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1.
    
The miscibility, crystallization behavior, and component interactions of two binary blends, poly(L ‐lactide) (L ‐PLA)/poly(vinylpyrrolidone) (PVP) and poly(D ,L ‐lactide) (DL ‐PLA)/PVP, were studied with differential scanning calorimetry and Fourier transform infrared (FTIR) spectroscopy. The composition‐dependent changes of the glass‐transition temperature (Tg) and degree of crystallinity (Xc) of the L ‐PLA phase indicated that L ‐PLA and PVP were immiscible over the composition range investigated. However, the sharp decrease of Xc with increasing PVP content in the second heating run demonstrated that the cold crystallization process of L ‐PLA was remarkably restricted by PVP. In DL ‐PLA/PVP blends, the existence of two series of isolated Tg's indicated that DL ‐PLA and PVP were phase‐separated, but evidence showed that there was some degree of interaction at the interface of the two phase, especially for the blends with low DL ‐PLA contents. FTIR measurements showed that there was no appreciable change in the spectra of L ‐PLA/PVP with respect to the coaddition of each component spectrum, implying the immiscibility of the two polymers. In contrast to L ‐PLA, the intermolecular interaction between DL ‐PLA and PVP was detected by FTIR; this was evidenced by the observation of a high‐frequency shift of the C?O stretching vibration band of PVP with increasing DL ‐PLA content, which suggested some degree of miscibility. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 973–979, 2003  相似文献   

2.
    
Blends of synthetic poly(propylene carbonate) (PPC) with a natural bacterial copolymer of 3‐hydroxybutyrate with 3‐hydroxyvalerate (PHBV) containing 8 mol % 3‐hydroxyvalerate units were prepared with a simple casting procedure. PPC was thermally stabilized by end‐capping before use. The miscibility, morphology, and crystallization behavior of the blends were investigated by differential scanning calorimetry, polarized optical microscopy, wide‐angle X‐ray diffraction (WAXD), and small‐angle X‐ray scattering (SAXS). PHBV/PPC blends showed weak miscibility in the melt, but the miscibility was very low. The effect of PPC on the crystallization of PHBV was evident. The addition of PPC decreased the rate of spherulite growth of PHBV, and with increasing PPC content in the PHBV/PPC blends, the PHBV spherulites became more and more open. However, the crystalline structure of PHBV did not change with increasing PPC in the PHBV/PPC blends, as shown from WAXD analysis. The long period obtained from SAXS showed a small increase with the addition of PPC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4054–4060, 2003  相似文献   

3.
    
Biopolyesters poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) with an 11 mol % 4HB content [P(3HB‐co‐11%‐4HB)] and a 33 mol % 4HB content [P(3HB‐co‐33%‐4HB)] were blended by a solvent‐casting method. The thermal properties were investigated with differential scanning calorimetry. The single glass‐transition temperature of the blends revealed that the two components were miscible when the content of P(3HB‐co‐33%‐4HB) was less than 30% or more than 70 wt %. The blends, however, were immiscible when the P(3HB‐co‐33%‐4HB) content was between 30 and 70%. The miscibility of the blends was also confirmed by scanning electron microscopy morphology observation. In the crystallite structure study, X‐ray diffraction patterns demonstrated that the crystallites of the blends were mainly from poly(3‐hydroxybutyrate) units. With the addition of P(3HB‐co‐33%‐4HB), larger crystallites with lower crystallization degrees were induced. Isothermal crystallization was used to analyze the melting crystallization kinetics. The Avrami exponent was kept around 2; this indicated that the crystallization mode was not affected by the blending. The equilibrium melting temperature decreased from 144 to 140°C for the 80/20 and 70/30 blends P(3HB‐co‐11%‐4HB)/P(3HB‐co‐33%‐4HB). This hinted that the crystallization tendency decreased with a higher P(3HB‐co‐33%‐4HB) content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

4.
    
