Thermal,mechanical, and surface characterization of starch–poly(vinyl alcohol) blends and borax‐crosslinked films

Starch–poly(vinyl alcohol) (PVA) blends with different compositions were prepared and crosslinked with borax by in situ and posttreatment methods. Various amounts of glycerol and poly(ethylene glycol) with a molecular weight of 400 were added to the formulations as plasticizers. The pure starch–PVA blends and the crosslinked blends were subjected to differential scanning calorimetry, thermogravimetry, and X‐ray photoelectron spectroscopic studies. Broido and Coats–Redfern equations were used to calculate the thermal decomposition kinetic parameters. The tensile strengths and elongation percentages of the films were also evaluated. The results suggested that the glass‐transition temperature (T_g) and the melting temperature strongly depended on the plasticizer concentration. The enthalpy relaxation phenomenon was dependent on the starch content in the pure blend. The crosslinked films showed higher stability and lower T_g's than pure PVA and starch–PVA blends, respectively. High‐resolution X‐ray photoelectron spectroscopy provided a method of differentiating the presence of various carbons associated with different environments in the films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1313–1322, 2005     

Preparation and characterization of LDPE/PVA blend films filled with glycerin‐plasticized polyvinyl alcohol

A series of LDPE/PVA blend films were prepared via a twin‐screw extruder, and their morphology, thermal property, oxygen and water vapor permeation, surface properties, and mechanical properties were investigated as a function of the PVA content. During the extrusion process of the blend films, glycerin improved the compatibility and processing conditions between LDPE and PVA. The melting temperature (T_m), melting enthalpy (ΔH_m), crystallinity (%), and thermal stability of the thermal decomposition temperature (T_5%) of the LDPE/PVA blend films decreased with increasing PVA content. The oxygen permeabilities of the blend films decreased from 24.0 to 11.4 cm³·cm (m²·day·atm)^?1 at 23°C. The WVTR increased from 7.8 to 15.0 g(m² day)^?1 and the water uptake increased from 0.13 to 9.31%, respectively. The mechanical properties of blend films were slightly enhanced up to 2% PVA and then decreased. The physical properties of the blend films strongly varied with the chemical structure and morphology depending on the PVA and glycerin. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41985.     

Influences of ethylene–butylacrylate–glycidyl methacrylate on morphology and mechanical properties of poly(butylene terephthalate)/polyolefin elastomer blends

Elastomer ethylene–butylacrylate–glycidyl methacrylate (PTW) containing epoxy groups were chosen as toughening modifier for poly(butylene terephthalate) (PBT)/polyolefin elastomer (POE) blend. The morphology, thermal, and mechanical properties of the PBT/POE/PTW blend were studied. The infrared spectra of the blends proved that small parts of epoxy groups of PTW reacted with carboxylic acid or hydroxyl groups in PBT during melt blending, resulting in a grafted structure which tended to increase the viscosity and interfere with the crystallization process of the blend. The morphology observed by scanning electron microscopy revealed the dispersed POE particles were well distributed and the interaction between POE and PBT increased in the PBT/POE/PTW blends. Mechanical properties showed the addition of PTW could lead to a remarkable increase about 10‐times in impact strength with a small reduction in tensile strength of PBT/POE blends. Differential scanning calorimetry results showed with increasing PTW, the crystallization temperature (T_c) and crystallinity (X_c) decreased while the melting point (T_m) slightly increased. Dynamic mechanical thermal analysis spectra indicated that the presence of PTW could improve the compatibility of PBT/POE blends. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40660.     

Thermal properties and non‐isothermal crystallization behavior of biodegradable poly(p‐dioxanone)/poly(vinyl alcohol) blends

Blends of two biodegradable semicrystalline polymers, poly(p‐dioxanone) (PPDO) and poly(vinyl alcohol) (PVA) were prepared with different compositions. The thermal stability, phase morphology and thermal behavior of the blends were studied by using thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). From the TGA data, it can be seen that the addition of PVA improves the thermal stability of PPDO. DSC analysis showed that the glass transition temperature (T_g) and the melting temperature (T_m) of PPDO in the blends were nearly constant and equal to the values for neat PPDO, thus suggesting that PPDO and PVA are immiscible. It was found from the SEM images that the blends were phase‐separated, which was consistent with the DSC results. Additionally, non‐isothermal crystallization under controlled cooling rates was explored, and the Ozawa theory was employed to describe the non‐isothermal crystallization kinetics. Copyright © 2006 Society of Chemical Industry     

