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1.
The morphology changes and surface thermodynamics of blends of amylopectin (AP)–poly(L ‐lactide) (PLA) were investigated over a wide range of temperatures and compositions using the inverse gas chromatography method. Twenty‐five solutes were selected such as alkanes, acetates, oxy, halogenated, and six‐member ring families. They provided a variety of specific interactions with the blends' surface. The morphology showed two regions, some others showed a de‐polymerization above 130°C. These zones enabled the estimation of Tg and Tm of AP, PLA, and the blends. Blending AP with PLA caused a decrease in AP's Tg value due to the reduction of the degree of crystallinity of the blend. Exothermic values of χ23 were obtained indicating the compatibility of AP and PLA at all temperatures and weight fractions of AP–PLA. The miscibility was favored at 75%AP, only 25%AP–75%PLA composition influenced the degree of crystallinity. The dispersive component of the surface energy of the blends ranged from 16.09 mJ/m2 for the pure AP as high as 58.36 mJ/m2 at 110°C when AP was mixed with PLA in a 50–50% ratio. The surface energy was at its highest value when the composition was 75% of AP, in good agreement with χ23 values. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

2.
The crystallization kinetics of pure poly(ε‐caprolactone) (PCL) and its blends with bisphenol‐A tetramethyl polycarbonate (TMPC) was investigated isothermally as a function of composition and crystallization temperature (Tc) using differential scanning calorimetric (DSC) and polarized optical microscope techniques. Only a single glass‐transition temperature, Tg, was determined for each mixture indicating that this binary blend is miscible over the entire range of composition. The composition dependence of the Tg for this blend was well described by Gordon–Taylor equation with k = 1.8 (higher than unity) indicating strong intermolecular interaction between the two polymer components. The presence of a high Tg amorphous component (TMPC) had a strong influence on the crystallization kinetics of PCL in the blends. A substantial decrease in the crystallization kinetics was observed as the concentration of TMPC rose in the blends. The crystallization half‐time t0.5 increased monotonically with the crystallization temperature for all composition. At any crystallization temperature (Tc) the t0.5 of the blends are longer than the corresponding value for pure PCL. This behavior was attributed to the favorable thermodynamics interaction between PCL and TMPC which in turn led to a depression in the equilibrium melting point along with a simultaneous retardation in the crystallization of PC. The isothermal crystallization kinetics was analyzed on the basis of the Avrami equation. Linear behavior was held true for the augmentation of the radii of spherulites with time for all mixtures, regardless of the blend composition. However, the spherulites growth rate decreased exponentially with increasing the concentration of TMPC in the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3307–3315, 2007  相似文献   

3.
Optically pure polylactides, poly(L ‐lactide) (PLLA) and poly(D ‐lactide) (PDLA), were blended across the range of compositions with poly(ε‐caprolactone) (PCL) to study their crystallization, morphology, and mechanical behavior. Differential scanning calorimetry and dynamic mechanical analysis (DMA) of the PLA/PCL blends showed two Tgs at positions close to the pure components revealing phase separation. However, a shift in the tan δ peak position by DMA from 64 to 57°C suggests a partial solubility of PCL in the PLA‐rich phase. Scanning electron microscopy reveals phase separation and a transition in the phase morphology from spherical to interconnected domains as the equimolar blend approaches from the outermost compositions. The spherulitic growth of both PLA and PCL in the blends was followed by polarized optical microscopy at 140 and 37°C. From tensile tests at speed of 50 mm/min Young's modulus values between 5.2 and 0.4 GPa, strength values between 56 and 12 MPa, and strain at break values between 1 and 400% were obtained varying the blend composition. The viscoelastic properties (E′ and tan δ) obtained at frequency of 1 Hz by DMA are discussed and are found consistent with composition, phase separation, and crystallization behavior of the blends. POLYM. ENG. SCI., 46:1299–1308, 2006. © 2006 Society of Plastics Engineers  相似文献   

