Physical and mechanical properties of plasticized butenediol vinyl alcohol copolymer/thermoplastic starch blend

The poly(vinyl alcohol) (PVOH) is an eco‐friend polymer and has an excellent oxygen barrier property due to its strong intermolecular force, but difficulty in processing with conventional extrusion process gives it a limitation for various industrial applications, especially packaging industry. Many studies have attempted to plasticize PVOH to improve its processability, but high cost of PVOH is still drawback for a variety of industrial applications. Therefore, PVOH often blended with other biodegradable polymers such as starch to acquire the cost benefit. Nowadays, the butenediol vinyl alcohol copolymer (BVOH) is getting a great attention due to its melt processability and bio‐degradability, but its high cost is barrier to the industrial application as well. In this study, thermoplastic starch (TPS)/plasticized BVOH (P‐BVOH) were prepared by melt mixing technique, and the plasticization effect of glycerol on starch and BVOH with different composition was observed for optimized processing condition. Based on our preliminary study, TPS was blended with varying amount of P‐BVOH (100:0, 90:10, 80:20, 70:30, 60:40, and 50:50 weight ratio). Physical, oxygen barrier, and mechanical properties of the TPS/P‐BVOH blends were evaluated by various analytical instruments to achieve balanced property and performance. J. VINYL ADDIT. TECHNOL., 25:109–116, 2019. © 2018 Society of Plastics Engineers     

Mechanical and microstructural properties of pectin/starch films

Films were made from blends of high methoxy pectin and high amylose starch gelatinized in a microwave oven in the presence and absence of glycerol at times ranging from 10 to 105 s. Three thermodynamic transitions were observed when storage modulus, loss modulus, and loss tangent were plotted against temperature. All three transitions gave minima when the transition temperature was plotted against time of gelatinization. Overall, there were only modest changes in these moduli over the range of gelatinization times studied, with little difference between films made with the starch gelatinized in either the presence or absence of glycerol. Starch granules were found to disappear at gelatinization times between 20 and 30 s, although much smaller starch particles seemed to recur at gelatinization times of 75 s and above. The minima found in the transition temperature and modulus plots were believed to result from a minimum in the amount of intermolecular interactions between the starch molecules. © 1995 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

Preparation and properties of plasticized starch/multiwalled carbon nanotubes composites

In this work we have studied the utilization of multiwalled carbon nanotubes (MWCNTs) as filler‐reinforcement to improve the performance of plasticized starch (PS). The PS/MWCNTs nanocomposites were successfully prepared by a simple method of solution casting and evaporation. The morphology, thermal behavior, and mechanical properties of the films were investigated by means of scanning electron microscopy, wide‐angle X‐ray diffraction, differential scanning calorimetry, and tensile testing. The results indicated that the MWCNTs dispersed homogeneously in the PS matrix and formed strong hydrogen bonding with PS molecules. Compared with the pure PS, the tensile strength and Young's modulus of the nanocomposites were enhanced significantly from 2.85 to 4.73 MPa and from 20.74 to 39.18 MPa with an increase in MWCNTs content from 0 to 3.0 wt %, respectively. The value of elongation at break of the nanocomposites was higher than that of PS and reached a maximum value as the MWCNTs content was at 1.0 wt %. Besides the improvement of mechanical properties, the incorporation of MWCNTs into the PS matrix also led to a decrease of water sensitivity of the PS‐based materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Modified cassava starch/poly(vinyl alcohol) blend films plasticized by glycerol: Structure and properties

We report a systematic investigation on the structure–property relationships in glycerol-plasticized poly(vinyl alcohol) (PVA)/cassava starch blends prepared via solution casting. In particular, PVA mixed with native, low-oxidized, high-oxidized, and pregelatinized cassava starches were characterized by means of SEM, XRD, FTIR, thermal analysis and mechanical testing and the immiscible systems were received. Burial tests over a period of several days suggested the preferential degradation of the starch and glycerol component (as indicated by the absence of FTIR signatures of those components) and the amorphous phase of PVA (as indicated by the enhanced crystallinity index of the degraded samples). The rheological properties of the blends seem to dictate their morphological characteristics that, in turn, have a profound impact on their mechanical properties. In that sense, the study highlights promising strategies for the development of a new family of polymeric materials that combine their biodegradable nature within superior mechanical properties. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48848.     