Structure and mechanical properties for binary blends composed of a poly(3‐hydroxybutyrate) (PHB) and a cellulose derivative, such as cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB), have been studied by means of dynamic mechanical analysis, isothermal crystallization measurements, and tensile testing. It is found that β relaxation temperature due to glass transition of PHB or PHB‐rich phase in the blends, in which the cellulose derivative has lower molecular weight, is almost the same as that of the pure PHB. On the other hand, the peak location is shifted to even lower temperature than that of the pure PHB by blending the cellulose derivative with higher molecular weight, although the cellulose derivative is a glassy polymer with high glass transition temperature. Further, the blend with lower β relaxation temperature exhibits ductile behavior with low modulus in uniaxial deformation. The difference in the structure and mechanical properties for the blends are found to be determined by the crystallization rate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3447–3452, 2007  相似文献   

5.
    
The hydrogen bonding, miscibility, crystallization, and thermal stability of poly(3‐hydroxybutyrate) (PHB)/4‐tert‐butylphenol (BOH) blends and poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) [P(3HB‐3HHx)]/BOH blends were investigated by Fourier transform infrared (FTIR) spectroscopy, solid‐state13C‐NMR, differential scanning calorimetry, wide‐angle X‐ray diffraction (WAXD), and thermogravimetric analysis. The results of FTIR spectroscopy and solid‐state13C‐NMR show that intermolecular hydrogen bonds existed between the two components in the blends and that the interaction was caused by the carbonyl groups in the amorphous phase of both polyesters and the hydroxyl groups of BOH. With increasing BOH content, the chain mobility of both the PHB and P(3HB‐3HHx) components was improved. After the samples were quenched, the detected single glass‐transition temperatures decreased with composition, indicating that both PHB/BOH and P(3HB‐3HHx)/BOH were miscible blends in the melt. Moreover, as BOH content increased, the melting temperatures of PHB and P(3HB‐3HHx) clearly decreased, which implied that their crystallization was suppressed by the addition of BOH. Although the crystallinity of PHB and P(3HB‐3HHx) components decreased with increasing BOH content in the blends, their crystal structures were hardly affected after they were blended with BOH, which was further proven by WAXD results. In addition, the thermal stability of PHB was improved by a smaller amount of BOH.  相似文献   

6.
    
The effect of end groups (2NH2) of poly(ethylene glycol) (PEG) on the miscibility and crystallization behaviors of binary crystalline blends of PEG/poly(L ‐lactic acid) (PLLA) were investigated. The results of conductivity meter and dielectric analyzer (DEA) implied the existence of ions, which could be explained by the amine groups of PEG gaining the protons from the carboxylic acid groups of PLLA. The miscibility of PEG(2NH2)/PLLA blends was the best because of the ionic interaction as compared with PEG(2OH, 1OH‐1CH3, and 2CH3)/PLLA blends. Since the ionic interaction formed only at the chain ends of PEG(2NH2) and PLLA, unlike hydrogen bonds forming at various sites along the chains in the other PEG/PLLA blend systems, the folding of PLLA blended with PEG(2NH2) was affected in a different manner. Thus the fold surface free energy played an important role on the crystallization rate of PLLA for the PEG(2NH2)/PLLA blend system. PLLA had the least fold surface free energy and the fast crystallization rate in the PEG(2NH2)/PLLA blend system, among all the PEG/PLLA systems studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

7.
    
A phase diagram of poly(vinylidene fluoride) (PVDF) and acrylic rubber (ACM) was plotted, and the effects of the extent of miscibility on the mechanical properties of the polymer blends were examined. A compressible, regular solution model was used to forecast the phase diagram of this blend. The model prediction, the lower critical solution temperature (LCST) over the upper critical solution temperature (UCST), was done qualitatively according to the experimentally determined phase diagram by differential scanning calorimetry (DSC), optical microscopy, and rheological analysis. These experimental methods showed that this system was miscible in ACM‐rich blends (>50% ACM) and partially miscible in PVDF‐rich blends. A wide‐angle X‐ray diffraction study revealed that PVDF/ACM blends such as neat PVDF had a characteristic α‐crystalline peak. The partially miscible blends displayed up to 350% elongation at break; this was a significant increment of this parameter compared to that of neat PVDF(20%). However, the miscible blends showed elongation of up to 1000% [again, a remarkable increase compared to chemically crosslinked ACM (220%)] and displayed excellent mechanical properties and tensile strength and a large elongation at break. For the miscible and partially miscible blends, two different mechanisms were responsible for this improvement in the mechanical properties. It was suggested that in the partially miscible blends, the rubbery depletion layer between the spherulite and the conventional rubber cavitations mechanism were responsible for the increase in the elongation at break, whereas for the miscible blends, the PVDF spherulite acted as a crosslinking junction. The stretched part of the tensile samples in the partially miscible blends showed characteristic β‐crystalline peaks in the Fourier transform infrared spectra, whereas that in the miscible blends showed α‐crystalline peaks. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1247‐1258, 2013  相似文献   