4.
Starch‐g‐polycaprolactone copolymers were prepared by two‐step reactions. The diisocyanate‐terminated polycaprolactone (NCO–PCL) was prepared by introducing NCO on both hydroxyl ends of PCL using diisocyanates (DI) at a molar ratio between PCL and DI of 2:3. Then, the NCO–PCL was grafted onto corn starch at a weight ratio between starch and NCO–PCL of 2:1. The chemical structure of NCO–PCL and the starch‐g‐PCL copolymers were confirmed by using FTIR and 13C‐NMR spectrometers, and then the thermal characteristics of the copolymers were investigated by DSC and TGA. By introducing NCO to PCL (Mn : 1250), the melting temperature (Tm ) was reduced from 58 to 45°C. In addition, by grafting the NCO–PCL (35–38%) prepared with 2,4‐tolylene diisocyanate (TDI) or 4,4‐diphenylmethane diisocyanate (MDI) onto starch, the glass transition temperatures (Tg 's) of the copolymers were both 238°C. With hexamethylene diisocyanate (HDI), however, Tg was found to be 195°C. The initial thermal degradation temperature of the starch‐g‐PCL copolymers were higher than that of unreacted starch (320 versus 290°C) when MDI was used, whereas the copolymers prepared with TDI or HDI underwent little change. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 986–993, 2000  相似文献   

5.
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 (Tg) and melting temperature (Tm) in PC and the blends were measured by DSC. The Tg of PC and PC in the PC/ABS and PC/LDPE blends decreased after aging. The Tg 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  相似文献   

6.
The poly(ε‐caprolactone) (PCL)/starch blends were prepared with a coextruder by using the starch grafted PLLA copolymer (St‐g‐PLLA) as compatibilizers. The thermal, mechanical, thermo‐mechanical, and morphological characterizations were performed to show the better performance of these blends compared with the virgin PCL/starch blend without the compatibilizer. Interfacial adhesion between PCL matrix and starch dispersion phases dominated by the compatibilizing effects of the St‐g‐PLLA copolymers was significantly improved. Mechanical and other physical properties were correlated with the compatibilizing effect of the St‐g‐PLLA copolymer. With the addition of starch acted as rigid filler, the Young's modulus of the PCL/starch blends with or without compatibilizer all increased, and the strength and elongation were decreased compared with pure PCL. Whereas when St‐g‐PLLA added into the blend, starch and PCL, the properties of the blends were improved markedly. The 50/50 composite of PCL/starch compatibilized by 10% St‐g‐PLLA gave a tensile strength of 16.6 MPa and Young's modulus of 996 MPa, respectively, vs. 8.0 MPa and 597 MPa, respectively, for the simple 50/50 blend of PCL/starch. At the same time, the storage modulus of compatibilized blends improved to 2940 MPa. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

7.
Blends of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate‐co‐4,4′‐ bibenzoate) (PETBB) are prepared by coextrusion. Analysis by 13C‐NMR spectroscopy shows that little transesterification occurs during the blending process. Additional heat treatment of the blend leads to more transesterification and a corresponding increase in the degree of randomness, R. Analysis by differential scanning calorimetry shows that the as‐extruded blend is semicrystalline, unlike PETBB15, a random copolymer with the same composition as the non‐ random blend. Additional heat treatment of the blend leads to a decrease in the melting point, Tm, and an increase in glass transition temperature, Tg. The Tm and Tg of the blend reach minimum and maximum values, respectively, after 15 min at 270°C, at which point the blend has not been fully randomized. The blend has a lower crystallization rate than PET and PETBB55 (a copolymer containing 55 mol % bibenzoate). The PET/PETBB55 (70/30 w/w) blend shows a secondary endothermic peak at 15°C above an isothermal crystallization temperature. The secondary peak was confirmed to be the melting of small and/or imperfect crystals resulting from secondary crystallization. The blend exhibits the crystal structure of PET. Tensile properties of the fibers prepared from the blend are comparable to those of PET fiber, whereas PETBB55 fibers display higher performance. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1793–1803, 2004  相似文献   

8.
Polymer blends of polybenzoxazine (PBA‐a) and polycaprolactone (PCL) of different molecular weights (Mn = 10,000, 45,000, and 80,000 Da) were prepared at various PBA‐a/PCL mass ratios and their properties were characterized. The results from dynamic mechanical analyzer (DMA) revealed two glass transition temperatures implying phase separation of the two polymers in the studied range of the PCL contents. Moreover, a synergistic behavior in glass transition temperature (Tg) was evidently observed in these blends with a maximum Tg value of 281°C compared with the Tg value of 169°C of the PBA‐a and about ?50°C of the PCL used. The blends with higher Mn of PCL tended to provide greater Tg value than those with lower Mn of PCL. The modulus and hardness values of PBA‐a were decreased while the elongation at break and area under the stress?strain curve were increased with an increase of the content and Mn of PCL, suggesting an enhancement of toughness of the PBA‐a. Scanning electron micrographs (SEM) of the sample fracture surface are also used to confirm the improvement in toughness of the blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41915.  相似文献   

