Composites of poly(lactic acid)/poly(butylene adipate-co-terephthalate) blend with wood fiber and wollastonite: Physical properties,morphology, and biodegradability

Poly(lactic acid) (PLA) was first melt blended with five weight percentages (10–50 wt %) of poly(butylene adipate-co-terephthalate) (PBAT) on a twin-screw extruder and then injection molded. The blend at 30 wt % PBAT exhibited the highest impact strength and elongation-at-break without phase inversion. The 70/30 (w/w) PLA/PBAT blend with high toughness improvement was selected for preparing both single and hybrid composites using an organic filler, wood fiber (WF) and inorganic filler, wollastonite (WT) with a fix total loading at 30 parts per hundred of resin (phr) throughout the experiment. Five WF/WT (phr/phr) ratios for the composites were 30/0, 10/20, 15/15, 20/10, and 0/30. The prepared composites were investigated for the mechanical and thermal properties, melt flow index (MFI), morphology, flammability, water uptake, and biodegradability as a function of composition. All the composites showed a filler-dose-dependent decrease in the impact strength, elongation-at-break, MFI, and thermal stability, but an increase in the tensile and flexural modulus, tensile and flexural strength, antidripping ability, and water uptake compared with the neat blend. The addition of WF and WT was also found to promote the biodegradability of the PLA/PBAT blend. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47543.     

Biodegradable Poly(butylene adipate-co-terephthalate) composites reinforced with bio-based nanochitin: Preparation,enhanced mechanical and thermal properties

The accumulation of nonbiodegradable petrochemical-based polymers in the environment motivates the development and use of low-cost, eco-friendly, and biodegradable polymers. A series of biodegradable poly(butylene adipate-co-terephthalate) composites reinforced by sustainably sourced nanochitin were successfully prepared using melt blending and compression molding methods. Structural, thermal, and mechanical characterizations of poly(butylene adipate-co-terephthalate) (PBAT)/nanochitin composites were performed. SEM revealed that the nanochitin was uniformly dispersed throughout the PBAT matrix at low contents (<2 wt %), while DSC analyses revealed a corresponding increase in the crystallinity (32.6% enhancement) of the PBAT matrix. The tensile strength and elongation at break of the PBAT/nanochitin composite containing 0.5 wt % nanochitin were higher by 82.5 and 64.2%, respectively, compared with pristine PBAT. The Chitin-0.5 composite also showed improved thermal stability compared with PBAT (the char yield improved by 8%) due to the uniform dispersion of nanochitin in the PBAT matrix. The enhanced performance of the PBAT/nanochitin composites, prepared without an added compatibilizer, informs the development of improved biodegradable PBAT-based polymers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48485.     

聚乳酸/聚(已二酸-对苯二甲酸丁二酯)共混物的非等温结晶动力学

采用熔融挤出法制备了聚乳酸/聚(已二酸-对苯二甲酸丁二酯)共混物。利用差示扫描量热仪研究了聚乳酸及其共混体系的非等温结晶过程。用经Jeziorny修正的Avrami方程和Mo法对其非等温结晶动力学进行了分析。结果表明:Avrami方程和Mo法都适用于处理聚乳酸及其共混体系的非等温结晶过程,共混物的结晶速率大于聚乳酸的结晶速率。此外,用Huffman-Lauritzen理论计算了非等温结晶的结晶活化能,发现共混体系的结晶活化能绝对值小于聚乳酸。     

Morphology,Thermal and Mechanical Properties of Biodegradable Poly(butylene succinate)/Poly(butylene adipate-co-terephthalate)/Clay Nanocomposites

Sodium montmorillonite (Na-MMT) was successfully modified by octadecylamine (ODA) through a cation exchange technique that showed by the increased of basal spacing of clay by XRD. The addition of the organoclay into the PBS/PBAT blends produced intercalated-type nanocomposites with improvements in tensile modulus and strength. The highest tensile strength of nanocomposite was observed at 1 wt% of organoclay incorporated. A TGA study showed that the thermal stability of the blend increased after the addition of the organoclay by 1 wt%. SEM micrographs of the fracture surfaces show that the morphology of the blend becomes smoother with presence of organoclay.     

