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1.
Bio‐degradable polymer blends of polylactic acid/thermoplastic starch (PLA/TPS) were prepared via direct melt blending varying order of mixing of ingredients fed into the extruder. The effect of interface interactions between PLA and TPS in the presence of maleic anhydride (MA) compatibilizer on the microstructure and mechanical properties was then investigated. The prepared PLA/TPS blends were characterized by scanning electron microscopy, differential scanning calorimetry (DSC), tensile, and rheological measurements. Morphology of PLA/TPS shows that the introduction of MA into the polymer matrix increases the presence of TPS at the interface region. DSC results revealed the reduction of glass transition temperature of PLA with contributions from both TPS and MA. The crystallization temperature was decreased by the addition of MA leading to reduction of overall crystallization of PLA/TPS blend. The mechanical measurements show that increasing MA content up to 2 wt % enhances the modulus of PLA/TPS more than 45% compared to the corresponding blends free of MA compatibilizer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44734.  相似文献   

2.
In this article, the spherulitic growth rate of neat and plasticized poly(lactic acid) (PLA) with triphenyl phosphate (TPP) was measured and analyzed in the temperature range of 104–142°C by polarizing optical microscopy. Neat PLA had the maximum value of 0.28 μm/s at 132°C, whereas plasticized PLA had higher value than that of neat PLA, but the temperature corresponding to the maximum value was shifted toward lower one with increasing TPP content. The isothermal crystallization kinetics of neat and plasticized PLA was also analyzed by differential scanning calorimetry and described by the Avrami equation. The results showed for neat PLA and its blends with various TPP contents, the average value of Avrami exponents n were close to around 2.5 at two crystallization temperatures of 113 and 128°C, the crystallization rate constant k was decreased, and the half‐life crystallization time t1/2 was increased with TPP content. For neat PLA and its blend with 15 wt % TPP content, the average value of n was 2.0 and 2.3, respectively, the value of k was decreased, and the value of t1/2 was increased with crystallization temperature (Tc). Further investigation into crystallization activation energy ΔEa of neat PLA and its blend with 15 wt % TPP showed that ΔEa of plasticized PLA was increased compared to neat PLA. It was verified by wide‐angle X‐ray diffraction that neat PLA and its blends containing various TPP contents crystallized isothermally in the temperature range of 113–128°C all form the α‐form crystal. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

3.
The morphology and miscibility of commercial poly(lactide) (PLA)/poly(β‐hydroxybutyrate) (PHB, from 5 to 20 wt %) blends prepared by melt extrusion method, were investigated using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) observations. The results show that for all the studied blend contents, PLA/PHB blends are immiscible. The effects of PHB and talc on the nonisothermal cold crystallization kinetics of PLA were examined using a differential scanning calorimetry (DSC) at different heating rates. PHB acted as a nucleating agent on PLA and the addition of talc to the blend yielded further improvement, since significant increase in the enthalpy peak was observed for samples containing 10 wt % PHB and talc (from 0.5 to 5 phr). The crystallization kinetics were then examined using the Avrami–Jeziorny and Liu–Mo approach. The simultaneous presence of PHB and talc induced a decrease of the crystallization half time. The evolution of activation energies determined with Kissinger's equation suggests that blending with PHB and incorporating talc promote nonisothermal cold crystallization of PLA. The synergistic nucleating effect of PHB and talc was also observed on isothermal crystallization of PLA from the melt. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

4.
Both poly(lactic acid) (PLA) and poly(butylene adipate‐co‐terephthalate) (PBAT) are fully biodegradable polyesters. The disadvantages of poor mechanical properties of PLA limit its wide application. Fully biodegradable polymer blends were prepared by blending PLA with PBAT. Crystallization behavior of neat and blended PLA was investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and wide angle X‐ray diffraction (WAXD). Experiment results indicated that in comparison with neat PLA, the degree of crystallinity of PLA in various blends all markedly was increased, and the crystallization mechanism almost did not change. The equilibrium melting point of PLA initially decreased with the increase of PBAT content and then increased when PBAT content in the blends was 60 wt % compared to neat PLA. In the case of the isothermal crystallization of neat PLA and its blends at the temperature range of 123–142°C, neat PLA and its blends exhibited bell shape curves for the growth rates, and the maximum crystallization rate of neat PLA and its blends all depended on crystallization temperature and their component. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