Viscoelastic properties of plasticized amylose films

The viscoelastic properties of amylose films plasticized with dimethyl sulfoxide were studied. The modulus–temperature curves of dimethyl sulfoxide-plasticized amylose are typical for semicrystalline polymers at the higher concentrations of amylose and pass to those of amorphous polymers with the decrease of amylose content. The glassy modulus is not affected by the incorporation of dimethyl sulfoxide, but the rubbery modulus and T_g are depressed with increased dimethyl sulfoxide. The change of T_g with plasticization can be represented by two approximately straight lines, one representing the lower concentration region of amylose and the other the higher one. The critical concentration is about 60% amylose. When the results of modulus–time measurements and x-ray diffraction are considered together, in a system of amylose–dimethyl sulfoxide, amylose exists as a semicrystalline polymer at high concentrations of amylose, and it acts intermediate between semicrystalline and amorphous polymers at lower concentrations below about 60%. From an extrapolation of the data of T_g of plasticized amylose, T_g of pure amylose appears to be approximately 330°C. The viscoelastic properties of amylose films plasticized with dimethyl sulfoxide–sorbitol mixtures were also studied.     

Effect of magnesium chloride hexahydrate on thermal and mechanical properties of starch/PVA films

Starch/poly(vinyl alcohol) (PVA) blend films were prepared from the aqueous solutions containing starch, PVA and magnesium chloride hexahydrate (MgCl₂.6H₂O). The interaction between MgCl₂.6H₂O and starch/PVA was studied by Fourier transform infrared spectroscopy. The plasticising effect of MgCl₂.6H₂O on starch/PVA film was studied by scanning electron microscopy (SEM), X-ray diffraction, thermogravimetric analysis, dynamic mechanical analysis and tensile testing respectively. The water content of starch/PVA films increased with the content of MgCl₂.6H₂O. The absorbed water can act as the plasticiser for starch/PVA film. The crystals of starch and PVA were destroyed, and the crystallinity of starch/PVA film decreased with the plasticising effect of MgCl₂.6H₂O and water. SEM micrographs showed that the compatibility between starch and PVA improved with the addition of MgCl₂.6H₂O. The toughness of starch/PVA film increased with the content of MgCl₂.6H₂O.     

Analysis of the influence of composition and processing parameters on the mechanical properties of biodegradable starch/pectin blends

The selection of the composition and processing conditions for carbohydrate-based blends is of fundamental importance for many applications and plays a role in determining the mechanical behavior of these biodegradable materials. In this study, starch/pectin (PEC) blends were obtained via melt technique and an investigation of the effects of composition and processing parameters on their mechanical properties was performed. The blends were prepared by adopting an experimental design and were characterized by uniaxial tensile tests, scanning electron microscopy, and phase imaging atomic force microscopy. The starch:PEC mass ratio showed the maximum influence on the tensile properties, which were independent on the processing parameters. It was suggested that as the degree of methyl esterification of PEC decreased, the modulus and tensile strength of the blends increased, and this effect was observed up to 50?wt% starch. AFM revealed the immiscibility between the polymers and this phenomenon was associated to the mechanical behavior of the blends.     

Effect of epoxy functionalized compatibilizer on the mechanical properties of low‐density polyethylene/plasticized tapioca starch blends

A series of low‐density polyethylene (LDPE) blends with varying proportions of plasticized tapioca starch have been used for the study of their mechanical properties. A functionalized epoxy resin, namely, poly(ethylene‐co‐glycidyl methacrylate) has been used as the compatibilizer. The impact and tensile properties have been measured by standard ASTM methods. The mechanical properties are seen to improve significantly with the addition of the epoxy compatibilizer, approaching values close to those of virgin LDPE. The scanning electron micrographs of the compatibilized blends show ductile failure which evidently contribute to improved mechanical properties. © 2001 Society of Chemical Industry     

Viscoelastic properties of plasticized amylose triacetate films

The viscoelastic properties of amylose triacetate films plasticized with diisobutyl phthalate were studied. The modulus–temperature curves of diisobutyl-phthalate-plasticized amylose triacetate are typical for amorphous polymers with the decrease of amylose triacetate content. The glassy modulus is not affected by the incorporation of diisobutyl phthalate, but the rubbery modulus and glass transition temperature are depressed with increased diisobutyl phthalate. The rubbery modulus appears at first to maintain for a wide temperature range, then disappears with increased diisobutyl phthalate. From the results of modulus–time measurements and x-ray diffraction patterns: in a system of amylose triacetate–diisobutyl phthalate, amylose triacetate exists as an amorphous polymer at all concentrations of amylose triacetate and it acts intermediately between semicrystalline and amorphous polymers at lower concentrations below about 90%.     

