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1.
In this study, the self‐made nano‐hydroxyapatite (HA) and poly(butylene adipate‐co‐butylene terephthalate) copolyesters (PBAT) were used as fillers, and composite films of HA/PLA (PLA, polylactide) and HA/PBAT/PLA systems were prepared. The micromorphology, mechanical properties, thermal properties, crystallinity, water vapor permeability and oxygen permeability of the composite films were studied. The results show that the self‐made HA has a porous rod‐like structure with a size of 30–50 nm. PBAT was dispersed uniformly in the HA/PLA matrix in the form of spherical particles and formed many pores and holes. The tensile strength, elongation at break and modulus of elasticity of HA/PLA composite films were increased by adding 10 wt% PBAT. The addition of HA and PBAT played a synergistic function in improving the crystallinity of the composite films. The water vapor and oxygen permeabilities of HA/PLA and HA/10%PBAT/PLA composite films can be regulated by adjusting the amount of HA. The results of this study indicate that composite films with higher water vapor and oxygen permeabilities exhibit great potential for applications in green packaging and fresh‐keeping packaging. © 2019 Society of Chemical Industry  相似文献   

2.
The crystallization behavior and water vapor permeability of a poly(lactic acid) (PLA) nanocomposite containing 5 wt % organic montmorillonite (OMMT) under oscillatory shear were investigated. Under the oscillatory shear, OMMT platelets exhibited a better intercalated structure and oriented along the flow direction, some of the OMMT platelets are exfoliated and dispersed in the form of single or few‐layer platelets. These well‐dispersed OMMT platelets acted as more effective nucleating and accelerating agent for the crystallization of PLA, as a result, the cold crystallization enthalpy was significantly decreased, the cold crystallization temperature was much closer to the melting temperature and the crystallinity is dramatically increased, which are observed for the first time. Moreover, the water vapor permeability is decreased by 36% due to the barrier effect of the well‐dispersed OMMT and the increased crystallinity of PLA, which increase the tortuous path that water molecules required to permeate. The mechanical properties are also enhanced owing to the well‐dispersed OMMT and increased crystallinity. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42321.  相似文献   

3.
Poly‐lactic acid (PLA) nanocomposite film was prepared with untreated and silane treated sepiolite through solution casting method. Sepiolite is found to be promising nano inorganic filler used to prepare biodegradable PLA nanocomposite films. The effect of sepiolite loading on the thermal, mechanical, gas permeability, and water vapor permeability (WVP) properties of the films was investigated. X‐ray diffraction analysis revealed the crystallinity index and well dispersed sepiolite in PLA/sepiolite thin films. By modifying sepiolite, depending on the nanoclay content, the mechanical properties of films were enhanced. PLA/sepiolite films exhibited improved gas barrier and WVP properties compared to neat PLA. The scanning electron microscope results demonstrated that there is a good interface interaction between sepiolite and PLA. The surface treatment of sepiolite increased the adhesion of the PLA matrix to the sepiolite nanoclay which yielded better mechanical properties of the films as compared to pure PLA. It was observed after 1.5% wt sepiolite, nano‐filler tended to agglomerate, therefore mechanical and barrier properties of films decreased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41428.  相似文献   

4.
Exacerbated environmental concerns about petroleum‐based plastics provide the impetus to foster sustainable poly(lactic acid) (PLA) based food packaging. Nonetheless, PLA has its foibilities such as its brittleness, higher gas permeability, and slow crystallization. With the intent to mitigate the above shortcomings, we report a maiden effort for the fabrication of PLA/crystalline silk nano‐discs (CSNs) based bionanocomposites by melt‐extrusion for high temperature engineering and food packaging applications. Acid hydrolyzed silk fibroin from muga silk (Antheraea assama) yields CSNs, a crystalline hydrophobic discotic nanofiller with diameter of ~50 nm and thickness ~3 nm. At optimum loadings of 1 wt % uniform dispersed CSNs with percolated network structures covering the entire matrix can be seen. Due to enhanced crystal nucleation density, water vapor, and oxygen permeability reduced by ~30% and ~70%, respectively. Enhancement in toughness, percentage elongation, and tensile strength up to ~65%, ~40%, and ~10%, respectively, is obtained. Onset of thermal decomposition for the PLA/CSN improved ~10 °C, confirming the role of CSN in enhancing melt stability. Accordingly, this investigation renders a novel non‐invasive approach for increasing the crystallinity with improvement in thermomechanical and barrier properties which make this bionanocomposite, a promising candidate for food packaging applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46671.  相似文献   