9.
The change of the glass transition temperatures (Tg) in the blend of poly(L ‐lactic acid) (PLLA) and the copolymers of poly(D,L ‐lactic acid) and poly(glycolic acid) (PDLLA‐PGA) with different D,L ‐lactic acid and glycolic acid composition ratio (50 : 50, 65 : 35, and 75 : 25) was studied by DSC. Dynamic mechanical measurement and tensile testing were performed at various temperatures around Tg of the blend. In the blend of PLLA and PDLLA‐PGA50 (composition ratio of PDLLA and PGA 50 : 50), Tg decreased from that of PLLA (about 58°C) to that of PDLLA‐PGA50 (about 30°C). A single step decrease was observed in the DSC curve around Tg between the weight fraction of PLLA (W(PLLA)) 1.0 and 0.7 (about 52°C) but two‐step changes in the curve are observed between W(PLLA) = 0.6 and 0.3. The Tg change between that of PLLA and that of PDLLA‐PGA and the appearance of two Tgs suggest the existence of PLLA rich amorphous region and PDLLA‐PGA copolymer rich amorphous region in the blend. A single step decrease of E′ occurs at around Tg of the pure PLLA but the two‐step decrease was observed at W(PLLA) = 0.6 and 0.4, supporting the existence of the PLLA rich region and PDLLA‐PGA rich region. Tensile testing for various blends at elevated temperature showed that the extension without yielding occurred above Tg of the blend. Partial miscibility is suggested for PLLA and PDLLA‐PGA copolymer blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2164–2173, 2004  相似文献   

10.
The miscibility, melting and crystallization behaviour of poly[(R)‐3‐hydroxybutyrate], PHB, and oligo[(R,S)‐3‐hydroxybutyrate]‐diol, oligo‐HB, blends have been investigated by differential scanning calorimetry: thermograms of blends containing up to 60 wt% oligo‐HB showed behaviour characteristic of single‐phase amorphous glasses with a composition dependent glass transition, Tg, and a depression in the equilibrium melting temperature of PHB. The negative value of the interaction parameter, determined from the equilibrium melting depression, confirms miscibility between blend components. In parallel studies, glass transition relaxations of different melt‐crystallized polymer blends containing 0–20 wt% oligo‐HB were dielectrically investigated between ?70 °C and 120 °C in the 100 Hz to 50 kHz range. The results revealed the existence of a single α‐relaxation process for blends, indicating the miscibility between amorphous fractions of PHB and oligo‐HB. © 2002 Society of Chemical Industry  相似文献   

11.
In polymer blends, the composition and microcrystalline structure of the blend near surfaces can be markedly different from the bulk properties. In this study, the enzymatic degradation of poly(ε‐caprolactone) (PCL) and its blends with poly(styrene‐co‐acrylonitrile) (SAN) was conducted in a phosphate buffer solution containing Pseudomonas lipase, and the degradation behavior was correlated with the surface properties and crystalline microstructure of the blends. The enzymatic degradation preferentially took place at the amorphous part of PCL film. The melt‐quenched PCL film with low crystallinity and small lamellar thickness showed a higher degradation rate compared with isothermally crystallized (at 36, 40, and 44°C) PCL films. Also, there was a vast difference in the enzymatic degradation behavior of pure PCL and PCL/SAN blends. The pure PCL showed 100% weight loss in a very short time (i.e., 72 h), whereas the PCL/SAN blend containing just 1% SAN showed ~50% weight loss and the degradation ceased, and the blend containing 40% SAN showed almost no weight loss. These results suggest that as degradation proceeds, the nondegradable SAN content increases at the surface of PCL/SAN films and prevents the lipase from attacking the biodegradable PCL chains. This phenomenon was observed even for a very high PCL content in the blend samples. In the blend with low PCL content, the inaccessibility of the amorphous interphase with high SAN content prevented the attack of lipase on the lamellae of PCL. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 868–879, 2002  相似文献   

12.
A thermal analysis study of blends of semicrystalline poly(vinyl alcohol) (PVA) with a pharmaceutical substance, buflomedil pyridoxal phosphate (BPP) is presented. Temperature‐modulated DSC (TMDSC) was used to determine the Tg as well as the crystallinity of blends with various polymer to drug ratios, for different annealing procedures. Positive deviations from a simple expression for the composition dependence of the glass transition of the blend were found. This result, together with the increased thermal stability of PVA–BPP blends, evidenced by TGA analysis, indicates the existence of specific interactions between the polar groups of the two components. The incorporation of dispersed BPP in the PVA matrix results in a composition‐dependent lowering of the polymer's Tm and degree of crystallinity. In addition, we found that, while melting of pure PVA is predominantly reversing, its melting in the blends acquires an increasingly higher nonreversing component with increasing BPP content in the blend. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1151–1156, 2004  相似文献   

