Effect of starch type on miscibility in poly(ethylene oxide) (PEO)/starch blends and cytotoxicity assays

This study reports results on the miscibility of polymer blends based on PEO and different starches (unmodified, cationic, and hydrophobic) and their respective cytotoxicity. Films of PEO/starch blends at different weight ratios (95/05, 90/10, 80/20, 70/30, 65/35, and 60/40), as well as films of pure PEO as control, were prepared by casting methodology. Several techniques, such as SEM, WAXS, FTIR, and FT-Raman spectroscopy were used in this study for evaluating blend miscibility. The results revealed that the miscibility of such blends is dependent on the type of starch used. Regarding the PEO/unmodified starch blends, it was concluded that the system is miscible in the ratio range from 90/10 to 65/35. Although the PEO/hydrophobic starch blends are miscible in all the studied range, blends of PEO and cationic starch are immiscible, regardless the blend ratio. The different samples presented distinct cytotoxic behaviors. PEO and hydrophobic starch presented no relevant toxicity (CC_50/72 > 2.5 mg/mL). Otherwise, the cationic starch was the most harmful for the cells. The blends presented cytotoxicity values between those of PEO and cationic starch.     

Crystallisation and miscibility of poly(ethylene oxide)/poly(vinyl chloride) blends

Isothermal crystallisation of blends of Poly(ethylene oxide) and Poly(vinyl chloride), PEO/PVC, was analysed by differential scanning calorimetry (DSC). The influence of the amorphous polymer, PVC, on crystallisation rate of PEO was investigated using pure PEO as reference. Pure PEO and PEO/PVC blends were submitted to different crystallisation temperatures (from 40 to 58°C) and crystallisation times (from 1 to 72 h). Using the Hoffman-Weeks plot procedure, the equilibrium melting temperature, T _m°, was determined for pure PEO and for PEO/PVC blends with compositions (in wt%): 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70 and 20/80. The lamellar thickness factor of PEO crystals for pure PEO and for the blends showed a strong decrease when the PVC content was higher than 60 wt%. A small depression in T _m° was verified as the composition of PVC was increased. From the depression in T _m° the polymer-polymer interaction parameter, ₁₂, was evaluated using the Nishi-Wang equation. The results indicate that the miscibility between PEO and PVC in the molten state depends on the blend composition. The crystallisation rate also depends on the blend composition: the richer in PVC is the blend, the slower the crystallisation process.     

Miscibility and melting properties of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate) blends

The miscibility and melting properties of binary crystalline blends of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate) (PEN/PTT) have been investigated with differential scanning calorimetry (DSC). The glass transition and cold crystallization behaviors indicated that in PEN/PTT blends, there are two different amorphous phases and the PEN/PTT blends are immiscible in the amorphous state. The polymer–polymer interaction parameter, , calculated from equilibrium melting temperature depression of the PEN component was −1.791 × 10⁻⁵ (300 °C), revealing miscibility of PEN/PTT blends in the melt state.     

Electrospun PHBV/PEO co-solution blends: Microstructure,thermal and mechanical properties

Blending allows to tailor and modulate the properties of selected polymers. Blends of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and polyethylene oxide (PEO) were fabricated by electrospinning in different weight ratios i.e. 100:0, 80:20, 70:30, 50:50, 0:100.In order to evaluate the influence of PEO addition on the final properties of PHBV, a complete microstructural, thermal and mechanical characterization of PHBV/PEO blends has been performed. The two neat polymeric membranes were also considered for the sake of comparison. The following characterization techniques were employed: scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy, simultaneous thermogravimetric and differential analyses (TG-DTA), differential scanning calorimetry (DSC), and uniaxial tensile tests.All electrospun mats consisted of randomly oriented and uniform fibers. It has been observed that the microstructure of PHBV/PEO was remarkably affected by blend composition. The average fiber size ranged between 0.5 μm and 2.6 μm. It resulted that the electrospun polymeric blends consisted of separate crystalline domains associated to an amorphous interdisperse phase. PHBV/PEO blends presented intermediate mechanical properties, in terms of tensile modulus and ultimate tensile stress, with respect to the two neat components.     