5.
In this work, lignin was used as a heterogeneous nucleating agent to increase polylactic acid (PLA) crystallinity. To enhance the gas barrier performance of PLA/LG composite films, two graft copolymers, polylactide-graft-glycidyl methacrylate (PLA-g-GMA) and polylactide-graft-poly (ethylene glycol) methyl ether methacrylate (PLA-g-PEGMA) were successfully synthesized and separately used as compatibilizers to modify PLA/LG composite properties such as interfacial adhesion, crystallinity, and mechanical properties. Since crystallites can act as obstacles to gas diffusion, the higher the crystallinity of the polymer matrix, the better gas barrier performance of the composite film will be. The crystallinity and crystalline structure of the PLA matrix was demonstrated by wide-angle X-ray diffraction and differential scanning calorimetry results. Since LG particles can act as efficient heterogeneous crystal nucleating agents, a roughly 50% reduction in oxygen permeability (PO2) was obtained by adding 1 phr LG to the PLA matrix (PLA/1LG). Following addition of 10 phr PLA-g-GMA to the PLA/LG composite, PLA/PLA-g-GMA/LG composite films showed lower gas barrier properties than PLA/LG composites without added compatibilizer. Moreover, the interfacial adhesion of PLA/LG composites was significantly improved after addition of PLA-g-GMA. Therefore, PLA/PLA-g-GMA/3LG showed the highest tensile strength, 33% higher than that of neat PLA. Following addition of 10 phr PLA-g-PEGMA to the PLA/LG composite, the long liner side chains of PLA-g-PEGMA were able to act as nucleating agents for PLA to promote the crystallization of PLA. Accordingly, PLA/PLA-g-PEGMA/3LG with 3 phr LG showed a roughly 86% reduction in PO2 when compared with neat PLA film.  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 biopolymer poly‐3‐hydroxybutyrate‐co‐3‐hydroxyvalerate (PHBV) is a promising material for packaging applications but its high brittleness is challenging. To address this issue, PHBV was blended with nine different biopolymers and polymers in order to improve the processing and mechanical properties of the films. Those biopolymers were TPS, PBAT, a blend of PBAT + PLA, a blend of PBAT + PLA + filler, PCL and PBS, and the polymers TPU, PVAc, and EVA. The extruded cast films were analyzed in detail (melting temperature, crystallinity, mechanical properties, permeation properties, and surface topography). A decrease in crystallinity and Young's modulus and an increase in elongation at break and permeability were observed with increasing biopolymer/polymer concentration. In PHBV‐rich blends (≥70 wt % PHBV), the biopolymers/polymers PCL, PBAT, and TPU increased the elongation at break while only slightly increasing the permeability. Larger increases in the permeability were found for the films with PBS, PVAc, and EVA. The films of biopolymer/polymer‐rich blends (with PBAT, TPU, and EVA) had significantly different properties than pure PHBV. A strong effect on the properties was measured assuming that at certain biopolymer/polymer concentrations the coherent PHBV network is disrupted. The interpretation of the permeation values by the Maxwell–Garnett theory confirms the assumption of a phase separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46153.  相似文献   

8.
The objective of this study was to investigate the effects of various solvents on the crystallinity and thermal expansion stability of PLA film. Three different PLA films were produced by the solvent casting technique; PLA in chloroform (PLA‐C), PLA in methylene chloride (PLA‐M), and PLA in methylene chloride: acetonitrile = 50: 50 (PLA‐MA). The PLA‐MA had higher % crystallinity, 46.15, than the PLA‐C, 24.03, and the PLA‐M, 14.25. With this increase in crystallinity, the PLA‐MA had improved thermal expansion stability as shown by very low accumulated dimensional changes at 20 to 100°C. Wide‐angle X‐ray diffraction identified multiple crystalline structures for the PLA‐MA. Film barrier properties were also measured. PLA‐MA had the lowest oxygen permeability. However, there was no significant difference in water vapor permeability among the three PLA films. The mechanical property tests revealed that the PLA‐C and PLA‐M were ductile while the PLA‐MA was brittle in behavior. The PLA‐MA was very hazy as compared with the PLA‐C and PLA‐M. This work has shown that the PLA‐MA had increased % crystallinity and, more importantly, it had improved thermal expansion stability which can be very beneficial for the flexible packaging industry. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

