are not additive, and only slight indications of phase inversion in the blends are observed at 5–10 wt-% ABS in the blends. Experimental densities of the blends are higher than calculated densities assuming volume additivity. The data are interpreted to mean that the PVC/ABS blends form a two-phase system composed of a soft polybutadiene (rubber) phase and a rigid PVC/styrene–acrylonitrile copolymer (SAN) phase of mutually compatible components. DTA and dynamic mechanical measurements also show a two-phase system. Sorption values of CO₂ and N₂ by equilibrium sorption measurements increase with increasing ABS content in the blends without the large fluctuations which have been observed for the sorption values obtained from the time lag method. Comparison of the two types of sorption values (from direct measurements and from P/D ratios) show larger deviations for CO₂ than for N₂. This suggests that the time lag method is not valid for permeants with polar character in heterogeneous two-phase systems where chemical immobilizing effect on the permeant molecules occurs.     

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     

Sorption and diffusion of aldehydes and ketones into natural rubber blends

Sorption and diffusion of aldehydes and ketones through different NR blends of bromobutyl (BIIR), chlorobutyl (CIIR), neoprene, EPDM, polybutadine, and SBR were studied at 25, 40, and 60°C. From the data, the Arrhenius activation parameter for diffusion, E_D, was determined. From the temperature dependence of the sorption constant, the enthalpy of sorption, ΔH, and entropy of sorption, ΔS, were also determined. The activation parameters are found to follow the conventional trend. Transport properties are affected by the nature of the interaction of solvent molecule, by its size, and also by the structural variation of the elastomers. For all the solvents, the polymer blends remained intact but the blends in the presence of benzaldehyde showed degradative reactions at higher temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 101–112, 1998     

Gas permeation of polymer blends. II. Poly(vinyl chloride)/acrylonitrile–butadiene copolymer (NBR) blends

The transport behavior of He, O₂, N₂, and CO₂ in a series of PVC/NBR polymer blends with varying acrylonitrile (AN) content in the NBR component has been studied at 25° and 50°C. In addition, measurements of density, crystallinity, and thermal expansion coefficients were carried out. The transport behavior of these blends is similar to previous result for PVC/EVA.¹. With increasing AN content in NBR, the permeability (P) and diffusivity (D) of the permeants decreased while the activation energy for diffusion (E_D) increased. For the polymer blends, better additivity of permeability and diffusivity was observed with increasing AN content in the NBR component. The polymer blends also showed increasing volume contraction with increasing AN content in the NBR component. These effects have been discussed as due mainly to increased polymer–polymer interaction causing reduced segmental mobility and increased compatibility of the two polymers. The sorption values calculated from P/D ratios were largely irregular and fluctuated with the blend composition. They were less reproducible than other transport parameters, i.e., P and D measured separately. Several reasons for the irregular sorption behavior were proposed.     

Boiling water aging of polycarbonate and polycarbonate/acrylonitrile–butadiene–styrene resin and polycarbonate/low‐density polyester blends

The effects of boiling water on the mechanical and thermal properties and morphologies of polycarbonate (PC), PC/acrylonitrile–butadiene–styrene resin (PC/ABS), and PC/low‐density polyester (PC/LDPE) blends (compositions of PC/ABS and PC/LDPE blends were 80/20) were studied. PC and the PC/ABS blend had a transition from ductile to brittle materials after boiling water aging. The PC/LDPE blend was more resistant to boiling water aging than PC and the PC/ABS blend. The thermal properties of glass‐transition temperature (T_g) and melting temperature (T_m) in PC and the blends were measured by DSC. The T_g of PC and PC in the PC/ABS and PC/LDPE blends decreased after aging. The T_g of the ABS component in the PC/ABS blend did not change after aging. The supersaturated water in PC clustered around impurities or air bubbles leading to the formation of microcracks, which was the primary reason for the ductile–brittle transition in PC, and the microcracks could not recover after PC was treated at 160°C for 6 h. The PC/ABS blend showed slightly higher resistance to boiling water than did PC. The highest resistance to boiling water of the PC/LDPE blend may be attributed to its special structural morphology. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 589–595, 2003     

Nonisothermal crystallization kinetics of ethylene–butene copolymer/low‐density polyethylene blends

Nonisothermal crystallization kinetics of the blends of three ethylene–butene copolymers with LDPE was studied using differential scanning calorimetry (DSC) and kinetic parameters such as the Avrami exponent and the kinetic crystallization rate (Z_c) were determined. It was found that the pure components and the blends have similar Avrami exponents, indicating the same crystallization mechanism. However, the crystallization rate of the blends was greatly influenced by LDPE. The Z_c of all the blends first increases with increasing LDPE content in the blends and reaches its maximum, then descends as the LDPE content further increases. The crystallization rate also depends on the short‐chain branching distribution (SCBD) of the ethylene–butene copolymers. The Z_c of the pure component with a broad SCBD is smaller, but its blends have a larger crystallization rate due to losing highly branched fractions after blending with LDPE. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 123–129, 2001     