5.
This article provides a detailed investigation of crystallization behavior and morphology of polylactic acid (PLA) in the presence of a nucleating agent: potassium salt of 5‐dimethyl sulfoisothalate, an aromatic sulfonate derivative (Lak‐301). Isothermal crystallization kinetics of PLA melt mixed with Lak at concentrations of 0.25–1 wt % was investigated at a range of crystallization temperature, 140–150 °C. To gain further insight on the effect of Lak, nonisothermal differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), polarized optical microscope (POM), heat deflection temperature (HDT), and rheology were also performed. At 0.25 wt % Lak, crystallinity of PLA increased from 10% to 45%, and in 1 wt % Lak, maximum crystallinity of 50% was achieved. With 1 wt % Lak, crystallization half time reduced to 1.8 min from 61 min for neat PLA at 140 °C. The isothermal crystallization kinetics was analyzed using Avrami model. Values of the Avrami exponent for PLA with Lak were mainly in the range of 3 indicating a three dimensional crystal growth is favored. Crystallization rate was found to increase with increase in Lak content. Observation from POM confirmed that the presence of Lak in the PLA matrix significantly increased the nucleation density. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43673.  相似文献   

6.
To enhance the crystallization kinetics of poly(lactic acid) (PLA), fibrous sepiolite was explored for nucleating the crystallization of PLA. PLA/sepiolite nanocomposites were prepared via the melt‐extrusion method. The effect of sepiolite on the crystallization behavior, spherulite growth and crystal structure of PLA were investigated by means of differential scanning calorimetry (DSC), polarized optical microscope (POM), wide angle X‐ray diffraction (WAXD), Fourier transform infrared (FTIR), and scanning election microscope (SEM). On the basis of DSC and POM results, the overall crystallization kinetics of PLA/sepiolite nanocomposites were significantly enhanced leading to higher crystallinity and nucleation density, faster spherulite growth rate (G) and lower crystallization half‐time (t1/2) compared with the neat PLA. Under non‐isothermal conditions, the PLA blend comprising 1.0 wt% of sepiolite still revealed two crystallization peaks upon cooling at a rate of 35°C/min. Above phenomena strongly suggested that sepiolite was an effective nucleating agent for PLA. FTIR and WAXD analyses confirmed that the crystal structure of PLA matrix was the most common α‐form. SEM micrographics illustrated the fine three‐dimensional spherulite structures with the lath‐shape lamellae regularly arranged in radial directions. POLYM. ENG. SCI., 55:1104–1112, 2015. © 2014 Society of Plastics Engineers  相似文献   

7.
The isothermal crystallization kinetics and morphology of the poly(lactic acid) (PLA) blends containing three different sizes of both spherical and fibrous poly(butylene terephthalate) (PBT) domains have been comparatively investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The dynamic DSC measurement reveals that PBT domains significantly increase the degree of crystallinity of the PLA. Furthermore, the Avrami model is employed to evaluate the crystallization kinetics under isothermal conditions and it is found that PBT acts as nucleating agent, leading to a high overall crystallization rate constant k and shortened crystallization half time t1/2. Furthermore, the crystallization rate of PLA is promoted with the incorporation of PBT with a large specific surface area. The average Avrami index n of all samples lies within the range of 3.3 ? 4.0, suggesting that morphologies of PBT do not affect the nucleation mechanism; however, the depression of equilibrium melting temperature in the blends ascribes the reductions of perfectness and size of the PLA crystallites. Besides, the nucleation of PLA crystallites around PBT fibers is probably faster than those around PBT spheres because the PBT chains oriented at the fiber surface as a result of flow‐induced crystallization during melt stretching may serve as the primary nuclei for PLA chains to drastically crystallize at the fiber surface. POLYM. ENG. SCI., 56:258–268, 2016. © 2015 Society of Plastics Engineers  相似文献   

8.
The crystallization kinetics of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) (PET/PEN) blends were investigated by DSC as functions of crystallization temperature, blend composition, and PET and PEN source. Isothermal crystallization kinetics were evaluated in terms of the Avrami equation. The Avrami exponent (n) is different for PET, PEN, and the blends, indicating different crystallization mechanisms occurring in blends than those in pure PET and PEN. Activation energies of crystallization were calculated from the rate constants, using an Arrhenius‐type expression. Regime theory was used to elucidate the crystallization course of PET/PEN blends as well as that of unblended PET and PEN. The transition from regime II to regime III was clearly observed for each blend sample as the crystallization temperature was decreased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 23–37, 2001  相似文献   