9.
Poly(lactic acid) (PLA) is a bio‐based and compostable polymer that has quickly developed into a competitive material, but the control of crystallinity is a bottleneck in extended utilization. The crystallization of PLA has been a rich topic because of the existence of two enantiomeric forms of poly(L‐lactic acid) (PLLA) and poly(d ‐lactic acid) (PDLA) can form stereocomplex (SC) crystal with high melting point that can be used to control the crystallization behaviors. The SC crystal was regarded as an effective nucleating agent for promoting the crystallization rate and crystallinity of PLA. We investigated cold crystallization of PLLA/PDLA (1:1) mixture with in situ WAXS measurements and found that the homo‐crystal of PLA formed earlier than the SC‐crystal in the mixture within the measured temperature range, which is different from the melting crystallization. The final crystalline structures are in correspondence with the melting and cold crystallization temperature, and the transition of homo‐PLA (δ to α) is not altered by the crystallization procedure. The SC‐crystal can be detected in both cold and melting crystallization of the mixture at the temperatures lower than 150 °C, which is conflict with the reported results. A new crystallization mechanism of the mixture was proposed to understand the crystallization behaviors in PLLA/PDLA mixtures. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45663.  相似文献   

10.
Environmental issues concerning petroleum‐based polymers have begun a growing emphasis to utilize sustainable poly(lactic acid) (PLA) based packaging. However, PLA has its own limitations such as brittleness, high gas permeabilities and slow crystallization rate. With the aim to alleviate these limitations, we made a maiden effort to use a food additive, sucrose palmitate (SP) as eco‐friendly filler for fabrication of PLA based bionanocomposites. FTIR analysis elucidated the presence of hydrogen bonding and intermolecular interaction between PLA and reinforcement. Ordered orientation of the SP in the PLA matrix visualized by TEM analysis revealed uniform dispersion of SP filler into PLA matrix. DSC and XRD results confirmed that the incorporated bio‐filler acted as a nucleating agent and thus partially contributed towards the crystallinity of PLA‐SP bionanocomposites. Enhancement in the tensile strength and elongation at break up to 83 and 56% respectively is obtained. The best positive influence for the oxygen barrier was confirmed for the PLA‐SP bionanocomposite film where the reduction in oxygen permeability by 69% is achieved in comparison to pure PLA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41320.  相似文献   

11.
We have investigated the relationship between amorphous structure and its gas permeability of poly(lactic acid) (PLA) using differential scanning calorimetry, wide‐angle X‐ray scattering, and small‐angle X‐ray scattering measurements. We focused on the hierarchical interlamellar amorphous structure of various gas‐permeable PLA films. The films crystallized just above Tg did not have any long‐spacing period peaks at the room temperature even with the existence of crystals; conversely, peaks could be observed from long spacing periods with heating. Therefore, the interlamellar amorphous density became as high as crystalline region one at the room temperature. These high‐density amorphous regions, the so‐called rigid‐amorphous phase, reduced the gas diffusion and permeation. In the case of samples crystallized above 90°C, the long spacing period peaks could be observed even at the room temperature. The amorphous region did not develop the rigid‐amorphous phase, and the gas permeability depended only on crystallinity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40626.  相似文献   

12.
The effects of exposure time and vapor pressure on the crystallization behaviors of bisphenol‐A polycarbonate (BAPC) films were investigated at 25°C by using differential scanning calorimetry (DSC). Double melting peaks were observed for various BAPC samples after vapor‐induced crystallization. The low temperature melting peak shifted to higher temperature and became sharper with increasing exposure time, and could be assigned to defective crystals with smaller crystal size. Crystallinity and average crystal dimension normal to (020) were calculated from wide‐angle X‐ray diffraction spectra. A good agreement was obtained between crystallinity values obtained from WAXD and those from DSC. The morphology of crystallized samples after various exposure time periods was examined by means of polarized optical microscopy. Nucleation occurred at the initial stage of vapor‐induced crystallization. Poor crystals become perfect through segment reorganization with increasing exposure time, and spherulites' growth was observed. The average diameter of spherulites increased from 2 μm for 1 h, to 7 and 16 μm after 3 and 56 h, respectively. POLYM. ENG. SCI., 46:729–734, 2006. © 2006 Society of Plastics Engineers  相似文献   