8.
    
Lignin does not show miscibility with commercial polyolefins. Therefore, industrial waste lignin was modified in two different ways and subsequently blended with commercial polypropylene (PP) up to 25 wt %. A Brabender electronic plasticorder was used for melt mixing at 190°C. The influence of different modifications on the mechanical properties and processing stability was studied for both polymer blends. The blends of PP and lignin modified (esterified) with maleic anhydride showed less deterioration in the mechanical properties compared to blends of PP and alkylated lignin with dichloroethane. Intermolecular interactions between the PP matrix and modified lignin were concluded on the basis of indicative values derived from various relevant theoretical models to the experimental data. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

9.
    
Polyhydroxybutyrate (PHB) is a biodegradable bacterial polyester emerging as a viable substitute for synthetic, semicrystalline, nonbiodegradable polymers. An elastomer terpolymer of acrylonitrile‐g‐(ethylene‐co‐propylene‐co‐diene)‐g‐styrene (AES) was blended with PHB in a batch mixer and in a twin‐screw extruder to improve the mechanical properties of PHB. The blends were characterized with differential scanning calorimetry, dynamic mechanical analysis, scanning electron microscopy, and impact resistance measurements. Despite the narrow processing window of PHB, blends with AES could be prepared via the melting of the mixture without significant degradation of PHB. The blends were immiscible and composed of four phases: poly(ethylene‐co‐propylene‐co‐diene), poly(styrene‐co‐acrylonitrile), amorphous PHB, and crystalline PHB. The crystallization of PHB in the blends was influenced by the AES content in different ways, depending on the processing conditions. A blend containing 30 wt % AES presented impact resistance comparable to that of high‐impact polystyrene, and the value was about 190% higher than that of pure PHB. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

10.
    
Miscibility and crystallization behaviors of biodegradable poly(butylene succinate‐co‐butylene terephthalate) (PBST)/poly(hydroxyl ether biphenyl A) (phenoxy) blends were investigated with various techniques in this work. PBST and phenoxy are completely miscible as evidenced by the single composition‐dependent glass transition temperature over the entire blend compositions. Nonisothermal melt crystallization peak temperature is higher in neat PBST than in the blends at a given cooling rate. Isothermal melt crystallization kinetics of neat and blended PBST was studied and analyzed by the Avrami equation. The overall crystallization rate of PBST decreases with increasing crystallization temperature and the phenoxy content in the PBST/phenoxy blends; however, the crystallization mechanism of PBST does not change. Moreover, blending with phenoxy does not modify the crystal structure but reduces the crystallinity degree of PBST in the PBST/phenoxy blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

11.
    
A combined use of solid plasticizer [poly(ethylene glycol), PEG] with a nominal Mw of 2000 g/mol and liquid plasticizer (epoxidized soybean oil, ESO) for plasticizing poly(lactic acid) (PLA) is proposed in this study. This plasticization method brought an obvious improvement in the melting flowability of the modified PLA, which has been verified by a lower balance torque during blending and a four times increase in the melt flow index compared to neat PLA. Meanwhile, the brittleness of this glassy polymer was also improved significantly; all composites with different contents of combined plasticizers displayed an obvious yield stage and toughness fracture surfaces. The mechanisms of the plasticizing effects were investigated by polarizing optical microscopy and scanning electron microscopy. The PLA/ESO/PEG blends formed a complex reinforcement structure. ESO existed as tiny droplets and uniformly dispersed in the PLA spherulites, and strip‐shaped PEG accumulated along the boundaries of interspherulites. The combined use of these two plasticizers, a liquid one and a solid one, had an excellent effect on plasticizing PLA, not only on melt flowability but also on mechanical properties. Thus, the application areas for PLA could be further expanded, such as melt blowing and melt extrusion. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46669.  相似文献   

12.
    