Effect of nanofillers characteristics and their selective localization on morphology development and rheological properties of melt-processed polylactide/poly(butylene adipate-co-terephthalate) blend composites

This article reports the effects of the characteristics and selective localization of nanofillers on the morphology development and rheological properties of melt-processed polylactide/poly(butylene adipate-co-terephthalate) (PLA/PBAT) blend composites. Four types of nanofillers (1 wt%) are used: nanoclay (Cloisite30B [C30B]), carbon nanotubes (CNTs), nanosilica, and graphene oxide (GO). Transmission electron microscopy studies reveal that C30B is localized mainly at the PLA/PBAT interface, whereas silica, GO, and CNT are localized in PBAT droplets, although some CNTs also appear toward the interface inside the PBAT. Despite their selective localization inside the PBAT, CNTs are found to be the most effective particles for droplet size reduction, whereas silica nanoparticles are ineffective. The CNT bundles recoil during melt blending, and eventually, their breakage facilitates droplet breakup. The effects of nanofiller localization and annealing under dynamic shear on the blend morphologies are also explored through rheological analysis. The results show an anomalous relationship with the morphologies of the composites. It is also found that both coalescence and thermal degradation are involved in the annealing process of the blends. Interestingly, the CNT-filled composites may have been transformed into co-continuous-like structures during annealing, unlike the other blends studied here.     

Physical Properties,Crystallization, and Thermal/Hydrolytic Degradation of Poly(L‐lactide)/Nano/Micro‐Diamond Composites

The effects of incorporated nano/micro‐diamond (NMD) on the physical properties, crystallization, thermal/hydrolytic degradation of poly(L ‐lactic acid) (PLLA) were investigated for a wide NMD concentration range of 0–10 wt.‐%. Incorporated NMD increased the tensile modulus and strength of PLLA films but decreased the elongation at break of PLLA films. Incorporated NMD accelerated the crystallization of PLLA during heating and cooling and increased the absolute crystallization enthalpy of PLLA films (except for an NMD concentration of 10 wt.‐% during cooling) but did not alter the crystallization mechanism. Incorporated NMD increased and decreased the thermal stability of PLLA films for NMD concentrations of 1–5 and 10 wt.‐%, respectively, and increased the hydrolytic degradation resistance of PLLA films.

     

聚丁二酸丁二醇酯/乙烯-醋酸乙烯共混物的形态与性能研究

用乙烯-醋酸乙烯橡胶（EVM）对聚丁二酸丁二醇酯（PBS）进行增韧改性,通过添加过氧化二异丙苯（DCP）使得PBS与EVM的相容性增强。结果表明,随着DCP含量的增大,PBS/EVM共混物的拉伸强度、断裂伸长率、肖氏硬度等力学性能先升高,随后又降低,其中拉伸强度由7 MPa 提高到17 MPa,100 %定伸应力由2 MPa提高到10 MPa;加入DCP使得PBS的结晶由受限结晶变为正常结晶;DCP的适宜添加量为0.3份。     

Effect of Poly(L-lactic acid) on Hydrolytic Degradation of Poly(glycolic acid)

The in-vitro degradation behavior of poly(glycolic acid) (PGA) rods and the composite rods containing poly(L-lactic acid) (PLLA) were investigated via mass loss, pH value change, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Since the degradation rate of PLLA is lower than that of PGA, PLLA/PGA composite rods exhibit a slower degradation rate in comparison with PGA. This finding indicated that it was possible to control the degradation rate of the composites by changing their composition. This result indicates that this kind of composite biomaterial may be applicable to devices for the need of prolonged degradation.     

聚丁二酸丁二醇酯的酶促降解研究

以聚丁二酸丁二酯（PBS）薄片为降解底物,利用角质酶对其进行降解研究,考察PBS的酶促降解行为。利用扫描电子显微镜、差示扫描量热仪和热重分析仪等方法对降解前后的PBS薄片进行了表征分析,并进一步采用质谱仪对降解产物进行分析。结果表明,在酶浓度2.5 U/mL、反应温度37 ℃以及pH 7.4的条件下,经16 h降解PBS薄片的降解率可达93.88 %,在降解时间为2 h时有最大降解速率32.97 μg/cm2·h;PBS薄片有片层脱落降解的现象,促进了角质酶的降解作用;随降解时间的延长,PBS相对结晶度逐渐降低,热稳性也呈现下降趋势;PBS被降解成单体或寡聚物。     

Effect of Organoclay on the Morphology and Properties of Poly(propylene)/Poly[(butylene succinate)‐co‐adipate] Blends

The effect of organically modified clay on the morphology and properties of poly(propylene) (PP) and poly[(butylene succinate)‐co‐adipate] (PBSA) blends is studied. Virgin and organoclay modified blends were prepared by melt‐mixing of PP, PBSA and organoclay in a batch‐mixer at 190 °C. Scanning electron microscopy studies revealed a significant change in morphology of PP/PBSA blend in the presence of organoclay. The state of dispersion of silicate layers in the blend matrix was characterized by X‐ray diffraction and transmission electron microscopic observations. Dynamic mechanical analysis showed substantial improvement in flexural storage modulus of organoclay‐modified blends with respect to the neat polymer matrices or unmodified blends. Tensile properties of virgin blends also improved in the presence of organoclay. Thermal stability of virgin blends in air atmosphere dramatically improved after modification with organoclay. The effect of organoclay on the melt‐state liner viscoelastic properties of virgin blends was also studied. The non‐isothermal crystallization behavior of homopolymers, virgin, and organoclay‐modified blends were studied by differential scanning calorimeter. The effect of incorporation of organoclay on the cold crystallization behavior of PP/PBSA blends is also reported.

