High performance materials based on a self‐assembled multiple‐percolated ternary blend

In this study, it will be shown that morphologically tailored tricontinuous ternary blends, comprising polybutylene succinate (PBS), polylactic acid (PLA), and poly (butylene adipate‐co‐terephthalate)(PBAT), can generate new materials with excellent properties. Detailed morphological analysis is used to establish that all three phases in the ternary 33%PBS/33%PLA/33%PBAT blend morphology are highly continuous with a phase structure dominated by complete wetting dynamics. PBS is shown to situate itself between PLA and PBAT. This melt processed, self‐assembled, multiple percolated, blend possesses a high elongation at break (567%), high Young's modulus (1130 MPa), high impact strength (271 J/m), and a storage modulus about 50% higher than pure PBS at room temperature. None of the neat materials demonstrate this combination of high properties and the synergy derives from the tricontinuous structure of the system. The ternary nature of the blend allows for a modulation of the crystallinity behavior as examined by differential scanning calorimeter and X‐ray Diffraction. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3005–3012, 2014     

Mechanical properties and morphological changes of poly(lactic acid)/polycarbonate/poly(butylene adipate‐co‐terephthalate) blend through reactive processing

The mechanical properties and morphological changes of poly(lactic acid) (PLA), polycarbonate (PC), and poly(butylene adipate‐co‐terephthalate) (PBAT) polymer blends were investigated. Several types of blend samples were prepared by reactive processing (RP) with a twin‐screw extruder using dicumyl peroxide (DCP) as a radical initiator. Dynamic mechanical analyses (DMA) of binary polymer blends of PC/PBAT indicated that each component was miscible over a wide range of PC/PBAT mixing ratios. DMA of PLA/PBAT/PC ternary blends revealed that PBAT is miscible with PC even in the case of ternary blend system and the miscibility of PLA and PBAT can also be modified through RP. As a result, the tensile strain and impact strength of the ternary blends was increased considerably through RP, especially for PLA/PBAT/PC = 42/18/40 (wt/wt/wt) with DCP (0.3 phr). Scanning electron microscopy (SEM) analysis of the PLA/PBAT/PC blends revealed many small spherical island phases with a domain size of approximately 0.05–1 μm for RP, whereas it was approximately 10 μm without RP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of poly(butylene adipate‐co‐terephthalate) and ultrafined wollastonite on the physical properties and crystallization of recycled poly(ethylene terephthalate)

Recycled poly(ethylene terephthalate) (rPET), obtained mainly from postconsumer bottles, was melt‐mixed with either poly(butylene adipate‐co‐terephthalate) (PBAT) or PBAT plus ultrafine wollastonite (～5 μm) at different weight ratios on a twin‐screw extruder and then injection‐molded. Among the five rPET/PBAT blends (10–50 wt% PBAT) evaluated, the 80/20 wt% rPET/PBAT blend exhibited the highest tensile strength and degree of crystallinity, a slight increase in the tensile strain, and a remarkable increase in the melt flow index, but a lower tensile modulus and thermal stability with respect to the neat rPET. This blend was subsequently filled with four loading levels of wollastonite (10–40 wt%), where the tensile properties (modulus, strain at break, and strength) and thermal stability of the blend were all improved by the addition of wollastonite in a dose‐dependent manner. Based on differential scanning calorimetry analysis, the crystallinity of rPET in the rPET/PBAT/wollastonite composites decreased in the presence of wollastonite, accompanied with a noticeable increase in the glass transition, cold crystallization, and crystallization temperatures, but only a slight change in the melting temperature was noted compared with those of the neat 80/20 wt% blend. Moreover, the addition of wollastonite at 30 wt% or higher showed a strong reduction in the melt dripping of the composites during combustion. J. VINYL ADDIT. TECHNOL., 23:106–116, 2017. © 2015 Society of Plastics Engineers     

Influence of plasticizers and cryogenic grinding on the high‐cooling‐rate solidification behavior of PBT/PET blends