The polyamide 66 (PA66)/poly(hydroxyl ether of bisphenol A) (PHE) blend was successfully prepared by twin‐screw extrusion without the addition of any compatibilizer. The PA66/PHE blends had a microphase‐separated structure that varied from a sea‐island structure to a cocontinuous structure, and the mechanical properties were higher than the anticipated values on the basis of the rule of mixtures, which showed a synergistic effect. Fourier transform infrared spectroscopy and dynamic mechanical analysis illustrated that there was hydrogen‐bonding interaction between the amide groups of the PA66 and the pendant hydroxyl groups of the PHE. This led to the some degree of compatibility and the improvement in the mechanical properties of the blends. The polarized optical microscopy observation showed that the PA66 spherulites of the blend became smaller and more imperfect compared to those of the pure PA66, and differential scanning calorimetry measurement also showed a decrease in the melting temperatures of PA66 of the blend. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40437.  相似文献   

13.
    
In this study, the dependence on the morphology and mechanical properties was analyzed when different amounts of polylactic acid are added to the polyethylene terephthalate polymer matrix using single-screw extrusion. Thermograms of the polymer blends obtained by differential scanning calorimetry couple to thermal gravimetric analysis show a displacement in the glass transition temperature with the amount of polylactic acid (1, 2.5, 5, and 7.5 wt%) added to the polymer matrix. Scanning electron microscopy and atomic force microscopy images showed two different kinds of morphology, both characteristics of miscible and partially miscible polymer blends. Fourier transform infrared spectroscopy measurements confirmed a physical interaction by hydrogen bond in the polymer blends. The impact resistance and tensile strength are reduced with the polylactic acid addition and are influenced by the fraction of segments of hydrogen bonded in the polyethylene terephthalate/polylactic acid blends as well as their miscibility.  相似文献   

14.
    
In order to improve the impact strength of PPS‐based strontium ferrite composite, the thermoplastic polyurethane (TPU) elastomer was added in the composite as a toughening agent. The composites were obtained by melt‐blending PPS, TPU and strontium ferrites in twin‐screw extruder. The crystalline state, thermal property, surface morphology and impact strength of the composites were investigated by using X‐ray diffraction, differential scanning calorimetry, thermoravimetric analysis, scanning electron microscope and izod impact test. The addition of TPU improves impact strength of PPS‐based strontium ferrite composite. When the addition of TPU increases to 11wt %, the impact strength of Sr‐ferrite/PPS/TPU composite is enhanced by 51.44% compared with the sample without TPU addition, and reaches to 5.77 kJ/m2. The occurrence of bonding interaction between PPS and TPU, demonstrated by a series of experiments, changes the structure and impact properties of PPS. Based on the experimental results, a possible mechanism is proposed to explain the improvement of Sr‐ferrite/PPS/TPU composites, which is different from the conventional toughening mechanism by the conformation of elastomers and the suppression of microcracks propagation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43564.  相似文献   

15.
    
Composites of poly(lactic acid) (PLA) with poly(butylene succinate) (PBS) and microcrystalline cellulose (MCC) as reinforcements of the polymer matrix were prepared by melt blending to improve the brittleness of PLA. As a reactive compatibilizer, a chain extender was used in an attempt to solve the composites’ interfacial problems and to improve their mechanical properties; Fourier transform infrared spectroscopy indicated that the chain extender functionally reacted with PLA, PBS, and MCC mainly through end carboxyls or end hydroxyls. Scanning electron microscopy indicated that the chain extender significantly improved the cohesive interfacial forces. Differential scanning calorimetry and X‐ray diffraction showed that the chain extender inhibited crystallization, and these effects were greater when its percentage was increased. The addition of chain extender improved the tensile and impact strength of the composites, and this improvement was proportional to the chain‐extender percentage. However, the elongation at break decreased when the chain‐extender percentage was over 0.5% because of mild crosslinking within the resin matrix. Rheology indicated that the complex viscosity and storage and loss moduli of the composites increased with increasing amount of chain extender; this indicated that the addition of chain extender improved the melt strength and processability of the composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44895.  相似文献   

16.
    