Improvement of ternary recycled polymer blend reinforced with date palm fibre

This paper investigates the study and preparation of date palm fibre reinforced recycled polymer blend composites. This is the first paper which describes the recycled polymer ternary blends of (1) recycled low density polyethylene (RLDPE), (2) recycled high density polyethylene (RHDPE) and (3) recycled polypropylene (RPP). The date palm fibre reinforced composites (C_D00) were prepared by maintaining constant weight% of fibre of 20 wt% without any fibre treatment. Maleic anhydride (MA) was used as the compatabilizer (1 and 2 wt%) and the effect of compatabilizer on the blend matrix composites was studied. The mechanical, thermal, morphological properties, water absorption and chemical resistance properties were evaluated for these composites and also studied for pure blend matrix (C₀₀). Date palm fibre improved the tensile strength and hardness of recycled polymer blend matrix. Further improvement was achieved with 1% MA (C_D1), which showed that 1% MA treated composites (C_D1) had higher tensile strength, modulus and hardness properties. Thermal stability and water absorption were improved by 1% MA. These improvements were demonstrated at the nanoscale level by the decrease in roughness appearing in Atomic Force Spectroscopic Microscopy analysis indicating that flow is better under this concentration. The SEM analysis also showed that the fibre matrix adhesion improved by adding 1 wt% (C_D1) of MA. The melting and crystallisation temperatures of the blends did not change with the addition of date palm fibre and MA, indicating that the additives did not influence the melting and crystallisation properties of the composites. The chemical resistance test results showed that these composites are resistance to all chemicals but more weight gain observed in solvents. 2 wt% of MA (C_D2) caused poor adhesion between the polymer chains and fibres as well as polymer chain scission.     

Crystallization of partially miscible linear low-density polyethylene/poly(ethylene-co-vinylacetate) blends

Miscibility and crystallization of linear low-density polyethylene (LLDPE)/poly(ethylene-co-vinylacetate) (EVA) blends were investigated by optical microscopy (OM) and differential scanning calorimetry (DSC). It was found that there existed liquid–liquid phase separation (LLPS) below 220 °C over the whole composition. However, the depression in the crystallization temperature, melting temperature and equilibrium melting temperature of LLDPE all indicated that this polymer pair was partially miscible. The crystallization and melting behavior of LLDPE were determined by the dilute effect of non-crystalline EVA and the probable co-crystallization of parts of EVA chains with LLDPE chains. The crystallization and melting behavior of EVA was determined by the competence between a nucleation effect of LLDPE crystals and partial miscibility between this polymer pair, which was different from that of LLDPE.     

Study on the compatibility and crystalline morphology of NBR/PEO binary blends

Compatibility property, as well as crystalline morphology, of NBR/PEO blends has been investigated by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and polarized optical microscopy (POM) thoroughly. There is no apparent shift of nitrile or ether groups in the FTIR spectra of NBR/PEO blends. Based on the calculations from glass transition temperature, the maximum volume fraction of PEO dissolved in NBR phase is about 6.41 % in blend with 5 wt% PEO content (PEO-5), indicating a weak intermolecular interaction in the NBR/PEO blends. From the characteristic absorption bands in the FTIR spectra, XRD and POM graphs, the crystallinity ratio of NBR/PEO blends decreases as the NBR content increases, which is further proved by DSC measurement that the crystallinity ratio and crystal melting temperature of pure PEO are 82.6 %, 69.9 °C, and that of PEO-5 are 16.9 %, 59.5 °C. This illuminates that the weak intermolecular interaction will affect the crystallinity ratio and crystal melting temperature of the NBR/PEO blends.     

Manufacture and research of TPS/PE biocomposites properties

In this paper the process of native starch preparing for modification by extrusion and manufacture of biocomposites is presented. The first aim of this study was to determine the mixing and granulating condition of native starch to obtain granulated native starch. For mixing and granulation of native starch Intensive Mixer manufactured by Maschinenfabrik Gustav Eirich was used. Mixing and granulation in a single process is a new method of preparation of powders for other processing. The main task of granulation is the elimination of dust emissions and the increase in density of powders. Granules are easy for dosage and more handy for transport and storage than powders, which is important from a technological point of view.The second aim of this study was to manufacture TPS/PE biocomposites. At first thermal modification of waxy maize starch was carried out with the use of a co-rotating twin screw extruder. During extrusion native starches have been deprived of their crystallinity and the obtained starch (TPS) has fully amorphous structure. XRD analysis revealed that semi crystalline phase of native starch after extrusion disappeared. During extrusion crystal structure of native starch is transformed into amorphous structure of thermoplastic starch (TPS), which was confirmed by XRD analysis.Reactive extrusion of obtained thermoplastic starch and high density polyethylene (HDPE) in the presence of polyethylene-grafted maleic anhydride (PE-g-MA) was done. To modify properties of TPS/PE blend polycaprolactone (PCL) was added in amount of 5 and 10 wt.%. The mass flow rate, static mechanical properties, thermal properties and morphology of obtained biocomposites were examined. The results show that the increased amount of TPS caused an increase in tensile strength and modulus of elasticity of prepared biocomposites. Addition of PCL to TPS/PE blends decreased tensile strength and modulus of elasticity. Moreover, higher amount of TPS and PCL in TPS/PE blends caused decrease of the elongation at break. On the other hand, using of PE-g-MA in TPS/PE blends cause increasing phase compatibility, which was confirmed by mechanical properties and morphology measurements.Biocomposites filled with higher TPS content (45 and 60 wt.%) possess lower resistance to hydrolytic degradation, which cause decrease of mechanical properties.It was found that higher amount of TPS in TPS/PE blends have small effect on mass flow rate and thermal properties estimated by differential scanning calorimetry (i.e. melting temperature, degree of crystallinity, melting enthalpy). This phenomenon have significant influence on processing of obtained biocomposites.     