The molecular, physical and mechanical properties of highly plasticized poly(vinyl chloride) membranes

Highly plasticized poly(vinyl chloride) membranes (200 parts per hundred resin, phr) form the basis of ion-selective electrodes. The effects that five different plasticizers with different chemical structures, polarities and molecular weights have on modified mechanical properties such as strength, secant stiffness, toughness and ductility were examined by puncture testing. As a function of membrane thickness, strength, toughness, and secant stiffness increase, while ductility remains constant. For maximal membrane strength and toughness, plasticizer should be roughly 1000. The optimal ratio of experimental plasticization level (phr_exp = 200) to the minimal level required for complete plasticization (phr_min) was found to be 2. A ‘tube’-like model for plasticizer interaction with polymer chains is proposed to explain the vast differences in the mechanical properties of membranes.     

Morphological,barrier, and mechanical properties of cassava starch films reinforced with cellulose and starch nanoparticles

A comparative performance study of cellulose and starch nanoparticles on plasticized starch reinforcement has been presented. Starch nanoparticles were obtained by ultrasound and acid hydrolysis, and cellulose nanoparticles were extracted by acid hydrolysis from microcrystalline cellulose and sisal fibers. The nanoparticles were characterized according to the zeta potential, the particle-size distribution, transmission electron microscopy, X-ray diffraction, and thermogravimetric analysis. The influence of the addition of these nanoparticles to starch films on the morphology, water vapor permeability (WVP), and mechanical properties of the nanocomposites films were investigated. The cellulose nanoparticles exhibited higher electrical stability than those originating from starch. Acid hydrolysis produced starch nanoparticles with higher crystallinity than ultrasound. All the nanoparticles significantly reduced the WVP. The cellulose nanoparticles significantly increased the tensile strength of the starch films; however, they reduced the flexibility of the nanocomposites. The results of this work support the application of starch and cellulose nanostructures for the development of reinforced biodegradable materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47001.     

Influence of the oxidation and acetylation of banana starch on the mechanical and water barrier properties of modified starch and modified starch/chitosan blend films

Banana starch was oxidized at three different levels and afterwards acetylated. The double‐modified starch was used for film preparation with the addition of chitosan. The physical, mechanical, and barrier properties were tested. The oxidation level increased the moisture content of the film, but the acetylation and the addition of chitosan decreased this characteristic. The oxidation level increased the whiteness of the film, but the second modification (acetylation) and the addition of chitosan to the blend did not affect this parameter. The solubility increased with the temperature and the oxidation level but decreased with the storage time of the film. The oxidation increased and the acetylation reduced the solubility with respect to the native starch film. The dual modification produced a solubility value less than that of its oxidized counterpart, and the addition of chitosan produced the highest solubility value. The addition of chitosan increased the tensile strength of the film, and the effect was higher with the oxidation level and longest storage time. The addition of chitosan produced a higher elongation value than that of its double‐modified film, but at the longest storage time, this parameter decreased. The water vapor permeability increased with the oxidation level because of the hydrophilic character, but the acetylation reduced this parameter because the acetylation increased the hydrophobic character of the starch due to the ester group. Films prepared with the double‐modified banana starch and the addition of chitosan had some improved physical, mechanical, and barrier properties, and they may be used in specific applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical properties of nanocomposites from sorbitol plasticized starch and tunicin whiskers