     

Preparation of Poly(ethylene terephthalate)/Poly(amino ether) Blends by means of the Addition of Poly(butylene terephthalate)

Summary: Blends based on poly(ethylene terephthalate), PET, with poly(amino ether) (PAE) contents up to 40% were obtained by the addition of 20% poly(butylene terephthalate) (PBT) to the PET matrix. PBT mixed with PET led to a decrease in the T_m of the matrix that was enough to produce homogeneous blends by mixing in the melt state. Despite the presence of a single peak observed by dynamic‐mechanical analysis, the blends were biphasic, with amorphous phases in which minor amounts of the other component, both reacted and mixed, were present. This presence of minor components gave a fine morphology and significant adhesion that, together with the higher orientation of PAE in the blends, produced blends with a clear synergism in the modulus of elasticity, notched impact strength similar to that of the neat components, and high ductility up to 30% PAE.

Young's modulus of the PET‐PBT/PAE blends.     

Strengthening of poly(butylene adipate-co-terephthalate) by melt blending with a liquid crystalline polymer

Poly(butylene adipate-co-terephthalate) (PBAT) is a soft biodegradable polymer with a low melting temperature. PBAT has been melt-blended with a liquid crystalline polymer (LCP) aiming at preparing a new biodegradable polymer blend with improved mechanical properties. The phase structure and crystalline morphologies of the PBAT/LCP blends were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). It was found that the LCP domains are precisely dispersed in the PBAT matrix and that these domains act as the nuclei for PBAT crystallization. The nonisothermal crystallization temperature from the melt was dramatically shifted from 50°C to about 95°C by the addition of 20% LCP. In addition, the tensile modulus of the prepared blends increases gradually with increasing LCP content, indicating the excellent strengthening effects of LCP on the PBAT matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical and Thermal Properties of Poly(Phthalazinone Ether Sulfone)/Poly(Ether Sulfone) Blends

The mechanical and thermal properties of poly(phthalazinone ether sulfone) (PPES)/poly(aryl ether sulfone) (PES) blends prepared by melt-mixing were investigated by dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA). The dynamic mechanical thermal analysis results show that the incorporated PES has a large influence on the heat stability of PPES. The DMTA results display that the blends with a single glass transition temperature, which increases with increasing PPES content, indicates that PPES and PES are completely miscible over the studied composition range. The thermodegradative behavior of PPES/PES blends was used to analyze their thermal stability. The Friedman technique was used to determine the kinetic parameters (i.e., the apparent activation energy and order of reaction of the degradation process). The results indicate that the presence of the PES component influences the thermal stability of the PPES. On the basis of the kinetic data derived from Friedman' approach, the lifetime estimates for pure PPES, pure PES, and the blends generated from the weight loss of 5% were constructed.     

Poly(lactide)/cellulose nanocrystal nanocomposites by high-shear mixing

There is currently considerable interest in developing stiff, strong, tough, and heat resistant poly(lactide) (PLA) based materials with improved melt elasticity in response to the increasing demand for sustainable plastics. However, simultaneous optimization of stiffness, strength, and toughness is a challenge for any material, and commercial PLA is well-known to be inherently brittle and temperature-sensitive and to show poor melt elasticity. In this study, we report that high-shear mixing with cellulose nanocrystals (CNC) leads to significant improvements in the toughness, heat resistance, and melt elasticity of PLA while further enhancing its already outstanding room temperature stiffness and strength. This is evidenced by (i) one-fold increase in the elastic modulus (6.48 GPa), (ii) 43% increase in the tensile strength (87.1 MPa), (iii) one-fold increase in the strain at break (∼6%), (iv) two-fold increase in the impact strength (44.2 kJ/m²), (v) 113-fold increase in the storage modulus at 90°C (787.8 MPa), and (vi) 10³-fold increase in the melt elasticity at 190°C and 1 rad/s (∼10⁵ Pa) via the addition of 30 wt% CNC. It is hence possible to produce industrially viable, stiff, strong, tough, and heat resistant green materials with improved melt elasticity through high-shear mixing.     