Two structurally different plasticizers (cyclic and linear) and the effect of cryogenic grinding on the solidification behavior at high cooling rates by a continuous cooling transformation approach of poly(butylene terephthalate)/poly(ethylene terephthalate), PBT/PET, blends are described. The solidification curve (density versus cooling rate) is confirmed as an effective tool to compare the differences in crystallization behavior under conditions mimicking processing. In comparison to the bulky cyclic plasticizer, the linear oligomeric one was found to have a more pronounced influence on the crystallization behavior. A 60/40 by weight PBT/PET blend shows a drop‐off of density at ～50 K/s. In the plasticized sample, the long‐range crystalline order appears up to a cooling rate of ～250K/s, making the blend comparable to pure PBT. Grinding the components before blending further improves crystallizability and synergy to the addition of the plasticizer. The results suggest the important role of local chain mobility in the solidification behavior at high cooling rates. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43083.     

Effect of blending sequence on the microstructure and properties of PBT/EVA‐g‐MAH/organoclay ternary nanocomposites

Ternary nanocomposites based on poly(butylene terephthalate) (PBT), maleic anhydride grafted poly(ethylene‐co‐vinyl acetate) (EVA‐g‐MAH), and organically modified montmorllonite (organoclays) were prepared through four different blending sequences in a Haake rheocord mixer: (1) To blend PBT, EVA‐g‐MAH and organoclays in one step; (2) First to prepare EVA‐g‐MAH/organoclay nanocomposite, then mix it with PBT to get the final nanocomposite; (3) To mix PBT with organoclays first, then the PBT/organoclay nanocomposite with EVA‐g‐MAH. (4) To mix organoclays with the PBT/EVA‐g‐MAH blend. The microstructure of the PBT/EVA‐g‐MAH/organoclay ternary hybrids was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). It was found that the blending sequence significantly influences the microstructure of PBT/EVA‐g‐MAH/organoclay ternary hybrids and the dispersion behavior of the organoclays in the polymer matrix. Tensile and impact properties of the hybrids were also studied. The results showed that the mixing sequence (2) gives the best tensile and impact strength due to its fine “sea‐island” morphology of PBT/EVA‐g‐MAH blend and good dispersion of the organoclays in the continuous PBT matrix.     

The vibration welding of polycarbonate/acrylonitrile‐butadiene‐styrene blends to themselves and to other resins and blends

The weldabilities of two commercial blends of polycarbonate (PC) and acrylonitrile‐butadiene‐styrene (ABS) to themselves and to several other resins and blends are assessed through 120 Hz vibration welds of 6.35‐ and 3.2‐mm‐thick specimens. While the thicker specimens of both blends have relative weld strengths of 83%, the thinner specimens in one of the grades have a lower relative weld strength of 73%. Welds of thicker specimens of both grades to PC have relative strengths of 85%. Again, welds of thinner specimens of one of the grades to PC have a lower relative strengths of 68%. Welds of the thinner specimens of this grade with ABS have relative strengths of 85%. Welds of this material with poly(butylene terephthalate) (PBT), a PC/PBT blend, modified poly(phenylene oxide), and a poly(phenylene oxide)/polyamide blend, have relative weld strengths of 45%, 26%, 76%, and 20%, respectively.     

The effect of recycling number on the mechanical,chemical, thermal,and rheological properties of PBT/PC/ABS ternary blends: With and without glass‐fiber