Glass‐transition and melting behavior of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

The glass‐transition temperatures and melting behaviors of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) (PET/PEN) blends were studied. Two blend systems were used for this work, with PET and PEN of different grades. It was found that T_g increases almost linearly with blend composition. Both the Gibbs–DiMarzio equation and the Fox equation fit experimental data very well, indicating copolymer‐like behavior of the blend systems. Multiple melting peaks were observed for all blend samples as well as for PET and PEN. The equilibrium melting point was obtained using the Hoffman–Weeks method. The melting points of PET and PEN were depressed as a result of the formation of miscible blends and copolymers. The Flory–Huggins theory was used to study the melting‐point depression for the blend system, and the Nishi–Wang equation was used to calculate the interaction parameter (χ₁₂). The calculated χ₁₂ is a small negative number, indicating the formation of thermodynamically stable, miscible blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 11–22, 2001     

Biodegradable poly(ethylene succinate) blends and copolymers containing minor amounts of poly(butylene succinate)

Poly(ethylene succinate) (PES), poly(butylene succinate) (PBS), and PES‐rich copolyesters were synthesized using an effective catalyst, titanium tetraisopropoxide. PES was blended with minor amounts of PBS for the comparison. The compositions of the copolyesters and the blends were determined from NMR spectra. Their thermal properties were studied using a differential scanning calorimeter (DSC), a temperature modulated DSC (TMDSC), and a thermogravimetric analyzer. No significant difference exists among the thermal stabilities of these polyesters and blends. For the blends, the reversible curves of TMDSC showed a distinct glass‐rubber transition temperature (T_g), however, the variation of the T_g values with the blend compositions was small. Isothermal crystallization kinetics and the melting behavior after crystallization were examined using DSC. Wide‐angle X‐ray diffractograms (WAXD) were obtained for the isothermally crystallized specimens. The results of DSC and WAXD indicate that the blends have a higher degree of crystallinity and a higher melting temperature than those of the corresponding copolymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Reactive blends of polyamide 6 with polyester elastomer using coupling agents

In situ compatibilized melt blends of polyamide 6 (PA‐6) with polyester elastomer (PEL) were prepared in a corotating twin‐screw extruder using two types of coupling agent (CA): diglycidyl ether of bisphenol A (DGEBA) and 1,4‐phenylene bis(2‐oxazoline) (PBO). The notched impact strength of PA‐6 and PA‐6/PEL blends increased with the addition of coupling agent, especially DGEBA, and the maximum impact toughening of the blend was obtained with 0.6 mol % DGEBA, the composition of minimum domain size observed from SEM. Viscosities of the untreated blends increased over those of the base resins at low frequencies. Viscosities of both the base resins and the blends increased with the addition of CA, and the effect was much more pronounced with DGEBA, especially for PA‐6 and PA‐6–rich blends. The crystallization temperature (T_c) of PEL increased over 10°C, whereas the T_c of PA‐6 decreased by 2–3°C in the blends. With the addition of coupling agents, the crystallization melting temperature (T_m) and T_c of PA‐6 decreased by up to 5°C with DGEBA, implying that the crystallization of PA‐6 is disturbed by the in situ formed PA‐6–CA–PEL or PA‐6–CA–PA‐6 type copolymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3966–3973, 2004     

Physical properties of PVA doped with algal glycerol

Physical behavior of membrane blends of poly(vinyl alcohol) (PVA) doped with different weight percentage (wt %) of algal glycerol is reported. Solid‐state PVA/glycerol membranes were prepared by the solution casting method. Electrical impedance measurements were conducted to test the effect of varying the percentage of glycerol on the conductivity of the membranes. The measurements were made in the frequency and temperature ranges 1 Hz–1 MHz and 303–423 K, respectively. It was observed that the ionic conductivity increased with the increase of glycerol concentration as well as temperature. The thermal properties of the films were characterized. It was found that the thermal properties, particularly the melting point (T_m), for PVA blends exhibit a reduced value proportional to the algal glycerol content. Fourier transform infrared spectroscopy was utilized to evaluate the interactions between the glycerol and PVA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4482–4489, 2013     