Nanocomposite materials were obtained using sorbitol plasticized waxy maize starch as matrix and tunicin whiskers as the reinforcement. The effect of filler load (0–25 wt % whiskers) and the relative humidity levels (0–98%) on the mechanical behavior of the films are discussed for linear and nonlinear deformation. The performance of the films is explained, based on the morphology and structural behavior of the composite materials (Mathew and Dufresne, Biomacromolecules 2002, 3, 609). The nanocomposites exhibit good mechanical strength due to the strong interaction between tunicin whiskers, matrix, plasticizer (sorbitol), and water, and due to the ability of the cellulose filler to form a rigid three‐dimensional network. The evolution of T_g as a function of relative humidity level and filler load is studied in detail. A decrease in crystallinity of the amylopectin phase is observed at high filler loads, due to the resistance to chain rearrangement imposed by the whiskers. The mechanical strength increased proportionally with filler loads, showing an effective stress transfer from the matrix to the whiskers. An even distribution of whiskers (as determined by SEM) and plasticizer in the matrix contributes to the mechanical performance. The mechanical properties of the nanocomposites showed a strong dependence on relative humidity conditions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rheological and mechanical properties of polypropylene/thermoplastic starch blend

Starch as an inexpensive and renewable source has been used as a filler for environmentally friendly plastics for about two decades. In order to improve the compatibility between hydrophilic starch granules and hydrophobic polypropylene (PP), glycerol used as a plasticizer for starch to enhance the dispersion and the interfacial affinity in thermoplastic starch (TPS)/PP blend. In this study, PP was melt blended with thermoplastic starch (TPS) using a single screw extrusion process and molded using injection molding process to investigate the rheological and mechanical properties of these blends. TPS viscosity measurements were performed on the single screw extruder. Rheological properties were studied using a capillary rheometer and the Bagley’s correction was performed. Mechanical analysis (stress–strain) was performed using Testometric M350-10KN. The rheological properties showed that the viscosity of TPS decreases with increasing glycerol content in TPS. Also, it was found that PP/TPS blends are pseudo plastic in nature and the flow activation energy of the blends is greater than that of PP. Mechanical results showed that strain at break of the blends is lower than that of PP, whereas the Young’s modulus of the blends is higher than that of PP.     

Processabilities and mechanical properties of surlyn-treated starch/LDPE blends

The esterification of the hydroxyl group of starch with DuPont Surlyn was considered as pretreatment method of starch before blending with polyolefins. In treating starch with Surlyn, two different raction conditions were taken to optimize reaction conditions. First, the esterification reaction was carried out in 110°C xylene with oleic acid as a catalyst. Second, the reaction out in a 90°C mixture of deionized water and xylene with ceric ammonium nitrate(CAN) as an initiator. Starch granules would be swollen above the gelatinization temperature in water. In both cases starch was midified by Surlyn to have good compatibility with low-density polyethylene (LDPE). The mechanical and theological properties were examined for blends of the treated starch and LDPE. This system may be one of the biodegradable polymer blends that sufficiently retain properties as a packaging film.     

Influence of plasticizer configurational changes on the mechanical properties of highly plasticized poly(vinyl chloride)

The effects of configurational changes among nine plasticizers were studied using puncture tests. Ion-selective poly(vinyl chloride) (PVC) membranes were plasticized with three citrate-related compounds (Citroflex A-4 (CFA4), Citroflex A-6 (CFA6), and Citroflex B-6 (CFB6)) and six sebacate-related compounds (dimethyl sebacate (DMS), diethyl sebacate (DES), dibutyl sebacate (DBS), dioctyl sebacate (DOS), dioctyl azelate (DOZ), and dioctyl adipate (DOA)). The strengths, stiffnesses, and toughnesses of the membranes increased at low PHR ratios (which are defined as the actual concentrations of plasticizer to PVC divided by the minimum concentrations of plasticizer required to isolate all of the PVC polar groups) and then monotonically decreased as plasticizer was added above these ratios. The ductilities increased up to PHR ratios of about 2.0 and decreased above PHR ratios of about 4.0. The citrate-related compounds could not be distinguished according to the mechanical properties. The DMS-, DES-, and DOA-plasticized membranes were generally stronger and stiffer than the DBS-, DOS-, and DOZ-plasticized membranes, but the ductilities were reduced using DMS, DES, and DOA. A nomogram was constructed to predict the strength, based on the plasticizer selection and PHR ratio. The strengths, stiffnesses, and toughnesses of the membranes decreased as the log (ionic conductivity, σ) increased, and the ranking of the configurational differences was similar to those of the mechanical properties versus PHR ratio.     