The recycling possibilities of poly(butylene terephthalate)/polycarbonate/acrylonitrile–butadiene–styrene (PBT/PC/ABS) ternary blend with and without glass‐fiber content were investigated using repeated injection molding process. In this study, PBT/PC/ABS ternary blends were reprocessed at five times and the results were presented after each recycling process. The recycling possibility of PBT/PC/ABS ternary blend was evaluated by measuring the mechanical, chemical, thermal, and rheological properties. Mechanical properties were determined by the tensile strength, yield strength, strain at break, elastic modulus, impact strength, flexural strength, and flexural modulus. Chemical and thermal properties were evaluated by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermal gravimetric analysis, and scanning electron microscopy. Rheological properties of the ternary blends were studied by melt flow index measurement. From the results, it was found that mechanical properties of recycled composites were better than virgin PBT/PC/ABS ternary blends. POLYM. COMPOS., 35:2074–2084, 2014. © 2014 Society of Plastics Engineers     

Engineered poly(lactic acid)‐talc biocomposites for melt processing: Effects of co‐blending with poly(butylene succinate) and poly(butylene terephthalate) on thermal and mechanical behavior

This article deals with the design and manufacturing of a novel class of PLA‐based material specifically engineered for injection molding, suitable for food contact and characterized by a good balance of mechanical properties and thermal resistance. A commercial PLA grade was modified by blending it with microlamellar talc as reinforcing filler, poly(butylene succinate) (PBS), and poly(butylene terephthalate) (PBT) as secondary polymeric phases. Ternary blend/talc biocomposites were achieved. The different constituents of the biocomposites were compatibilized by reactive compounding extrusion using maleic anhydride (MAH) grafted PLA (PLA‐MA). The thermal properties of the compounds prior and after injection molding were characterized by differential scanning calorimetry. The mechanical response of the injection molded materials was evaluated by flat indentation and flexural tests. The mechanical properties of the PLA/talc‐based biocomposites and crystallinity of PLA can be controlled by fine tuning the blend by the addition of PBS and PBT in the formulation. In particular, biocomposites characterized by good strength and toughness can be obtained by injection molding, without affecting thermal stability. Based on the experimental findings, the PLA‐based formulations pose; therefore, solid bases for replacing oil‐based plastics in several markets, specifically in the segment of food and pharmaceutical packaging. POLYM. ENG. SCI., 59:264–273, 2019. © 2018 Society of Plastics Engineers     

Hydrolytic degradation of biodegradable polyesters under simulated environmental conditions

In this study, the durability of poly(butylene succinate) (PBS), poly(butylene adipate‐co‐terephthalate) (PBAT), and PBS/PBAT blend was assessed by exposure to 50°C and 90% relative humidity for a duration of up to 30 days. Due to the easy hydrolysis of esters, the mechanical properties of PBS and PBAT were significantly affected with increasing conditioning time. The PBS, PBAT, and PBS/PBAT showed an increase in modulus as well as a decrease in tensile strength and elongation at break with increased exposure time. Furthermore, the impact strength of PBAT remains unaffected up to 30 days of exposure. However, it was clearly observed that the fracture mode of PBS/PBAT changed from ductile to brittle after being exposed to high heat and humid conditions. This may be attributed to the hydrolysis products of PBS accelerating the degradation of PBAT in the PBS/PBAT blend. The differential scanning calorimetry results suggested that the crystallinity of the samples increased after being exposed to elevated temperature and humidity. This phenomenon was attributed to the induced crystallization from low molecular weight polymer chains that occurred during hydrolysis. Therefore, low molecular weight polymer chains are often favored to the crystallinity enhancement. The increase in crystallinity eventually increased the modulus of the conditioned samples. The enhanced crystallinity was further confirmed by polarizing optical microscopy analysis. Moreover, the hydrolysis of the polyesters was evaluated by scanning electron microscopy, rheology, and Fourier transform infrared spectroscopy analysis. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42189.     