Rheological and mechanical properties of poly (ethylene acrylic acid) and low density polyethylene blends

Rheological properties of poly (ethylene‐acrylic acid) (PEA) and low density poly ethylene (LDPE) blends having varied amounts of LDPE from 0 to 100% have been evaluated at different temperatures (115, 120, and 130°C) and shear rates (61.33–613.30 s^?1) using a Monsanto processability tester. A reduction in the melt viscosity of the PEA/LDPE blends was noticed with increasing the shear rate. The observed positive deviation in the experimental melt viscosities of the blends is an indication of the synergy present in the blends during melt processing. The activation energy (E_a) of flow calculated using Arrhenius relation for PEA, LDPE, and their respective blends lies in the range 29.98–40.56 kJ mol^?1. The experimental activation energy of flow of the blends was higher than that obtained from the additivity rule. Highest activation energy was noticed for the blends containing 60–80% by weight of LDPE in PEA/LDPE blends, which is an indication for the miscibility of the blends at these ratios. The physicomechanical properties such as density, tensile behavior, tear strength, and hardness (Shore A) of PEA, LDPE, and their blends have been evaluated as a function of varying amounts of LDPE. The obtained physicomechanical properties of the PEA/LDPE blends lie in between that of pure polymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphology,thermomechanical properties,and biodegradability of low density polyethylene/starch blends

The biodegradability of low density polyethylene (LDPE)/starch and LDPE/starch/starch acetate (STAc) blends was tested and observed to be dependent on STAc content. The binary and ternary blends containing up to a maximum concentration of 30% starch were examined for their thermal, mechanical, and morphological properties. The blends with no STAc or 2.5% STAc show almost no adherence of two phases. With 10% STAc, dispersion of starch was observed to increase with some adherence to LDPE. Tensile strength, elongation at break, and Izod impact strength of the blends decreased with increased starch content. However, incorporation of STAc along with starch improved all these properties, particularly elongation at break and toughness. The melt flow index was also improved on partial substitution of starch by STAc. Maximum biodegradability was observed for the blends containing 30% (starch + STAc). Cell growth was observed to increase with increasing concentration of (starch + STAc) in the blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2791–2802, 1999     

Effect of cellulose nanofibers and acetylated cellulose nanofibers on the properties of low‐density polyethylene/thermoplastic starch blends

The aim of this study was to evaluate the effect of cellulose nanofibers (CNFs) and acetylated cellulose nanofibers (ACNFs) on the properties of low‐density polyethylene/thermoplastic starch/polyethylene‐grafted maleic anhydride (LDPE/TPS/PE‐g‐MA) blends. For this purpose, CNFs, isolated from wheat straw fibers, were first acetylated using acetic anhydride in order to modify their hydrophilicity. Afterwards, LDPE/TPS/PE‐g‐MA blends were reinforced using either CNFs or ACNFs at various concentrations (1–5 wt%) with a twin‐screw extruder. The mechanical results demonstrated that addition of ACNFs more significantly improved the ultimate tensile strength and Young's modulus of blends than addition of CNFs, albeit elongation at break of both reinforced blends decreased compared with the neat sample. Additionally, biodegradability and water absorption capacity of blends improved due to the incorporation of both nanofibers, these effects being more pronounced for CNF‐assisted blends than ACNF‐reinforced counterparts. © 2018 Society of Chemical Industry     

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     

Tailored biodegradable films via extrusion blow molding using PBS,PBAT, and TPS

Research to replace synthetic polymers with biodegradable polymers is on the rise because common plastics have generated serious ecosystem problems. Films with thermoplastic starch (TPS), poly(butylene succinate) (PBS), poly(butylene adipate-co-butylene terephthalate (PBAT), and citric acid (CA) were produced by blown extrusion. They were characterized by blow-up ratio (BUR), water vapor permeability (WVP), soluble ratio (SR), water sorption isotherm, and thermogravimetric (TG) techniques. Films were uniform and showed BUR > 205%. The different proportions of PBS and PBAT significantly influenced the WVP of the films. All samples had WVP with an order of magnitude similar to other blends with high starch content (10⁻⁶ g m⁻¹ day⁻¹ Pa⁻¹). CA efficiently decreased the WVP of the PBS/PBAT/TPS formulations (15/15/70% and 20/10/70% by mass) by 25.2% and 24.7% compared to the acid-free formulations. There was no significant difference in SR (19.0%–20.1%). These materials were sensitive to moisture since the equilibrium moisture content increased pronouncedly from water activity of 0.5. Films showed good thermal stability, with a maximum decomposition temperature close to pure polyesters. CA did not increase the thermal stability of blends, probably because of the low content used (0.1%). Given the outcomes of this study, these films could be deemed appropriate for applications in food packaging.     

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