13.
Polylactic acid (PLA) films were surface modified by gamma ray irradiation‐induced grafting of N‐vinyl pyrrolidone (NVP). The in vitro degradation behavior of polylactic acid grafting N‐vinyl pyrrolidone (PLA‐g‐PVP) copolymer was analyzed in terms of weight loss, molecular weight, and thermal properties. Grafting NVP significantly accelerated the degradation of PLA. The mass losses of the copolymers, which were less than that of pure PLA at the beginning of the degradation period, sharply accelerated with increasing degradation time. Moreover, the crystallization temperature decreased with increasing degradation time in the same graft ratio, and the degree of crystallinity increased. Cytotoxicity experiments and animal experiments in vivo were carried out to evaluate the biocompatibility of PLA‐g‐PVP copolymer. Varying graft ratios of PVP could control the degradation rate of copolymers, and thus broadening the applications of this material, such as in tissue engineering scaffolds, drug delivery, and prevention of postsurgical adhesion. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

14.
Poly(lactic acid) based nanocomposite films were prepared by melt compounding and subsequent flat film extrusion. After characterizing the nanocomposites with the help of transmission electron microscopy and wide angle X‐ray diffraction to estimate the nanoclay distribution in the matrix material, the oxygen and water vapor permeability of untreated and annealed nanocomposite films were analyzed. A reduction to 34% of both permeability values could be realized by the addition of 6 wt % Cloisite 30B and subsequent annealing to realize maximum crystallinity. Experimental permeability as a function of nanoclay concentration was successfully described by the Tortuous Path Model. In addition, the correlation between oxygen permeability and relative humidity was analyzed for pure PLA and PLA based nanocomposite films. For both untreated films oxygen permeability decreased almost linearly between 0% and 96% RH to approximately 70% of the respective value for the dry sample. Annealed PLA films, on the other hand, showed a similar behavior up to 70% RH but an increase in oxygen permeation for higher moisture content. This is explained by the observed reduction in crystallinity generating more free volume, bringing the system closer to the amorphous case where permeability is generally higher. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44424.  相似文献   

15.
Amorphous‐made poly(L ‐lactide) [i.e., poly(L ‐lactic acid) (PLLA)], poly(L ‐lactide‐co‐D ‐lactide)[P(LLA‐DLA)](77/23), and P(LLA‐DLA)(50/50) films and PLLA films with different crystallinity (Xc) values were prepared, and the effects of molecular weight, D ‐lactide unit content (tacticity and optical purity), and crystallinity of poly(lactide) [i.e., poly(lactic acid) (PLA)] on the water vapor permeability was investigated. The changes in number‐average molecular weight (Mn) of PLLA films in the range of 9 × 104–5 × 105 g mol?1 and D ‐lactide unit content of PLA films in the range of 0–50% have insignificant effects on their water vapor transmission rate (WVTR). In contrast, the WVTR of PLLA films decreased monotonically with increasing Xc from 0 to 20%, while leveled off for Xc exceeding 30%. This is probably due to the higher resistance of “restricted” amorphous regions to water vapor permeation compared with that of the “free” amorphous regions. The free and restricted amorphous regions are major amorphous components of PLLA films for Xc ranges of 0–20% and exceeding 30%, respectively, resulting in the aforementioned dependence of WVTR on Xc. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006  相似文献   

16.
The effect of different annealing treatments with supercritical carbon dioxide (SCCO2) on the structural and mechanical properties of semicrystalline poly‐L ‐lactic acid (L ‐PLA) was investigated. 2000, 27,000, 100,000, and 350,000 g mol?1 molecular weight L ‐PLA polymers were used in the study. The solid‐state processing of L ‐PLA at temperatures lower than the effective melting point led to solvent‐ and thermal‐induced crystallization. Solvent‐induced and isothermal crystallization mechanisms could be considered similar regarding the increase of polymer chain mobility and mass‐transfer in the amorphous region; however, quite different microstructures were obtained. SCCO2 solvent‐induced crystallization led to polymers with high crystallinity and melting point. On the contrary, SCCO2 thermal‐induced crystallization led to polymers with high crystallinity and low melting point. For these polymers, the hardness increased and the elasticity decreased. Finally, the effect of dissolving SCCO2 in the molten polymer (cooling from the melt) was analyzed. Cooling from the melt led to polymers with high crystallinity, low melting point, low hardness, and low elasticity. Distinctive crystal growth and nucleation episodes were identified. This work also addressed the interaction of SCCO2‐drug (triflusal) solution with semicrystalline L ‐PLA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