Preparation and characteristics of β-chitin and poly(vinyl alcohol) blend

Mechanical properties of blend films of β-chitin and poly(vinyl alcohol) (PVA) in dry and wet states were improved compared to those of homopolymers. Fourier transformed infra-red (FTi.r.) spectra of the blend showed the transition of hydroxyl and carbonyl stretching bands upon blending. The subtraction infra-red spectra of blend 70/30 indicated that the blend showed an intermolecular interaction and the reduction of crystallinity compared with those of pure β-chitin. Wide angle X-ray diffraction (WAXD) patterns of the blend also exhibited the loss of crystallinity of β-chitin and PVA upon blending. The blends, however, showed a mixed-crystal structure. Dielectric analysis of the blend showed the transition of α and β relaxation peaks of β-chitin upon blending, appeared at 182° and 97°, respectively. For blends, the temperature of the maximum loss (T_max) of β-chitin appeared at around 182° shifted to a lower temperature region. Differential scanning calorimetric analysis of the blend also showed the transition of melting endotherms of the blend. Transmission electron microscope (TEM) studies of blends using ruthenium tetraoxide as a staining agent were examined to reveal the micro-structure and miscibility of the blends. The TEM micrograph of blend 70/30 shows some microseparations, but it is still believed to be miscible in the blends.     

Solvent effects on the miscibility of poly(methyl methacrylate)/poly(bisphenol a carbonate) blends

Blends of atactic or syndiotactic poly(methyl methacrylate) (designated as aPMMA or sPMMA) and poly(bisphenol A carbonate) (PC) were prepared from solution casting. Tetrahydrofuran (THF) and chloroform were used as solvent. Experimental results indicated that the as‐cast blends from THF were quite different from the chloroform‐cast ones. After film preparation, THF‐cast blends did not show any visible phase separation. However, chloroform‐cast blends formed a phase‐separated structure. The as‐cast PC from either solvent was not completely amorphous, and had a melting point at 239–242°C, indicating a certain degree of crystallinity. In contrast, the quenched samples of aPMMA/PC blends prepared from the two solvents behaved virtually the same. They both showed aPMMA dissolves better in PC, but PC solubility in aPMMA is very little. Using sPMMA instead of aPMMA to blend with PC, different results were obtained. The quenched sPMMA/PC blends cast from THF showed only one T_g. However, immiscibility (i.e., two T_gs) was found in the same blend system when cast from chloroform. THF was believed to cause the observation of single T_g due to the following kinetic reason. sPMMA and PC were still trapped together even after THF removal in a homogeneous, but nonequilibrium state below the glass transition. Therefore, the quenched sPMMA/PC blends were not truly thermodynamically miscible. From the results of aPMMA or sPMMA with PC, increasing syndiotacticity seemed to improve the miscibility between PMMA and PC. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2842–2850, 2001     

Mechanical and thermal properties of glass bead–filled nylon‐6

The mechanical and thermal properties of glass bead–filled nylon‐6 were studied by dynamic mechanical analysis (DMA), tensile testing, Izod impact, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) tests. DMA results showed that the incorporation of glass beads could lead to a substantial increase of the glass‐transition temperature (T_g) of the blend, indicating that there existed strong interaction between glass beads and the nylon‐6 matrix. Results of further calculation revealed that the average interaction between glass beads and the nylon‐6 matrix deceased with increasing glass bead content as a result of the coalescence of glass beads. This conclusion was supported by SEM observations. Impact testing revealed that the notch Izod impact strength of nylon‐6/glass bead blends substantially decreased with increasing glass bead content. Moreover, static tensile measurements implied that the Young's modulus of the nylon‐6/glass bead blends increased considerably, whereas the tensile strength clearly decreased with increasing glass bead content. Finally, TGA and DSC measurements indicated that the thermal stability of the blend was obviously improved by incorporation of glass beads, whereas the melting behavior of the nylon‐6 remained relatively unchanged with increasing glass bead content. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1885–1890, 2004     

