Blends of polylactide and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) with low content of hydroxyvalerate unit: Morphology,structure, and property

The Polylactide (PLA)/poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) blends with four different weight ratios were prepared by melt mixing. PLA and PHBV in PLA/PHBV blends were immiscible while the weak interaction between PLA and PHBV existed. The PHBV domains below 2 μm were dispersed in PLA matrix uniformly. The addition of PHBV made the crystallization of PLA easier due to PHBV acting as nucleating agent. PLA spherulites in PLA/PHBV blends presented various banded structures. In addition, the crystallinity of neat PLA was lower than those of PLA/PHBV blends. With the increase of PHBV content in PLA/PHBV blends, the crystallinity of PLA/PHBV blends increased. PHBV could enhance significantly the toughness of PLA. However, with the increase of PHBV content, the yield stress (σ_y), tensile modulus (E), and the yield strain (ε_y) of PLA/PHBV blends decreased gradually. In addition, incorporation of PHBV to PLA caused a transformation from an optical transparent to an opaque system. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42689.     

Reactive compatibilization and performance evaluation of miscanthus biofiber reinforced poly(hydroxybutyrate‐co‐hydroxyvalerate) biocomposites

Dicumyl peroxide (DCP) initiated reactive compatibilization of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV)/miscanthus fibers (70/30 wt %) based biocomposite was prepared in a twin screw extruder followed by injection molding. In the presence of DCP, both the flexural and the tensile strength of the PHBV/miscanthus composites were appreciably higher compared with PHBV/miscanthus composite without DCP as well as neat PHBV. The maximum tensile strength (29 MPa) and flexural strength (51 MPa) were observed in the PHBV/miscanthus composite with 0.7 phr DCP. The enhanced flexural and tensile strength of the PHBV/miscanthus/DCP composites are attributed to the improved interfacial adhesion by free radical initiator. Unlike flexural and tensile strength, the modulus of the PHBV/miscanthus/DCP composites was found to slightly lower than the PHBV/miscanthus composite. The modulus difference in the PHBV/miscanthus composite with and without DCP has good agreement with the observed crystallinity. However, the flexural and tensile modulus of all the prepared biocomposites was at least two fold higher than the neat PHBV. The storage modulus value of the PHBV/miscanthus and PHBV/miscanthus/DCP biocomposites follows similar trend like tensile and flexural modulus. The melting temperature and crystallization temperature of PHBV/DCP and PHBV/miscanthus/DCP samples were considerably lower compared with the neat PHBV and PHBV/miscanthus composites. The surface morphology revealed that the PHBV/miscanthus/DCP composites have good interface with less fiber pull‐outs compared with the corresponding counterpart without DCP. This suggests that the compatibility between the matrix and the fibers is enhanced after the addition of peroxide initiator. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44860.     

Preparation and characterization of poly(lactic acid)/recycled polypropylene blends with and without the coupling agent,n-(6-aminohexyl)aminomethyltriethoxysilane

Blends of polylactide (PLA) and recycled polypropylene (rPP) were prepared by melt-processing using a corotating twin-screw extruder and subsequent pelletizing of the extrudates for injection molding. The PLA/rPP blends were characterized by Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), rheometer (MCR-102), scanning electron microscopy(SEM), tensile tests, and impact measurements. The results indicate that the PLA/rPP blend is immiscible and has a two-phase structure. TGA revealed enhancement of the thermal stability of the blends upon addition of rPP. The storage modulus, loss modulus, and complex viscosity of the blends increased with rPP concentration. Mechanical studies showed that introduction of rPP results in a decrease in tensile strength and modulus and enhancement of the impact strength of PLA in the blends. The effects of a silane coupling agent on the morphology and on the tensile and impact properties of the rPP blends of silane-modified PLA were also examined. SEM studies suggest that silane is an effective interfacial modifier. Thus, better interfacial adhesion was observed with silane-modified blends as compared with unmodified blends. Silane also improved the mechanical properties of the modified blends. The blends reached maximum tensile strength at 1.5 wt.% silane (relative to modified PLA content), and impact strength increased with increasing silane concentration. These results confirm the enhancing effect of silane on modified PLA/rPP blends.     