17.
This study investigated the influence of high‐pressure processing on the morphology and permeability of low‐density polyethylene (LDPE) films used for food packaging. This was done by monitoring the crystallinity, melting temperature (Tm), and oxygen transmission rate (OTR) of the materials before and after the pressure treatments. A first set of pouches made from the LDPE films were filled with 95% ethanol then pressured at 200, 400, 600, and 800 MPa for 5 and 10 min at 25 and 75°C. The crystallinity and Tm of the films were measured using differential scanning calorimetry (DSC). X‐ray diffraction (XRD) was also used to determine the crystallinity. A second set of LDPE pouches were similarly made but a half of them were filled with 95% ethanol and the other half filled with distilled water. These second set of pouches were pressured at 200, 600, and 800 MPa then their OTR tested. Results of the DSC experiments showed that the Tm increased with increasing pressure intensity but the crystallinity changes were not detectible. The XRD method on the other hand, showed significant (P < 0.05) crystallinity increases with increasing pressure treatments. The gas permeability analyses showed decreasing OTR's with increasing high‐pressure intensity treatments. The OTR in the pouches filled with the 95% ethanol was slightly lower than that of the pouches filled with water. These findings allowed us to better anticipate the behavior of LDPE films used to package high‐pressure processed foods. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

18.
The oxygen and water vapor permeability at high relative humidity was studied for composite films formed by incorporation of three different bentonites (MMT) into an ethylene‐modified, water‐soluble poly(vinyl alcohol), EPVOH. The oxygen permeability decreased linearly with an increased addition of hydrophilic MMTs. X‐ray diffraction and Fourier transform infrared spectroscopy suggested a homogeneous distribution in the thickness direction with disordered and probably exfoliated structures for hydrophilic MMTs. In contrast, organophilic modified clay showed an intercalated structure with the clay preferentially located at the lower film surface, a combination which was however efficient in reducing the water vapor‐ and oxygen permeabilities at low addition levels. Composite films of EPVOH and Na+‐exchanged MMT resulted in high resistance to dissolution in water, which was ascribed to strong interactions between the components resulting from matching polarities. Annealing the films at 120°C resulted in enhanced resistance to water dissolution and a further reduction in oxygen permeability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42229.  相似文献   

19.
A multi‐functional epoxy (ADR) was used to improve compatibilization of poly(lactic acid) (PLA)/ thermoplastic polyester elastomer (TPEE) blends. Influence of ADR on isothermal melt crystallization of the blends was investigated. The results show that isothermal melt crystallization rate of the samples increases with ADR loading. It can be attributed to a nucleation enhancement resulted from an increase of molecular weight and melt viscosity created by the chain extension/branched process of PLA in the presence of ADR. In addition, the maximum crystallinity of the samples shows a decrease with increasing ADR loading because of the chain extended and branched reaction. Quenched and crystallized samples were fabricated using compression molding under different cooling conditions in‐mold. Effects of crystallinity and ADR on mechanical performances of the PLA/TPEE sample were investigated. With increasing the crystallinity, the PLA/TPEE sample shows a marked enhancement in heat resistance. However, the tensile ductility of the crystallized PLA/TPEE sample drastically decreases due to the formation of firm crystal crosslinking and the incompatibility between PLA and TPEE. It is notable that the tensile ductility of the crystallized samples is improved with the introduction of ADR owing to its reactive compatibilization effect. Finally, the crystallized PLA/TPEE/ADR samples with improved heat resistance and relative higher ductility are obtained. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46343.  相似文献   

20.
A series of aliphatic diacyl adipic dihydrazides (ADHs) with different alkyl moieties were synthesized by the reaction between adipic dihydrazide and acyl chloride. Then these ADHs were solution blended with PLA respectively and were evaluated as nucleating agents. Through the investigation of nonisothermal and isothermal crystallization, it was found that both the crystallization rate and the crystallinity of PLA could be enhanced by adding only 1 wt % of ADHs. Especially for ADH‐Oc (ADH‐Octyl), the crystallization rate of PLA increased about 4 times at 105°C. Optical morphology showed that and the size of PLA spherulites decreased and the nucleation density increased with the existence of ADH‐Oc. Meanwhile, the crystal structure of PLA were not discerniblly affected after the addition of ADHs as found by wide‐angle X‐ray diffraction. Thus, this study suggested these ADHs compounds are simple and potential nucleating agents to enhance crystallization ability of PLA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42028.  相似文献   

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