Morphology,interfacial and mechanical properties of polylactide/poly(ethylene terephthalate glycol) blends compatibilized by polylactide-g-maleic anhydride

Polylactide/poly(ethylene terephthalate glycol) (PLA/PETG 80/20 wt) blends compatibilized with polylactide-g-maleic anhydride (PLA-g-MAH) were prepared by melt blending and the rheological, morphological and mechanical properties of the blends were studied. PLA/PETG (80/20 wt) blend formed a typical sea-island morphology, while upon compatibilization, the size and size distribution of the dispersed phase decreased significantly and the 3 wt% PLA-g-MAH compatibilized blend exhibited the smallest phase size and the narrowest distribution of the dispersed particles. The interfacial tension between PLA and PETG was determined from the morphological characteristics and the viscoelastic response of PLA/PETG blends via using two emulsion models. A minimum for PLA/PETG blend containing 3 wt% PLA-g-MAH was observed from both Palierne model and G–M model. The elongation-at-break increased by ∼320%, from 6.9% for PLA to 28.7% for the blend containing 3 wt% PLA-g-MAH without significant loss in the tensile modulus and tensile strength.     

Electrospun chitosan/PEDOT nanofibers

Plasma-modified chitosan and poly(3,4-ethylenedioxythiophene) were blended to obtain conducting nanofibers with polyvinyl alcohol as a supporting polymer at various volumetric ratios by electrospinning method. Chemical compositions and molecular interactions among nanofiber blend components were determined using Fourier transform infrared spectroscopy (FTIR). The conducting blends containing plasma-modified chitosan resulted in a superior antibacterial activity and thinner fiber formation than those containing chitosan without plasma-modification. The obtained nanofiber diameters of plasma-modified chitosan were in the range of 170 to 200 nm and those obtained from unmodified chitosan were in the range of 190 to 246 nm. The electrical and electrochemical properties of nanofibers were also investigated by four-point probe conductivity and cyclic voltammetry measurements.     

PAN–PEO solid polymer electrolytes with high ionic conductivity

The transparent and flexible solid polymer electrolytes (SPEs) are fabricated from polyacrylonitrile–polyethylene oxide (PAN–PEO) copolymer. The formation of the copolymer is confirmed by Fourier-transform infrared spectroscopy (FTIR) and Gel permeation chromatography (GPC) measurements. The effects of acrylonitrile (AN) wt% content and M_n(PEO) on ionic conductivity are investigated by alternating current (ac) impedance spectroscopy. By controlling and adjusting the AN wt% content and doping PEO with high molecular weight, the ionic conductivity of SPEs is optimized. The ionic conductivity of PAN–PEO solid polymer electrolytes is found to be high 6.79 × 10⁻⁴ S cm⁻¹ at 25 °C with an [EO]/[Li] ratio of about 10, and are electrochemically stable up to about 4.8 V versus Li/Li⁺. The conductivity and interfacial resistance remain almost constant even at 80 °C.     

Thermal,mechanical and rheological properties of polylactide toughened by expoxidized natural rubber

This paper concerns on the use of epoxidized natural rubber (ENR) as toughening agent for polylactide (PLA). ENR with epoxidation content of 20 mol% (ENR20) and 50 mol% (ENR50) were separately melt blended with PLA using an internal mixer. DSC results suggested that PLA/ENR blends were amorphous after melt blending while they were crystalline and revealed two melting peaks in the thermograms after being annealed at 100 °C. Mechanical tests showed that the introduction of ENR reduced the tensile modulus and strength but enhanced the elongation and the impact strength of PLA. The impact strength of the 20 wt% ENR20/PLA and ENR50/PLA blends increased to 6-fold and 3-fold, respectively, compared to that of pure PLA. This enhancement was due to a good interfacial adhesion between ENR and PLA. Both ENR20/PLA and ENR50/PLA blends performed very strong shear thinning behavior, and the complex viscosity, storage and loss modulus of the blends also increased after blending with ENR.     