Toughening of polylactide with epoxy-functionalized methyl methacrylate–butyl acrylate copolymer

Glycidyl methacrylate-functionalized methyl methacrylate–butyl acrylate (GACR) core–shell structure copolymers were synthesized to toughen polylactide (PLA). With an increase in GACR content, the PLA/GACR blends showed decreased tensile strength and modulus; however, the elongation at break and the impact strength were significantly increased compared with that of PLA. The brittle fracture of neat PLA was gradually transformed into ductile fracture by the addiction of GACR. From dynamic mechanical analysis, the rigidity of the PLA/GACR blends was decreased with the increase of GACR content. The addition of GACR decreased the degree of crystallinity of PLA. The GACR was found to aggregate to form clusters with size increasing with increasing GACR content by transmission electron microscope analysis. The clusters dispersed in PLA matrix uniformly. It was found that PLA demonstrated large area, plastic deformation (shear yielding) and cavities in the blend upon being subjected the tensile and impact tests, which was an important energy-dissipation process and led to a toughened and transparent blend.     

聚乳酸／聚（3⁃羟基丁酸⁃co⁃3⁃羟基戊酸酯）共混材料3D打印线材改性研究

采用熔融共混法制备聚乳酸／聚（3?羟基丁酸?co?3?羟基戊酸酯）（PLA/PHBV），以及分别添加苯乙烯?甲基丙烯酸缩水甘油酯共聚物（ADR）、柠檬酸三丁酯（TBC）的共混物PLA/PHBV/ADR和PLA/PHBV/TBC，通过注塑和熔融沉积成型（FDM）技术制备了标准测试样条，研究了添加ADR和TBC后对PLA/ PHBV共混材料及三维（3D）打印样品热学性能和力学性能的影响。结果表明，PHBV结晶度均降低，加入ADR的注塑样品断裂伸长率最大提高到32 %，加入TBC的注塑样品拉伸强度和冲击强度提高，断裂伸长率提高到2.8 %；加入ADR的3D打印制品拉伸强度降低，断裂伸长率提高，添加TBC的3D打印制品相容性得到了明显的提升，通过扫描电子显微镜（SEM）观察无明显的颗粒相，拉伸强度在改性前后无明显变化。     

Tensile properties in the oriented blends of high-density polyethylene and isotactic polypropylene obtained by dynamic packing injection molding

In this article, tensile properties have been discussed in terms of phase morphology, crystallinity and molecular orientation in the HDPE/iPP blends, prepared via dynamic packing injection molding, with aid of scanning electron microscopy (SEM), differential scanning calorimetry (DSC) as well as two dimensional X-ray scattering (2D WAXS). For the un-oriented blends, the tensile properties (tensile strength and modulus) are mainly dominated by the phase morphology and interfacial adhesion related to the influenced crystallization between HDPE and iPP component. A maximum in tensile strength and modulus is found at iPP content in the range of 70-80 v/v%. As for the oriented blends, however, the presence of dispersed phase in the blends, independent of phase morphology and crystallinity, always makes tensile properties to be deteriorated through reducing molecular orientation of matrix. It is molecular orientation of matrix that determines the tensile properties of oriented blends. In the blends with HDPE as matrix, steep decreasing of tensile properties is related to the rapid reducing of molecular orientation of HDPE, whereas in the blends with iPP as a major component, slight decreasing of molecular orientation of iPP results in slight reducing of tensile properties. Other factors, such as interfacial properties and phase morphology, seem to be little contribution to the modulus and tensile strength.     