Thermal and mechanical properties of poly(vinyl alcohol) plasticized with glycerol

Thermomechanical behavior of membranes based on blends of poly(vinyl alcohol) (PVA) with different weight percentage (wt %) of glycerol has been studied. Solid‐state PVA/Glycerol polymer membranes were prepared by a solution casting method. The films were studied for thermal characteristics by differential scanning calorimetry (DSC) and thermogravimetric analysis and for the mechanical properties including hardness and modulus by nanoindentation method. The dispersion of glycerol within the polymer matrix was examined using scanning electron microscopy. Fourier transform infrared spectroscopy was used to confirm the formation of hydrogen bonding between the plasticizer and PVA in their blends and also to provide information on compatibility and physical interactions between the glycerol and PVA. It was found that the thermal properties particularly the melting point (T_m) for PVA blends exhibit a reduced value proportional to the glycerol content. The hardness and elastic modulus were also found to decrease with an increase in plasticizer content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation,Characterization, and Evaluation of Poly(p-azidoaniline) as Thermal Stabilizer for Low Density Polyethylene Films

A series of electrically conducting low density polyethylene/poly(p-azidoaniline) blends containing different loadings of poly(p-azidoaniline) was prepared. The resistance of these blends to accelerated thermal oxidation at 90°C for different time intervals was investigated. The thermal degradation mechanism was determined by attenuated total reflection-Fourier transform infrared technique. The values of melting temperature (T_m), enthalpy of fusion (ΔH_m), and degree of crystallinity showed significant increase upon poly(p-azidoaniline) addition. X-ray diffraction patterns also confirmed increase in degree of crystallinity upon blend formation. Furthermore, scanning electron microscopy observations showed efficient thermal stabilization of low density polyethylene/poly(p-azidoaniline) blends. The mechanical properties showed significant role of poly(p-azidoaniline) as thermal stabilizer for low density polyethylene.     

Effects of epoxy content on dynamic mechanical behaviour of PEI‐toughened dicyanate–novolac epoxy blends

By varying the cyanate/epoxy ratio, three polyetherimide(PEI)‐modified bisphenol A dicyanate–novolac epoxy resin blends with different epoxy contents were prepared. The effects of epoxy content on the dynamic mechanical behaviour of those blends were investigated by dynamic mechanical thermal analysis. The results showed that the glass transition temperature of the cyanate–epoxy network (T_g1) in the modified blend decreases with epoxy content. When the epoxy content increases, both the width of the glass transition of the cyanate–epoxy network and its peak density are depressed substantially. Although the tangent delta peak value of PEI is basically independent of epoxy content, the T_g of PEI (T_g2) decreases with epoxy content. T_g1 is independent of the PEI loading. When T_g1 is lower than T_g2, however, the T_g1 in the blend with revised phase structure is substantially lower than other blends. Copyright © 2004 Society of Chemical Industry     

Improvement of the processability of poly(ether ketone ketone) by the addition of a thermotropic liquid crystalline polymer

The addition of a thermotropic liquid crystalline, wholly aromatic copolyester, TLCP, improved the melt processability of poly(ether ketone ketone), PEKK. The tensile strength and modulus of the blends also improved with increasing TLCP, but the elongation at break decreased significantly. The blends were phase‐separated, but the polymers were partially miscible as evident from shifts of the glass transition temperature (T_g) of each component towards that of the other component in the blend. Similarly, the melting points (T_m) of both components were depressed by blending. When the crystallization temperature was above T_m of the TLCP, the PEKK crystallization rate in the blend was slower than for the pure material, while crystallization was faster when the temperature was below T_m of the TLCP. Polym. Eng. Sci. 44:541–547, 2004. © 2004 Society of Plastics Engineers.     