Gamma irradiation aging of NBR/CSM rubber nanocomposites

The effect of gamma-irradiation on the acrylonitrile butadiene/chlorosulphonated polyethylene rubber blends (NBR/CSM) based nanocomposites containing carbon black (CB) and silica filler (Si) were investigated by TG-DTG and ATR-FTIR techniques. The silica (with primary particle size of 22 nm) was added in content of 0, 10, 20 and 30 phr and carbon black (with primary particle size 40–48 nm) was added in content of 30 phr and rubber blend compounds were prepared. The obtained elastomeric materials were aging to different γ-irradiation doses (100, 200 and 400 kGy). The cure and mechanical properties of obtained nanocomposites were determined. Incorporating 20 phr of silica to the control NBR/CSM rubber blends containing 30 phr CB resulted 152% increase in tensile strength, 116%, in elongation at break and 142% modulus at 100% elongation, according to synergistic effect between the fillers. FTIR measurements of aged samples estimated the formation of alcohols, ethers and small amounts of lactones, anhydrides, esters and carboxylic acids after exposure to lower doses of γ-radiation (100 kGy). On the basis of the obtained spectra the formation of shorter polyene sequences and aromatic rings in aged elastomeric samples are assumed. The results show that 30 phr of carbon black (CB) and 20 phr of silica are needed for the best gamma aging resistance of NBR/CSM rubber nanocomposites. The result of radiation exposure is decrease in mechanical properties. The dose at which ultimate mechanical properties decreased was at 200 kGy. TG-DTG measurements estimated decrease in thermal stability of gamma-irradiated NBR/CSM rubber blend based nanocomposites. Silica reinforced NBR/CSM rubber blend had better radiation resistant than carbon black. Rough and heterogeneity of fracture surfaces has been observed for NBR/CSM rubber blends filled with silica. More uniform morphology of fracture surfaces according to high polymer–filler interaction and low filler–filler interaction has been observed for CB/Si filled NBR/CSM rubber blend.     

Composition-dependent physical properties of poly[(vinylidene fluoride)-co-trifluoroethylene]–poly(ethylene oxide) blends

Polymer blends based on poly(vinylidene fluoride-co-trifluoroethylene) copolymers, P(VDF-TrFE), and poly(ethylene oxide), PEO, with varying compositions have been prepared by solvent casting. In this way, P(VDF-TrFE) crystallizes from the solution while solvent evaporates, while PEO crystallizes from the melt during cooling to room temperature. The surface morphology of the polymer blends indicates the transition from the fibrillar microstructure typical of PVDF-TrFE to the spherulite structure characteristic of PEO. The vibration mode characteristics of P(VDF-TrFE) are not influenced by the presence of PEO in the polymer blend. Confinement of PEO in the P(VDF-TrFE) phase change the conformation of PEO from trans to helix, increasing this transformation for increasing P(VDF-TrFE) content in the polymer blends. Sequential crystallization of the two polymers produce separated amorphous phases whose independent cooperative conformational motions are revealed by two main dynamic-mechanical relaxations. No chemical interaction seems to exist between the polymers within the blend.     

杜仲胶/天然橡胶共混物的分子动力学模拟和耗散粒子动力学模拟

应用分子动力学(MD)和耗散粒子动力学(DPD)模拟方法对杜仲胶(TPI)、天然橡胶(NR)的相容性进行了研究。采用MD模拟方法,在COMPASS力场下,对纯物质在不同聚合度下的溶度参数、一系列共混比的TPI/NR共混物内聚能密度、Flory-Huggins作用参数进行了模拟计算,确定了纯物质单链的聚合度,经判断各比例共混物的相容性均较好;采用DPD模拟方法对TPI/NR共混体系的相结构进行了研究,从等密度图可以进一步判断共混体系的相容性;分析比较两种纯物质的径向分布函数,揭示了其相互作用的本质;经过分析比较静态力学性能,发现共混比为1/3的TPI/NR共混物性能最佳,其结论与实验结果一致。     

Phase behaviour, mechanical properties and thermal stability of thermosetting polymer blends of unsaturated polyester resin and poly(ethylene oxide)