13.
Transesterification has been investigated in poly(ε‐caprolactone) (PCL)–epoxy blends. In the hot melt process, the hydroxyl on diglycidyl ether of bisphenol‐A (DGEBA) monomers is too low to give a noticeable transesterification reaction. In the postcure process, model reactions reveal that the hydroxyls from a ring‐opening reaction are able to react with the esters of PCL. In the meantime, the PCL molecular weight decrease and its distribution becomes broader. Nuclear magnetic resonance spectra reveal that fraction of the tertiary hydroxyls converts to secondary hydroxyls. In the cured DGEBA–3,3′‐dimethylmethylene‐di(cyclohexylamine)–PCL blend, a homogeneous morphology is achieved. PCL segments are grafted onto the epoxy network after postcuring and result in the lower Tg observed in the differential scanning calorimetry thermogram. A higher transesterification extent also results in broader transition peaks by dynamic mechanical analysis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 75–82, 1999  相似文献   

14.
Many biopolymers and synthetic polymers composites were developed by different researchers for environmental protection and for cost reduction. One of these composites is polycaprolactone (PCL) and vital wheat gluten or wheat flour composites were prepared and compatibilized with polymeric diphenylmethane diisocyanate (pMDI) by blending and compression‐molding. PCL/pMDI blend exhibited glass transition (Tg) at ?67°C (0.20 J/g/°C) and vital gluten at 63°C (0.45 J/g/°C), whereas no Tg was recorded for wheat flour. Although Tg was unmistakable for either PCL or gluten, all composite exhibited one Tg, which is strong indication of interaction between PCL and the fillers. Several samples amongst the blended or compression‐molded composites exhibited no Tg signifying another confirmation of interaction. The ΔH of the endothermic (melting) and the exothermic (crystallization) for PCL was decreased as the percentage of gluten or flour increased, whereas the overall ΔH was higher for all composites compared to the theoretical value. The presence of pMDI appeared to strengthen the mechanical properties of the composites by mostly interacting with the filler (gluten or flour) and not as much with PCL. The FTIR analysis ruled out covalent interaction between PCL, pMDI, or the fillers but suggested the occurrence of physical interactions. Based on the data presented here and the data published earlier, the presence of pMDI did not change the nature of interaction between PCL and gluten, but it improved the mechanical properties of the composite. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

15.
Dynamic viscoelastic properties for miscible blends of poly(?‐caprolactone) (PCL) and poly(styrene‐co‐acrylonitrile) (SAN) were measured. It was found that the time–temperature superposition principle is applicable over the entire temperature range studied for the blends. The temperature dependency of the shift factors aT can be expressed by the Williams–Landel–Ferry equation: log aT = ?8.86(T ? Ts)/(101.6 + T ? Ts). The compositional dependency of Ts represents the Gordon–Taylor equation. The zero‐shear viscosities are found to increase concavely upward with an increase in weight fraction of SAN at constant temperature, but concavely downward at constant free volume fraction. It is concluded that the relaxation behavior of the PCL/SAN blends is similar to that of a blend consisting of homologous polymers. It is emphasized that the viscoelastic functions of the miscible blends should be compared in the iso‐free volume state. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2037–2041, 2001  相似文献   

16.
We have investigated the enhancement in miscibility, upon addition of bisphenol A (BPA) of immiscible binary biodegradable blends of poly(ε‐caprolactone) (PCL) and poly(L ‐lactide) (PLLA). That BPA is miscible with both PCL and PLLA was proven by the single value of Tg observed by differential scanning calorimetry (DSC) analyses over the entire range of compositions. At various compositions and temperatures, Fourier transform infrared spectroscopy confirmed that intermolecular hydrogen bonding existed between the hydroxyl group of BPA and the carbonyl groups of PCL and PLLA. The addition of BPA enhances the miscibility of the immiscible PCL/PLLA binary blend and transforms it into a miscible blend at room temperature when a sufficient quantity of the BPA is present. In addition, optical microscopy (OM) measurements of the phase morphologies of ternary BPA/PCL/PLLA blends at different temperatures indicated an upper critical solution temperature (UCST) phase diagram, since the ΔK effect became smaller at higher temperature (200°C) than at room temperature. An analysis of infrared spectra recorded at different temperatures correlated well with the OM analyses. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1146–1161, 2006  相似文献   