E-BA-GMA三嵌段共聚物对PLA/PBAT体系的增韧改性研究

研究了乙烯-丙烯酸正丁酯-甲基丙烯酸缩水甘油酯三嵌段共聚物(E-BA-GMA)作为增韧剂对聚乳酸(PLA)/对苯二甲酸、己二酸、1,4-丁二醇三元共聚酯(PBAT)共混物的力学性能、流动性能、热性能和断面形貌的影响。结果表明:E-BA-GMA的环氧官能团与PBAT/PLA体系的端羧基和端羟基发生反应,使得PBAT与PLA的相容性得到改善,共混物的冲击性能得到了明显的提高;E-BA-GMA的加入导致结晶温度向低温方向偏移和结晶度下降。     

Effect of Maleic‐Anhydride Grafting on the Physical and Mechanical Properties of Poly(L‐lactic acid)/Starch Blends

MA is grafted onto both PLLA and starch in an internal mixer in the presence of DCP in a one‐step reactive compatibilization process. The effect of maleation of MA on the physical and mechanical properties and morphology of the blends was assessed. The onset decomposition temperature of the PLLA/starch blends decreased as the starch content increases due to the lower thermal stability of starch and the low effect of the maleation reaction on the thermal stability of the blends. PLLA/starch blends without grafted MA showed higher crystallinity as the starch content increased. Reactive compatibilized blends with less than 20 wt% starch had higher storage modulus, indicating that the compatibility between the two phases was improved.

     

Mechanical and Rheological Properties of Poly(ethylene terephthalate)/ Polypropylene Blends

Poly(ethylene terephthalate) and polypropylene (PET/PP) were compounded and pelletized with a single-screw extruder. Standard ASTM tensile test specimens were made by injection moulding. The blends are stronger and stiffer than the plain PP specimens. The addition of a compatibilizer, EPOLENE E-43, is found to improve the strength and stiffness of the blends at loadings of 50% and 70% PET. At 10% PET loading, E-43 has the opposite effect of slightly reducing the tensile properties. All the blends are more brittle relative to either plain PET or PP. The addition of E-43 results in negligible improvement in the elongation at break. E-43 is also found to be an effective lubricant in improving the processability of the blends. The blends with E-43 added have lower viscosities and less shear-thinning characteristics than those without E-43. © 1997 SCI.     

P3/4HB/PBS共混物的物理性能及微生物降解

将不同比例的聚(3-羟基丁酸-co-4-羟基丁酸)共聚酯(P3/4HB)和聚丁二酸丁二酯(PBS)进行物理共混,通过FTIR、DSC、TG和SEM研究了复合材料的力学性能、亲水性能、热稳定性和结晶性。当PBS的添加量为10%时,复合材料的力学性能较好。与纯P3/4HB相比,拉伸强度增加了154%,达到了18.6 MPa;断裂伸长率增加了82%,为638%;弹性模量约下降94 MPa。复合物水溶解性能较小,只有0.34%,抗水性增强。DSC分析表明,2种聚合物的相容性较好。PBS的添加降低了材料的熔点,增加了结晶性能,同时减缓了材料的结晶速率。TG分析结果表明,复合材料稳定性增强,加工窗口拓宽了32℃。采用Pseudomonas.mendocina DS04-T菌株降解复合材料,当降解时间为120 h时,复合材料降解率为92.5%。     

Partially Bio-Based Polyester Bead Foams via Extrusion Foaming of Poly(butylene terephthalate)/Poly(butylene furanoate) Blends

The interest in bio-based alternatives to classical polyesters such as poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) is steadily growing to achieve a more sustainable approach to polymer materials. In this study, PBT/poly(butylene furanoate) (PBF) blends are prepared, characterized and extrusion foamed. PBF as a bio-based polyester offers two advantages. The ecological footprint of the material is reduced, and additionally, it can be used in Diels-Alder reactions at the blend surface to support fusion of the foamed beads. The blending behavior of the polyesters is investigated using samples prepared in a microcompounder, particularly focused on the miscibility of the blends and transesterification reactions. The blends are thermodynamically immiscible but show a certain degree of transesterification according to nuclear magnetic resonance (NMR) spectroscopy. The morphology of blend beads produced by an extrusion foaming process is analyzed regarding their cell density, cell size distribution, and open-cell content. It is shown that PBF has a positive effect on the bead foam morphology. The use of a bifunctional linker designed for chemical fusion of the bead surfaces allows to obtaining of molded parts, in contrast to beads containing pure PBT.