9.
A batch processing method is used to fabricate foams comprising of a blend of poly(lactic acid) (PLA) and Novatein, a protein‐based thermoplastic. Various compositions of Novatein/PLA are prepared with and without a compatibilizer, PLA grafted with itaconic anhydride (PLA‐g‐IA). Pure Novatein cannot form a cellular structure at a foaming temperature of 80 °C, however, in a blend with 50 wt % of PLA, microcells form with smaller cell sizes (3.36 µm) and higher cell density (8.44 × 1021 cells cm?3) compared to pure PLA and blends with higher amounts of PLA. The incorporation of 50 wt % of semicrystalline Novatein stiffens the amorphous PLA phase, which restrains cell coalescence and cell collapse in the blends. At a foaming temperature of 140 °C, NTP30–PLA70 shows a unique interconnected porous morphology which can be attributed to the CO2‐induced plasticization effect. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45561.  相似文献   

10.
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   

11.
The influence of lignin (L) on the thermal properties and kinetics of crystallization of isotactic polypropylene (PP) is reported in this article. PP blends containing 5 and 15 wt % of L were prepared by mixing the components in a screw mixer. An increase of the thermal degradation temperature of the blends was observed as a function of L content. The crystallization and thermal behavior of the pure PP and of the PP/L blends were analyzed by differential scanning calorimetry (DSC). Isothermal crystallization kinetics were described by means of the Avrami equation, which suggests a three‐dimensional growth of crystalline units, developed by heterogeneous nucleation. The isothermal growth rate of PP spherulites was studied using a polarizing optical microscope. The enhancement of PP crystallization rate for the PP/L blends was observed and ascribed to the nucleating action of lignin particles. Non‐isothermal crystallization kinetics were applied, according to the results elaborated by Ziabicki and the method modified by Jeziorny. The kinetic crystallizability of the PP is not influenced by the L present in the blend. In the presence of L, PP can simultaneously crystallize in both the α and β crystalline forms, and the ratio between the α and β forms was determined by X‐ray diffraction analysis. Two melting peaks relative to the two crystalline form of PP were observed for the PP/L blends, for all isothermal crystallization temperatures investigated by means of DSC. The equilibrium melting temperature for α‐form of pure PP was obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1435–1442, 2004  相似文献   

12.
This study explores the plasticizing effect of coconut oil (CO) on PLA for evaluating its suitability for flexible packaging. Changes in morphological, mechanical, thermal, rheological, barrier and optical properties of melt compounded Poly(lactic acid)–Coconut oil (PLA–CO) blend were investigated by varying the mixing ratio. Water vapor permeability of blends decreased by 58% at 7 wt % plasticizer content. The tensile strength showed a decreasing trend with increasing plasticizer percentage while the % elongation showed an increasing trend. At 7 wt % plasticizer content tensile strength decreased from 60 to 41 MPa and % elongation increased from 12% to 54%. Molecular weight (Mn) and onset of degradation (Tonset), upon 1 wt % plasticizer addition showed a reduction of 6% and 0.6%, respectively, which were well within permissible limits required for polymer processing. The melt flow properties of the blends were slightly improved (~16%) upon 5 wt % addition of CO. Transparency of the PLA films was improved by addition of plasticizer. FTIR spectra of PLA‐CO sample confirmed the interaction between PLA and coconut oil via hydrogen bonding. At higher loading, coconut oil shows very limited compatibility with PLA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45390.  相似文献   