17.
Atactic poly(methylmethacrylate), aPMMA, was blended with poly(3‐D(−)hydroxybutyrate), PHB, up to a maximum composition of 25% of polyester, at 190°C in a Brabender‐like apparatus. The resulting blends quenched from the melt to room temperature were completely amorphous, and exhibited a single glass transition using DSC and DMTA, indicating miscibility of the components for this time–temperature history. Tensile experiments showed that at room temperature the 10/90 and 20/80 PHB/aPMMA blends exhibited higher values of strain at break, and slight decreases of the modulus and stress at break compared to neat aPMMA. The tensile energy at break was almost twice that of neat aPMMA. Tensile tests were also performed at 80°C, at which point the 25/75 and 20/80 PHB/aPMMA blends are above Tg, while the 10/90 and neat aPMMA are below Tg. The stress–strain curves obtained were functions of the physical state of the amorphous phase, and also depended on the difference between the test temperatures and Tg. In particular, comparing the neat aPMMA and the blends, decreases of the modulus and stress at break and a respectable increase in the strain at break were observed in the latter. Finally, the results were commented considering the thermal degradation of PHB in the melt during the blend preparation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 746–753, 2000  相似文献   

18.
In this article, polyamide 6 (PA6), maleic anhydride grafted ethylene‐propylene‐diene monomer (EPDM‐g‐MA), high‐density polyethylene (HDPE) were simultaneously added into an internal mixer to melt‐mixing for different periods. The relationship between morphology and rheological behaviors, crystallization, mechanical properties of PA6/EPDM‐g‐MA/HDPE blends were studied. The phase morphology observation revealed that PA6/EPDM‐g‐MA/HDPE (70/15/15 wt %) blend is constituted from PA6 matrix in which is dispersed core‐shell droplets of HDPE core encapsulated by EPDM‐g‐MA phase and indicated that the mixing time played a crucial role on the evolution of the core‐shell morphology. Rheological measurement manifested that the complex viscosity and storage modulus of ternary blends were notable higher than the pure polymer blends and binary blends which ascribed different phase morphology. Moreover, the maximum notched impact strength of PA6/EPDM‐g‐MA/HDPE blend was 80.7 KJ/m2 and this value was 10–11 times higher than that of pure PA6. Particularly, differential scanning calorimetry results indicated that the bulk crystallization temperature of HDPE (114.6°C) was partly weakened and a new crystallization peak appeared at a lower temperature of around 102.2°C as a result of co‐crystal of HDPE and EPDM‐g‐MA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

19.
The effect of poly(caprolactone) (PCL) on the positive temperature coefficient of resistivity characteristics of polycarbonate (PC)/nickel (Ni)‐coated graphite (40 wt%) composites was investigated. The PTC trip temperature of PC/Ni‐coated graphite composites appeared at 155°C. On addition of PCL to PC/Ni‐coated graphite composites, the PTC trip temperature reduced to 125°C, well below the Tg of the PC (∼147°C), as well as the PC/PCL (∼136°C) blend. It is noteworthy that the observed PTC effect for PC/PCL (8 wt%)/Ni‐coated graphite (40 wt%) composites is highly reproducible during many heating cycles. The coefficient of thermal expansion (CTE) of PC was increased in presence of PCL. Thus, the mismatch in CTE of the PC and Ni‐coated graphite at a temperature well below the Tg of PC was enough to disrupt the continuous network structure that increased the resistivity of the composites. Storage modulus of PC/PCL/Ni‐coated graphite composites was higher than PC/Ni‐coated graphite composites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers  相似文献   

20.
Di(isononyl) cyclohexane‐1,2‐dicarboxylate (DINCH) was used as a new plasticizer for poly(lactic acid) (PLA), and the effects of DINCH and tributyl citrate ester (TBC) on the morphology, mechanical and thermal properties, and durability of PLA were compared. DINCH has limited compatibility with PLA, leading to PLA/DINCH blends with phase separation in which DINCH forms spherical dispersed phase. TBC is compatible with PLA and evenly distributed in PLA. Plasticized PLA with 10 and 20 phr DINCH have a constant glass transition temperature (Tg) of 50°C and are stiff materials with high elongation at break and impact strength. TBC could significantly decrease the Tg and increase the crystallinity of PLA, and PLA/TBC (100/20) blend is a soft material with a Tg of 24°C. The durability of plasticized PLA was characterized by weight loss measurement under water immersion, mechanical properties, and thermal analysis. The results reveal that PLA/DINCH blends have better water resistance and aging resistance properties than PLA/TBC blends, which is attributed to the relatively high hydrophobicity of DINCH and high Tg of PLA/DINCH blends. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers  相似文献   

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