Considering the complementary properties of poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride‐trifluoroethylene) [P(VDF‐TrFE)], it appears that their blends have the potential to be promising candidates for device applications. We report the evolution of morphology, ferroelectric, and mechanical properties (modulus and hardness) and their dependence on preparation temperature for PVDF–P(VDF‐TrFE) blends. From ferroelectric hysteresis measurements it was found that P(VDF‐TrFE) rich blends treated at higher temperature show significant values of remanent polarization. Remanent polarization values show a fourfold increase in these P(VDF‐TrFE) rich blends treated at higher temperature. Interestingly, blends prepared from high temperature showed greater value of remanent polarization even though they were found to consist of smaller amount of electroactive phase as compared to their low temperature treated counterpart. Nanoindentation experiments revealed that high temperature treatment improves the modulus of blends by at least 100%. This report attempts to tie these findings to the morphology and crystallinity of these blends. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45955.  相似文献   

17.
    
Polypropylene blends containing a dispersed phase of scrap rubber dusts obtained from sport shoes manufacture; midsole (M, vulcanized EVA foam) and outsole (O, vulcanized rubber blend of NR, SBR, and BR) were studied. The influence of various compatibilizers on the mechanical properties of these blends were investigated. Significant development of impact strength was attained by using 6 and 10 phr of styrene–ethylene–butylene–styrene (SEBS) and maleic anhydride‐grafted styrene–ethylene–butylene–styrene (SEBS‐g‐MA) as compatibilizers for both compounds filled with midsole and outsole dusts. The tensile strength of each compound was slightly decreased when the compatibilizer loading increased, whereas the elongation at break was significantly increased. The enhancements of the impact strength and the elongation at break are believed to arise from reduction of interfacial tension between two phases of the rubber and the PP, which results in some reduction of the particle size of the fillers. Scanning electron microscopy (SEM) confirmed the evidence of the reduction of scrap rubber dust into small rubber particle sizes in the compound, and also showed the occurrence of some fibrils. Optical microscopy (crossed polars) observations suggested that the addition of the rubber dust resulted in a less regular spherulite texture and less sharp spherulite boundaries. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 148–159, 2002  相似文献   

18.
    
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 (Tg'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  相似文献   

19.
    
The strain‐induced crystallization of natural rubber (NR) was investigated by the measurement of the tear energy of a crosslinked blend consisting of NR and noncrystalline styrene–butadiene rubber (SBR). When NR was dispersed into the SBR matrix, the tear energy of SBR increased at various temperatures and tear rates. After the application of the principle of time–temperature superposition to the tear energy according to the Williams–Landel–Ferry equation, two distinct curves were found for the NR/SBR blend with respect to the reduced tear rate, despite the fact that the tear energy of SBR or the SBR/SBR blend gave its own single composite curve. When the fatty acid in the NR/SBR blend was removed by acetone extraction, the tear energy of the blend drew a single composite curve. The conversion of the two curves into the single composite curve for the NR/SBR blend suggested that the tear energy depended on the strain‐induced crystallization of NR dispersed in the SBR matrix, which was suppressed by the removal of the fatty acid. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 613–619, 2005  相似文献   

20.
    
Blends of an amorphous polylactide (PLA) with three different thermoplastic polyurethane (TPU) grades having various hard segment (HS) contents are prepared at the blending ratio of 85/15 wt% through a twin-screw extruder (TSE) at processing temperatures of 150 and 190°C. Blends of a semicrystalline PLA with 15 wt% of the noted TPU grades are also processed in the TSE at 190°C to investigate the matrix crystallization effect on the morphology and property enhancements. The rheological experiments reveal that the increase in TPU HS content significantly increases the phase compatibility between PLA and TPU as also suggested by the finer morphology of the TPU phase, although the use of lower HS TPUs is more favorable to enhance the ductility and impact properties of the blends.  相似文献   

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