Thermal,mechanical, and morphological properties of polylactic acid toughened with an impact modifier

Polylactic acid (PLA) was melt‐blended with different amount (0 to 50 wt %) of a commercially available ethylene acrylate copolymer impact modifier. PLA/impact modifier blends were prepared via an internal mixer and compression molded into test specimens. The thermal, mechanical, and morphological properties of the blends were investigated. The addition of impact modifier decreased the ability of PLA to crystallize and/or recrystallize. The degree of crystallinity of PLA decreased while the cold crystallization temperature shifted to higher temperatures with increasing the impact modifier content. PLA/impact modifier blends were partially miscible. This was confirmed by the dynamic mechanical analysis (DMA) tests. With increasing the impact modifier content, the blends showed some improvement in the elongation at break and notched impact strength indicating the toughening effects of the impact modifier. In contrast, the yield stress and tensile modulus decreased with the increase in the impact modifier content. Scanning electron microscopy (SEM) micrographs revealed that the toughening mechanisms among others involved shear yielding or plastic deformation of the PLA matrix induced by interfacial debonding between the PLA and the impact modifier domains. PLA with 30 wt % impact modifier showed comparable yield stress and tensile modulus and better elongation at break and impact strength (+90%) than those of polypropylene (PP). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123:2715–2725, 2012     

Effect of different biopolymers and polymers on the mechanical and permeation properties of extruded PHBV cast films

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.     

Properties of silanized nypa fruticans filled polylactic acid/recycled low density polyethylene biocomposites

The biocomposites of Nypa Fruticans (NF) and Polylactic acid (PLA)/recycled low density polyethylene (rLDPE) were prepared using Brabender EC PLUS. The effect of NF content and silane coupling agent on mechanical, thermal, and morphological properties were studied. The results show that addition of NF in PLA/rLDPE biocomposites have decreased the tensile strength, elongation at break, and crystallinity of biocomposites. The Young's modulus of biocomposites and thermal stability increased with the increasing NF content. The surface of NF fillers were silanized to improved the interfacial adhesion between the NF filler and PLA/rLDPE matrix. It was found that the tensile strength, Young's modulus, crystallinity of PLA, and thermal stability of silanized biocomposites higher as compared to untreated biocomposites. The enhancement of the properties of biocomposites with silane treatment was proven by SEM studied. The silanized biocomposites showed better interfacial interaction and adhesion between NF and PLA/rLDPE matrix. POLYM. ENG. SCI., 55:1733–1740, 2015. © 2014 Society of Plastics Engineers     

Highly toughened polylactide by renewable Eucommia ulmoides gum

Polylactide (PLA) derived from natural sources has attracted increasing interest and has provided a promising alternative to traditional plastics derived from petroleum sources. With no loss of environmental friendly features, PLA was highly toughened by Eucommia ulmoides gum (EUG) derived from Eucommia ulmoides oliv. The dynamic mechanical analysis, scanning electron microscopy (SEM), and differential scanning calorimetry results show that the PLA–EUG blends were immiscible systems. SEM micrographs revealed that EUG particles were well dispersed in the PLA matrix with number‐average particle diameters of 2–4 μm. The mechanical properties indicated that the tensile strength decreased with increasing EUG contents, but the elongation at break and the impact strength were enhanced. The notched impact strength of the blends improved by 5.9‐fold compared to that of neat PLA. The PLA–EUG blends exhibited distinct shear‐thinning behavior; this indicated good processability, and the storage modulus and loss modulus of the PLA–EUG blends increased with EUG content. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46017.     