13.
The crystallization and transition temperatures of poly(ethylene terephthalate) (PET) in blends with polycarbonate (PC) is considered using thermal analysis. Additives typically used in commercial polyester blends, transesterification inhibitor and antioxidant, are found to enhance the crystallization rate of PET. Differential scanning calorimetry (DSC) reveals two glass transition temperatures in PET/PC blends, consistent with an immiscible blend. Optical microscopy observations are also consistent with an immiscible blend. Small shifts observed in the Tg of each component may be due to interactions between the phases. The degree of crystallinity of PET in PET/PC blends is significantly depressed for high PC contents. Also, in blends with PC content greater than 60 wt %, two distinct crystallization exotherms are observed in dynamic crystallization from the melt. The isothermal crystallization kinetics of PET, PET modified with blend additives, and PET in PET/PC blends have been evaluated using DSC and the data analyzed using the Avrami model. The crystallization of PET in these systems is found to deviate from the Avrami prediction in the later stages of crystallization. Isothermal crystallization data are found to superimpose when plotted as a function of time divided by crystallization half-time. A weighted series Avrami model is found to describe the crystallization of PET and PET/PC blends during all stages of crystallization. © 1996 John Wiley & Sons, Inc.  相似文献   

14.
New bio‐based diblock copolymers were synthesized from poly(lactic acid) (PLA) and natural rubber (NR). NR polymer chains were modified to obtain hydroxyl telechelic natural rubber oligomers (HTNR). Condensation polymerization between PLA and HTNR was performed at 110°C during 24 or 48 h. The molecular weight of PLA and HTNR and the molar ratio PLA : HTNR were varied. The new ester linkage in the diblock copolymers was determined by 1H‐NMR. The molecular weight of the diblock copolymers determined from SEC agreed with that expected from calculation. The thermal behavior and degradation temperature were determined by DSC and TGA, respectively. The diblock copolymers were used as a toughening agent of PLA and as a compatibilizer of the PLA/NR blend. PLA blended with the diblock copolymer showed higher impact strength, which was comparable to the one of a PLA/NR blend. The former blend showed smaller dispersed particles as showed by SEM images, indicating the increase in miscibility in the blend due to the PLA block. The compatibilization was effective in the blends containing ~10 wt % of rubber. At a higher rubber content (>10 wt %), coalescence of the NR and diblock copolymer was responsible of the larger rubber diameter in the blends, which causes a decrease of the impact strength. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41426.  相似文献   

15.
The melting, crystallization behaviors, and nonisothermal crystallization kinetics of the ternary blends composed of poly(ethylene terephthalate), poly(trimethylene terephthalate) (PTT) and poly(buthylene terephthalate) (PBT) were studied with differential scanning calorimeter (DSC). PBT content in all ternary blends was settled invariably to be one‐third, which improved the melt‐crystallization temperature of the ternary blends. All of the blend compositions in amorphous state were miscible as evidenced by a single, composition‐dependent glass transition temperature (Tg) observed in DSC curves. DSC melting thermograms of different blends showed different multiple melting and crystallization peaks because of their various polymer contents. During melt‐crystallization process, three components in blends crystallized simultaneously to form mixed crystals or separated crystals depending upon their content ratio. The Avrami equation modified by Jeziorny and the Ozawa theory were employed to describe the nonisothermal crystallization process of two selected ternary blends. The results spoke that the Avrami equation was successful in describing the nonisothermal crystallization process of the ternary blends. The values of the t1/2 and the parameters Zc showed that the crystallization rate of the ternary blends with more poly(ethylene terephthalate) content was faster than that with the lesser one at a given cooling rate. The crystal morphology of the five ternary blends investigated by polarized optical microscopy (POM) showed different size and distortional Maltese crosses or light spots when the PTT or poly(ethylene terephthalate) component varied, suggesting that the more the PTT content, the larger crystallites formed in ternary blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

16.
Miscibility, isothermal melt crystallization kinetics, spherulitic morphology and growth rates, and crystal structure of completely biodegradable poly(ε‐caprolactone) (PCL)/tannic acid (TA) blends were studied by differential scanning calorimetry, polarized optical microscopy, and wide angle X‐ray diffraction in detail in this work. PCL and TA are miscible as evidenced by the single composition dependent glass transition temperature over the whole compositions range and the depression of equilibrium melting point of PCL in the PCL/TA blends. Isothermal melt crystallization kinetics of neat PCL and an 80/20 PCL/TA blend was investigated and analyzed by the Avrami equation. The overall crystallization rates of PCL decrease with increasing crystallization temperature for both neat PCL and the PCL/TA blend; moreover, the overall crystallization rate of PCL is slower in the PCL/TA blend than in neat PCL at a given crystallization temperature. However, the crystallization mechanism of PCL does not change despite crystallization temperature and the addition of TA. The spherulitic growth rates of PCL also decrease with increasing crystallization temperature for both neat PCL and the PCL/TA blend; moreover, blending with TA reduces the spherulitic growth rate of PCL in the PCL/TA blend. It is also found that the crystal structure of PCL is not modified in the PCL/TA blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