Crystallization,melting behavior,and morphology of BPP/HDPE blend

The crystallization, melting behavior, and morphology of a low ethylene content block propylene–ethylene copolymer (BPP) and a high-density polyethylene (HDPE) blend were studied. It was found that the existence of ethylene–propylene rubber (EPR) in BPP has more influence on the crystallization of HDPE than on that of PP. This leads to the decreasing of the melting temperature of the HDPE component in the blends. It is suggested that the EPR component in BPP shifted to the HDPE component during the blending process. The crystallinity of the HDPE phase in the blends decreased with increasing BPP content. The morphology of these blends was studied by polarized light microscopy (PLM) and SEM. For a BPP-rich blend, it was observed that the HDPE phase formed particles dispersed in the PP matrix. The amorphous EPR chains may penetrate into HDPE particles to form a transition layer. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 2469–2475, 1998     

Study of the miscibility and crystallization behavior of poly(ethylene oxide)/poly(vinyl alcohol) blends

The miscibility and crystallization behavior of poly(ethylene oxide)/poly(vinyl alcohol) (PEO/PVA) blends were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and polarizing optical microscopy. Because the glass‐transition temperature of PVA was near the melting point of PEO crystalline, an uncommon DSC procedure was used to determine the glass‐transition temperature of the PVA‐rich phase. From the DSC and DMA results, two glass‐transition temperatures, which corresponded to the PEO‐rich phase and the PVA‐rich phase, were observed. It was an important criterion to indicate that a blend was immiscible. It was also found that the preparation method of samples influenced the morphology and crystallization behaviors of PEO/PVA blends. The domain size of the disperse phase (PVA‐rich) for the solution‐cast blends was much larger than that for the coprecipitated blends. The crystallinity, spherulitic morphology, and isothermal crystallization behavior of PEO in the solution‐cast blends were similar to those of the neat PEO. On the contrary, these properties in the coprecipitated blends were different from those of the neat PEO. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1562–1568, 2004     

Miscibility and phase structure of binary blends of poly(L‐lactide) and poly(vinyl alcohol)

Blend films of poly(L ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA) were obtained by evaporation of hexafluoroisopropanol solutions of both components. The component interaction, crystallization behavior, and miscibility of these blends were studied by solid‐state NMR and other conventional methods, such as Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). The existence of two series of isolated and constant glass‐transition temperatures (T_g's) independent of the blend composition indicates that PLLA and PVA are immiscible in the amorphous region. However, the DSC data still demonstrates that some degree of compatibility related to blend composition exists in both PLLA/atactic‐PVA (a‐PVA) and PLLA/syndiotactic‐PVA (s‐PVA) blend systems. Furthermore, the formation of interpolymer hydrogen bonding in the amorphous region, which is regarded as the driving force leading to some degree of component compatibility in these immiscible systems, is confirmed by FTIR and further analyzed by ¹³C solid‐state NMR analyses, especially for the blends with low PLLA contents. Although the crystallization kinetics of one component (especially PVA) were affected by another component, WAXD measurement shows that these blends still possess two isolated crystalline PLLA and PVA phases other than the so‐called cocrystalline phase. ¹³C solid‐state NMR analysis excludes the interpolymer hydrogen bonding in the crystalline region. The mechanical properties (tensile strength and elongation at break) of blend films are consistent with the immiscible but somewhat compatible nature of these blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 762–772, 2001     

Compatibility studies of sulfonated poly(ether ether ketone)–poly(ether imide)–polycarbonate ternary blends

Binary blends of the sulfonated poly(ether ether ketone) (SPEEK)–poly(ether imide) (PEI) and SPEEK–polycarbonate (PC), and ternary blends of the SPEEK–PEI–PC, were investigated by differential scanning calorimetry. SPEEK was obtained by sulfonation of poly(ether ether ketone) using 95% sulfuric acid. From the thermal analysis of the SPEEK–PEI blends, single glass transition temperature (T_g) was observed at all the blend composition. For the SPEEK–PC blends, double T_gs were observed. From the results of thermal analysis, it is suggested that the SPEEK–PEI blends are miscible and the SPEEK–PC blends are immiscible. Polymer–polymer interaction parameter (χ₁₂) of the SPEEK–PEI blends was calculated from the modified Lu and Weiss equation, and found to range from −0.011 to −0.825 with the blend composition. For the SPEEK–PC blends, the χ₁₂ values were calculated from the modified Flory–Huggins equation, and found to range from 0.191 to 0.272 with the blend composition. For the SPEEK–PEI–PC ternary blends, phase separation regions that showed two T_gs were found to be consistent with the spinodal curves calculated from the χ₁₂ values of the three binary blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2488–2494, 2000