聚乳酸/淀粉复合材料的制备及性能研究

采用熔融共混的方法制备了聚乳酸/淀粉复合材料。通过力学测试、DSC、DMA和SEM等分析,研究了聚乳酸和淀粉在不同质量配比下,复合材料力学性能、热性能、吸水率的变化,并研究了增容剂环氧树脂对复合材料性能的影响。通过研究发现,随着淀粉含量的增加,复合材料力学性能下降,结晶度减小,储能模量降低,吸水率增大;环氧树脂的加入能提高复合材料的力学性能;SEM分析表明,聚乳酸/淀粉复合材料的断裂面呈脆性断裂特征。     

SEBS-g-MAH增韧聚乳酸的性能研究

采用哈克密炼机制备了聚乳酸(PLA)与马来酸酐接枝苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚弹性体(SEBS-g-MAH)的共混物,并对共混物的力学性能、流变性能和微观结构进行了分析。结果表明,共混物的拉伸强度随着SEBS-g-MAH含量的增加而下降,断裂伸长率随着SEBS-g-MAH含量的增加而增大。当SEBS-g-MAH的含量为30 %时,共混物的冲击强度提高了2.5倍,共混物的韧性得到提高。随着SEBS-g-MAH含量的增加,PLA熔体黏度的变化趋势与SEBS-g-MAH越来越相似,即熔体黏度随着频率的增大而下降。扫描电镜分析表明,MAH基团改善了两相间的界面作用,增韧作用明显。     

Biodegradable poly(lactic acid)/poly(butylene succinate)/wood flour composites: Physical and morphological properties

This work sought to improve the toughness and thermal stability of poly(lactic acid) (PLA) by incorporating poly(butylene succinate) (PBS) and wood flour (WF). The PLA/PBS blends showed a PBS‐dose‐dependent increase in the impact strength, elongation at break, degree of crystallinity, and thermal stability compared to the PLA, but the tensile strength, Young's modulus, and flexural strength were all decreased with increasing PBS content. Based on the optimum impact strength and elongation at break, the 70/30 (w/w) PLA/PBS blend was selected for preparing composites with five loadings of WF (5–30 phr). The impact strength, tensile strength, flexural strength, and thermal stability of the PLA/PBS/WF composites decreased with increasing WF content, and the degree of crystallinity was slightly increased compared to the 70/30 (w/w) PLA/PBS blend. Based on differential scanning calorimetry, the inclusion of PBS and WF into PLA did not significantly change the glass transition and melting temperatures of PLA in the PLA/PBS blends and PLA/PBS/WF composites. From the observed cold crystallization temperature of PLA in the samples, it was evident that the degree of crystallinity of PLA in all the blends and composites was higher than that of PLA. The PLA/PBS blend and PLA/PBS/WF composite degraded faster than PLA during three months in natural soil, which was due to the fast degradation rate of PBS. POLYM. COMPOS., 38:2841–2851, 2017. © 2016 Society of Plastics Engineers     

PP／PET／EPDM-g-GMA共混物结构与性能研究

通过反应共混制备了PP／PET／EPDM—g-GMA共混物。用扫描电镜和图像处理软件对共混物形貌进行定性和定量分析，用偏光显微镜观察共混物等温结晶形态，最后测量共混物的力学性能。结果表明：在PP／PET共混物中加入EPDM-g—GMA后，两相相容性改善，进一步加入成核剂后分散相尺寸更小、粒径分布更均匀；PP球晶随PET的混入而减小；在PP／PET体系中加入EPDM-g—GMA起到反应增容和橡胶增韧的协同效应，使缺口冲击强度由未加增容剂时的2．0kJ／m^2提高至6．6k．1／m^2，弹性模量较PP提高了38％；PP／PET共混物的拉伸强度随PET含量的增加下降，在相同PET含量的情况下，加入EPDM—g-GMA后，共混物的拉伸强度与未增容体系基本一致。     

Miscibility of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) with high molecular weight poly(lactic acid) blends determined by thermal analysis

An important strategy used in the polymer industry in recent years is blending two bio‐based polymers to attain desirable properties similar to traditional thermoplastics, thus increasing the application potential for bio‐based and bio‐degradable polymers. Miscibility of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) with poly(L ‐lactic acid) (PLA) were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Three different grades of commercially available PLAs and one type of PHBV were blended in different ratios of 50/50, 60/40, 70/30, and 80/20 (PHBV/PLA) using a micro‐compounder at 175°C. The DSC and TGA analysis showed the blends were immiscible due to different stereo configuration of PLA polymer and two distinct melting temperatures. However, some compatibility between PHBV and PLA polymers was observed due to decreases in PLA's glass transition temperatures. Additionally, the blends do not show clear separation by SEM analysis, as observed in the thermal analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