The results of dynamic mechanical analysis reveal that crosslinked polyester resin (PER)/poly(ethylene oxide) (PEO) blends show a composition dependent glass transition temperature, Tg, which suggests that the blends studied are homogeneous in the amorphous state. The initial dynamic storage modulus, E', decreases with increasing PEO content up to 30 wt% in the blends, whereas E for both the 60/40 and 40/60 PER/PEO blends is close to that for the 80/20 PER/PEO blend and much larger than that for the 70/30 PER/PEO blend. The addition of crystalline PEO has a remarkable effect on the mechanical properties of crosslinked PER. Tensile testing shows that the elongation at break first increases greatly and then decreases slightly, whereas the Young's modulus and the tensile strength first decrease and then increase slightly with increasing PEO content in the blends. The variation of tensile properties was considered to be due to both the plasticization effect and the crystallization effect of PEO in the blends. The impact strength remains almost unchanged with increasing PEO content in the blends studied. No dramatic decrease of thermal stability for PER/PEO blends was observed for the blends with PEO content up to 30 wt%.     

Structural,electrical and electrochemical parameters of PEO–NaClO3 composite for battery applications

Polyethylene oxide–NaClO₃ composite have been prepared by solution casting technique with different weight percentages as a polymer electrolyte for battery application. The prepared composites were characterized by various tools like XRD, FTIR and SEM. The X-ray diffraction analysis shows the complexation of polymer with salt and existence of both crystalline and amorphous phases. From FTIR spectra confirms the formation of PEO–NaClO₃ composites. SEM images shows the grains are highly agglomerated and its average size increases with increase in salt ratio. Frequency dependence of dielectric property and ac electrical conductivity of polymer electrolytes were studied within the frequency range of 50 Hz to 5 MHz using complex impedance analysis technique. Ionic conductivity follows Arrhenius type behavior as a function of temperature. The fabricated cell of 25 wt.% of PEO–NaClO₃ composites generated high current of 1.79 A.     

淀粉接枝共聚物在淀粉/聚乳酸共混体系中的作用

研究了淀粉／聚乳酸共混体系的相容性，考察了淀粉－聚醋酸乙烯酯和淀粉－聚乳酸接枝共聚物对淀粉／聚乳酸共混体系相容性的影响。发现上述两种接枝共聚物均可有效地增加淀粉与聚乳酸的相容性，从而提高共混体系的耐水性的力学性能。     

Sorption and diffusion of compressed carbon dioxide in polycaprolactone for the development of porous scaffolds

In this work different phenomena related to sorption of carbon dioxide in polycaprolactone (PCL) have been investigated systematically. The use of compressed carbon dioxide is discussed for obtaining porous scaffolds from this biocompatible polymer. In order to determine the plasticization effect of carbon dioxide on the degree of foaming it is necessary to discuss sorption data with respect to morphological features of the polymer at conditions nearby the melting point. The amount of carbon dioxide dissolved and the kinetics of the sorption process are found to depend strongly on temperature and pressure. The solubility takes values of up to 25 wt.% being favoured by a melting and glass transition temperature depression which can be observed along with an enhanced mass transfer rate. In general, CO₂ sorption in PCL increases linearly with pressure. When decompressing, microfoaming occurs which enhances the rate of gas release. Changes in morphology and crystallinity occur as a consequence of the pressure treatment. Compared to the melting temperature at atmospheric pressure there is a dramatic reduction observed under pressure where melting occurs already at a temperature below 40 °C. Even after pressure-treatment, there is a remaining change in melting temperature and crystallinity observed. Optimum conditions for obtaining adequate porous scaffolds of PCL are a relatively slow decompression after treatment at 17 MPa and 35 °C.     

Thermomechanical properties of a polymer blend: Investigation of a third phase

This paper deals with immiscible blends of poly(ethylene terephthalate) with polycarbonate obtained by melt mixing. Miscibility of the polyester blends is influenced by transesterification reactions, that are catalyzed either by catalyst residues in the polyesters or by catalysts added on purpose in the blend. These reactions convert the initial homopolymers into block and even random copolymers and affect both the miscibility of the system and the adhesion between the phases. The effect of catalysts and stabilizers on the morphology of PET/PC 50/50 blends was investigated using dynamic mechanical thermal analysis, rheology, microscopy and tensile tests. PET/PC 50/50 containing 0.05 wt.% of lanthanide acetyl acetonate exhibit a irreversible transition occurring at temperature higher than the glass transitions of PET and PC. This transition induces a large increase of the shear modulus and it was attributed to the formation of a third phase in the blend.