Structure development and properties of high-speed melt spun poly(butylene terephthalate)/poly(butylene adipate-co-terephthalate) bicomponent fibers

Ultra-high-speed bicomponent spinning of poly(butylene terephthalate) (PBT) as sheath and biodegradable poly(butylene adipate-co-terephthalate) (PBAT) as core was accomplished with the take-up velocity up to 10 km/min. The structure development of the individual component and the properties of PBT/PBAT fibers were investigated through the measurements on differential scanning calorimetry, wide-angle X-ray diffraction, birefringence and tensile test. Due to the mutual interaction between two polymer-melts along the spinline, the processability of both components in PBT/PBAT bicomponent spinning was improved compared with those of corresponding single component spinnings. Furthermore, in PBT/PBAT fibers, the structure development of PBT component was found to be greatly enhanced, which led to the improvement in its thermal and mechanical properties; whereas the structure development of PBAT component was significantly suppressed, in which nearly non-oriented structure was observed in both crystalline and amorphous phases.     

Strong and ductile poly(butylene adipate‐co‐terephthalate) biocomposites fabricated by oscillation shear injection molding

Poor interfacial properties and uncontrollable phase morphology encountered during the fabrication of poly(butylene adipate‐co‐terephthalate) (PBAT)/thermal plastic starch (TPS) biocomposites, result unfortunately in low mechanical performances and thus limit its applications. Here an approach in terms of phase morphology controlling, i.e., extrusion compounding followed by oscillation shear injection molding (OSIM), is proposed to construct in situ TPS fiber and skin‐core structure consisting of TPS fiber and droplet in skin layer, and spherical TPS in core layer, which tremendously benefits the mechanical properties. Specifically, the tensile strength, modulus and ductility for the biocomposites with various loadings of TPS, even when TPS loading as high as 55 wt %, outperform pure PBAT sample fabricated by conventional injection molding (CIM) with the increment of 51%, 308% in strength and modulus, respectively. Meanwhile, the elongation at breakage can maintain at 196%. The unprecedented establishment of high‐performance PBAT/TPS biocomposites is in great need for potential applications, such as green packaging. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43312.     

The vibration welding of poly(butylene terephthalate) and a polycarbonate/poly(butylene terephthalate) blend to each other and to other resins and blends

Vibration welding is used to assess the weldability of poly(butylene terephthalate) (PBT) and a polycarbonate/poly(butylene terephthalate) blend (PC/PBT) to each other and to other resins and blends: PBT to PC/PBT, PBT to modified poly(phenylene oxide) (M-PPO), PBT to polyetherimide (PEI) and PEI to a 65 wt% mineral-filled polyester blend (65-PF-PEB), PBT to a poly(phenylene oxide)/polyamide blend (PPO/PA), PC/PBT to M-PPO, and PC/PBT to PPO/PA. Based on the tensile strength of the weaker of the two materials in each pair, the following relative weld strengths have been demonstrated: PBT to PC/PBT,98%; PBT to PEI, 95%; 65-PF-PEB to PEI, 92%; and PC/PBT to M-PPO, 73%. PBT neither welds to M-PPO nor to PPO/PA, and PC/PBT does not weld to PPO/PA.     

The Mechanical,Thermal, Rheological and Morphological Properties of PLA/PBAT Blown Films by Using Bis(tert‐butyl dioxy isopropyl) Benzene as Crosslinking Agent

Blown films of poly(lactic acid) (PLA)/poly(butylene adipate‐co‐terephthalate) (PBAT) blends were prepared, bis(tert‐butyl dioxy isopropyl) benzene (BIBP) as crosslinking agent. From wide‐angle X‐ray diffraction results, PLA/PBAT/BIBP involved all the diffraction peaks were consistent with PLA and PBAT. For the DSC curves of PLA/PBAT/BIBP films, there were two glass transition temperature and two melt temperature, there existed two step decomposition in the thermogravimetric curves. Both Han plots and Cole–Cole plots indicated high homogeneity of the 40/60/0.1 PLA/PBAT/BIBP blend. SEM micrographs of the films revealed more ductile deformation with increasing PBAT content and 40/60/0.1 sample had better miscible compared with others. For the PLA/PBAT/BIBP films, tensile tests indicated that the elongation at break were increased with increasing PBAT content and the values of the tensile strength in the machine direction were higher than those in the transverse direction. The addition of PBAT, enhanced the toughness of the PLA/PBAT/BIBP films. From tear test and heat sealing test, the 40/60/0.1 PLA/PBAT/BIBP film exhibited the highest tear strength and the highest sealing strength among all the samples. POLYM. ENG. SCI., 59:E227–E236, 2019. © 2018 Society of Plastics Engineers     