Structure and properties of soy protein films plasticized with hydroxyamine

Two kinds of transparent films of soy protein were successfully prepared by plasticizing with diethanolamine (DEA) and triethanolamin (TEA). The films were hot pressed at 140°C and 20 MPa, and characterized with Fourier transform infrared spectroscopy, scanning electron microscope, ultraviolet–visible spectrometer, differential scanning calorimetry (DSC), thermogravimetric analysis, and tensile testing. The results indicated that films with triethanolamine plasticizers possessed better optical transmittance (more than 80% at 800 nm) than those with diethanolamine and glycerol. All of the sheets exhibited only one T_g in DSC curves. Moreover, the soy protein plastics with TEA had higher thermal stability and mechanical properties, as well as lower water uptake than those with DEA and glycerol, as a result of the strong interaction between TEA and protein molecules. The soy protein materials will be promising for the application in the fields of package and container, substituting for the nongreen polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology,biodegradability, mechanical,and thermal properties of nanocomposite films based on PLA and plasticized PLA

In this study, melt intercalation method is applied to prepare poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG)‐plasticized PLA nanocomposite films including 0, 3, and 5% organoclay (Cloisite 30B) using a laboratory scale compounder, which is connected to a microcast film device. To evaluate the nanomorphology and the dispersion state of the clays, X‐ray diffraction (XRD) and transmission electron microscopy (TEM) are conducted. Tensile tests are performed to characterize the mechanical behavior of the films. Biodegradation rate is determined by degradation tests in composting medium. Differential scanning calorimeter (DSC) is applied to observe the thermal behavior of the films. XRD and TEM show that the exfoliation predominantly occurrs in plasticized PLA nanocomposites, whereas unexfoliated agglomerates together with exfoliated clays are observed in the nonplasticized PLA. Tensile tests indicate that the addition of 3% clay to the neat‐PLA does not affect the strength; however, it enhances the modulus of the nanocomposites in comparison to neat‐PLA. Incorporation of 3% clay to the plasticized PLA improves the modulus with respect to PLA/PEG; on the other hand, the strain at break value is lowered ～ 40%. The increase in the rate of biodegradation in composting medium is found as in the order of PLA > PLA/PEG > 3% Clay/PLA/PEG > 5% Clay/PLA/PEG > 3% Clay/PLA. DSC analysis shows that the addition of 3% clay to the neat PLA results in an increase in T_g. The addition of 20% PEG as a plasticizer to the neat‐PLA decreases T_g about 30°C, however incorporation of clays increases T_g by 4°C for the plasticized PLA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Interrelation of mechanical and optical properties of plasticized epoxy polymers

A series of cold-setting epoxy polymers, plasticized with different amounts of plasticizer, ranging between 0 and 90% by weight of the amount of the epoxy prepolymer, were studied for their mechanical, optical, and fracture behavior properties. Quantities defining the mechanical properties were considered: the elastic modulus E, Poisson's ratio v, and fracture tensile stress σ_f. These were accurately measured with electric strain gauges in specimens tested in a 5-ton Instron tester. The optical behavior was characterized by the stress optical coefficients of the materials in both principal directions, α and β, as well as by the coefficient of optical anisotropy, ζ. The values of these quantities were measured by a Fizeau interferometric method. Finally, the optical method of caustics was applied to cracked epoxy polymer specimens to provide a new experimental technique for determining the stress optical properties of these polymers in terms of their mechanical properties. This method was used to check the previous results found by established experimental methods.     

Correlation of mechanical and acoustical properties of plasticized epoxy polymers

In the present experimental work the influence of the percentage of plasticizer on the mechanical and acoustical properties of the plasticized epoxy polymers was studied. The velocity c_l of the longitudinal waves and the acoustic attenuation coefficient α were evaluated from the acoustical properties. Also the influence of curing time of plasticized epoxy polymers on the acoustical properties, c_l and α, was examined and it was found out that these quantities tend to their limiting values when the polymerization is completed. Furthermore, the determined acoustical properties are correlated with the corresponding mechanical properties for the same materials, which were also considered in earlier papers. So, a simple and quick experimental nondestructive technique is provided for the evaluation of the elastic properties, as well as of the epoxy polymers composition, by determining the velocity c_l of the longitudinal waves only.