17.
Polylactide/polyethylene blends (PLA/PE) and their nanocomposites were prepared via the melt blending process. The effects of organoclay, compatibilizer (PE‐g‐MA), and PE content on morphology, linear viscoelastic properties of the melt and cold crystallization of the samples have been studied. The Palierne model is applied to predict the rheological behavior of unfilled blends. It implies that there is a quantitative agreement between model and experimental data for low PE content blend. From WAXD and the rheological behavior, it is shown that organoclay exhibits a higher extent of intercalation and dispersion in PLA/PE/organoclay nanocomposite than in PLA/organoclay nanocomposite. The DSC results present that the addition of compatibilizer into blend nanocomposite increases cold crystallization temperature of PLA by about 3°C. This can be explained by the role of compatibilizer in transfer of a part of organoclay from PLA matrix to droplets resulting in increase of PLA chain mobility and, therefore, slightly greater cold crystallization temperature. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41300.  相似文献   

18.
In this work, a novel polymer blend containing poly(lactic acid) (PLA) as a biocompatible and biodegradable thermoplastic and acrylic rubber (ACM) is prepared and the miscibility and phase structure of the blend and its nanocomposite (PLA/ACM/nanosilica) are investigated through theoretical and experimental methods. To predict the phase diagram of the blend, a compressible regular solution model was employed, in which an upper critical solution temperature was observed. The model predicted that PLA/ACM blends are immiscible over the whole composition range at temperatures below 260 °C. Performing scanning force microscopy on the blend showed phase separated structures for the blends containing different amounts of the PLA and ACM. This was in accordance with the results of dynamic mechanical analysis, which revealed two distinct glass transition temperatures for the studied blends. The effect of nanometer sized silica particle on morphology and rheological properties of these blends was also investigated. Scanning force microscopy results showed much reduction of droplet size in the blends containing 2 wt % nanosilica. This was attributed to the suppression effect of nanosilica on the droplets coalescences. Rheological measurements confirmed the interaction of both components with the silica nanofiller. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45499.  相似文献   

19.
The miscibility and crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (P(HB‐co‐HV))/poly(vinyl acetate) (PVAc) blends have been investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that P(HB‐co‐HV)/PVAc blends were miscible in the melt over the whole compositions. Thus the blend exhibited a single glass transition temperature (Tg), which increased with increasing PVAc composition. The spherulitic morphologies of P(HB‐co‐HV)/PVAc blends indicated that the PVAc was predominantly segregated into P(HB‐co‐HV) interlamellar or interfibrillar regions during P(HB‐co‐HV) crystallization because of the volume‐filled spherulites. As to the crystallization kinetics study, it was found that the overall crystallization and crystal growth rates decreased with the addition of PVAc. The kinetics retardation was primarily attributed to the reduction of chain mobility and dilution of P(HB‐co‐HV) upon mixing with higher Tg PVAc. The overall crystallization rate was predominantly governed by the spherulitic growth rate and promoted by the samples treated with the quenched state because of the higher nucleation density. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 980–988, 2006  相似文献   

20.
The morphology of nonisothermally crystallized poly(phenylene sulfide) (PPS) and its blend with poly (ether ether ketone) (PEEK) have been observed by polarized optical microscope (POM) equipped with a hot stage. The nonisothermal crystallization behavior of PPS and PEEK/PPS blend has also been investigated by differential scanning calorimetry (DSC). The maximum crystallization temperature for PEEK/PPS blend is about 15°C higher than that of neat PPS, and the crystallization rate, characterized by half crystallization time, of the PEEK/PPS blend is also higher than that of the neat PPS. These results indicate that the PEEK acts as an effective nucleation agent and greatly accelerates the crystallization rate of PPS. The Ozawa model was used to analyze the nonisothermal crystallization kinetics of PPS and its blends. The Avrami exponent values of neat PPS are higher than that of its blend, which shows that the presence of PEEK changed the nucleation type of PPS from homogeneous nucleation to heterogeneous nucleation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

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