Rheological behavior of polyester blend and mechanical properties of the polypropylene–polyester blend fibers

The article deals with method of preparation, rheological properties, phase structure, and morphology of binary blend of poly(ethylene terephthalate) (PET)/poly(butylene terephthalate) (PBT) and ternary blends of polypropylene (PP)/(PET/PBT). The ternary blend of PET/PBT (PES) containing 30 wt % of PP is used as a final polymer additive (FPA) for blending with PP and subsequent spinning. In addition commercial montane (polyester) wax Licowax E (LiE) was used as a compatibilizer for spinning process enhancement. The PP/PES blend fibers containing 8 wt % of polyester as dispersed phase were prepared in a two‐step procedure: preparation of FPA using laboratory twin‐screw extruder and spinning of the PP/PES blend fibers after blending PP and FPA, using a laboratory spinning equipment. DSC analysis was used for investigation of the phase structure of the PES components and selected blends. Finally, the mechanical properties of the blend fibers were analyzed. It has been found that viscosity of the PET/PBT blends is strongly influenced by the presence of the major component. In addition, the major component suppresses crystallinity of the minor component phase up to a concentration of 30 wt %. PBT as major component in dispersed PES phase increases viscosity of the PET/PBT blend melts and increases the tensile strength of the PP/PES blend fibers. The impact of the compatibilizer on the uniformity of phase dispersion of PP/PES blend fibers was demonstrated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4222–4227, 2006     

Melting,crystallization behaviors,and nonisothermal crystallization kinetics of PET/PTT/PBT ternary blends

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 (T_g) 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 t_1/2 and the parameters Z_c 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     

Influence of phthalic anhydride and bioxazoline on the mechanical and morphological properties of biodegradable poly(lactic acid)/poly[(butylene adipate)‐co‐terephthalate] blends

Poly(lactic acid) (PLA)/poly[(butylene adipate)‐co‐terephthalate] (PBAT) blends were fabricated by melt blending, with 2,2′‐(1,3‐phenylene)bis(2‐oxazoline) (BOZ) and phthalic anhydride (PA) used as compatibilizers. It was found that a small amount of BOZ or PA greatly increased the elongation at break of the PLA/PBAT blends without sacrificing their high tensile strength. Scanning electron microscopy results revealed that the PBAT particles became finer and were uniformly dispersed in the matrix when the compatibilizers were incorporated, which indicated that the interfacial bonding and compatibilization between PLA and PBAT were improved in the presence of the compatibilizers. Compared with PLA/PBAT blends, the molecular weight of PLA/PBAT/PA/BOZ blends was increased due to chain‐extending reactions. Differential scanning calorimetry results suggested PBAT decreased the crystallization rate and crystallinity of PLA in the blends. Moreover, the glass transition temperature of PBAT was further decreased when the compatibilizers were used. © 2013 Society of Chemical Industry     

Reactive modification and compatibilization of poly(lactide) and poly(butylene adipate‐co‐terephthalate) blends with epoxy functionalized‐poly(lactide) for blown film applications

Biodegradable blown films comprising of poly(lactide) (PLA) and poly(butylene adipate‐co‐terephthalate) (PBAT) were produced using epoxy functionalized‐poly(lactide) (EF‐PLA) reactive modifiers for rheological enhancement and compatibilization. The epoxy groups on the EF‐PLA modifiers react with PBAT forming an in situ copolymer that localizes at the blend interphase resulting in compatibilization of the polymer blend components. The EF‐PLA modified polymer blends have improved melt strength and the resultant films showed better processability as seen by increased bubbled stability. This allowed for blown films with higher PLA content (70%) compared to the unmodified control films (40%). The static charge build‐up typically experienced with PLA film blowing was decreased with the inclusion of EF‐PLA yielding films with better slip and softness. The compatibilization effect of the EF‐PLA modifiers resulted in significant improvement in mechanical properties. For example, dart test performance was up to four times higher than the control, especially at higher PLA concentrations. Therefore, the rheological enhancement and compatibilization effects of the EF‐PLA reactive modifiers make them ideally suited to create high PLA content films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43310.     

PLA/PBAT共混物的降解性能研究

通过双螺杆挤出机和吹膜机组制备不同比例的聚乳酸/聚对苯二甲酸己二酸丁二酯（PLA/PBAT）共混物薄膜,测量共混物的热性能、力学性能,并观察其相形貌,计算共混物在堆肥条件下的生物降解率,研究共混物降解前后的结构、热力学行为和元素的变化。结果表明,PLA与PBAT是不相容体系,加入PBAT后PLA的韧性得到改善;PLA的生物降解率高于PBAT,共混物的生物降解率随着PBAT含量的增加而降低,且在降解初期,PLA的降解产物会促进PBAT的水解;PLA、PBAT及其共混物在堆肥降解前期只是大分子链水解为小分子链的过程,不发生分子链的结构变化;PLA及PBAT的降解会先发生在无定形区,共混物中PLA在无定形区的降解速度受到PBAT的影响而变慢,且共混物中PLA、PBAT的降解行为发生变化,无定形区与结晶区的降解同时发生;共混物在堆肥试验初期的降解以水解为主。     

Poly(butylene terephthalate)/ poly(ethylene‐co‐alkyl acrylate)/ carbon black conductive composites: Influence of composition and morphology on electrical properties

Poly(butylene terephthalate)/Poly(ethylene‐co‐alkyl‐acrylate)/carbon black (PBT‐EXA‐CB) blends, prepared through extrusion, were characterized as electrical conductive materials. In the composition range studied (55 ≤ PET % ≤ 75 w/w 5.5 ≤ CB % ≤ 11.1 w/w), various conductive behaviors were observed depending mainly on composition and poly(olefin) crystallinity. The observed positive temperature coefficient (PTC) is quite small compared to poly(olefin)‐CB systems, and our blends do not present a negative temperature coefficient (NTC) on complete melting of the CB‐containing phase, thus offering new possibilities for a regular electric power control. Volume expansion of both PBT and EXA was postulated to be the main parameter responsible for the thermal resistivity evolution through the range +20 to +170°C. A double‐percolation system between both the co‐continuous polymer phases and CB‐particles included in the poly(olefin) phase is postulated to explain these results.     

Morphology and properties of PBT/nylon 6/EVA‐g‐MAH ternary blends prepared by reactive extrusion

Morphology and properties of poly(butylene terephthalate) (PBT)/nylon 6 (PA6)/EVA‐g‐MAH ternary blends were investigated. The blends were prepared in a corotating, intermeshing, twin‐screw extruder. The incorporation of maleic anhyride (MAH) grafted onto ethylene‐vinyl acetate copolymer (EVA) (EVA‐g‐MAH) in the PBT/PA6 binary blends decreased the tensile and flexural strength but increased the impact strength, while the mechanical properties of the PBT/PA6 blends were decreased with increasing PA6 content regardless of the presence or absence of the EVA‐g‐MAH. The morphology studies of the ternary blends showed gross phase separation. The rheological properties of the ternary blends suggested that excessively high reactivity between amine end groups of PA6 and MAH grafted onto EVA makes the compatibility between PBT and PA6 worse, although EVA‐g‐MAH was expected to work as a compatibilizer for PBT/PA6 blends. The degree of reactivity between functional groups in PBT, PA6, and EVA‐g‐MAH was also examined by investigating the effect of blending sequence on the properties of the ternary blends.