扩链剂TMP-6000对聚乳酸/聚（3-羟基丁酸-co-3 -羟基戊酸酯）共混物性能的影响

以扩链剂TMP-6000为增容剂,采用熔融共混制备了聚乳酸（PLA）和聚（3羟基丁酸co3羟基戊酸酯）（PHBV）复合材料,研究了TMP-6000对PLA/PHBV复合材料的结晶行为、微观结构、力学性能的影响。结果表明,无定形PLA的加入抑制了PHBV的结晶,TMP-6000的加入使得PLA/PHBV复合材料的结晶能力变弱,提高了PLA的冷结晶温度,且当TMP-6000含量为0.5 %（质量分数,下同）时,PLA的冷结晶峰开始消失,且适量的TMP-6000使得PHBV的玻璃化转变温度（Tg）升高;TMP-6000的加入使得PHBV均匀分散于PLA基体中,且当TMP-6000含量为0.7 %时,PLA与PHBV的相容性最好;TMP-6000的加入显著提高了PLA/PHBV复合材料的分子量;TMP-6000提高了PLA与PHBV之间的结合力,提高了复合材料的拉伸强度,但断裂伸长率有稍微地降低。     

The Effects of Process Engineering on the Performance of PLA and PHBV Blends

The effects of process engineering in the fabrication of PHBV, PLA and their blends prepared by melt blending are studied. The elongation of an optimized blend can be improved by 148 and 250% over the virgin PHBV and PLA polymers, respectively. DSC shows that the two polymers are immiscible in blends of any composition. The crystallinity of PHBV is hindered by the presence of PLA. UV‐Vis demonstrates the opacity of the blend with incorporation of PHBV to the PLA phase. The observed tensile modulus of the optimized sample is compared with theoretical values from the rule of mixtures. Gordon‐Taylor's equation is applied on the glass transition temperatures for theoretical modeling to explain the miscibility of the polymers.

     

Effect of clay type and polymer matrix on microstructure and tensile properties of PLA/LLDPE/clay nanocomposites

Polylactide (PLA)/linear low‐density polyethylene (LLDPE), (PLA/LLDPE), blends and nanocomposites were prepared by melt mixing process with a view to fine tune the properties. Two different commercial‐grade nanoclays, Cloisite® 30B (30B) and Cloisite® 15A (15A) were used. A terpolymer of ethylene, butylacrylate (BA) and glycidylmethacrylate (GMA) was used as a reactive compatibilizer. The influence of type of clay on the morphology and mechanical properties of two PLA‐rich and LLDPE‐rich blend systems was studied. Morphological analysis using X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy revealed that the organoclay layers were dispersed largely at the interface of PLA/LLDPE. Decreasing the PLA content changed the morphology from droplet‐in matrix to coarse co‐continuous. In comparison with 30B, due to less affinity of 15A towards compatibilizer and PLA phase, the reduction of the size of dispersed phase was less than that of the equivalent 30B composites. The mechanical results demonstrated that the composites containing both types of organoclay exhibited higher modulus but lower elongation and tensile strength as compared to the neat blends. The injection molded nanocomposites were shown to have the sequential fracture behavior during tensile test. The tensile testing results on the neat blends and nanocomposites showed significant increase in elongation at break and decrease in the modulus as compared with the neat PLA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 749‐758, 2013     

Effects of nanosilica filler surface modification and compatibilization on the mechanical,thermal and microstructure of PP/EPR blends

Polypropylene/ethylene-propylene rubber/nanosilica (PP/EPR/nano-SiO₂) composites were prepared by a melt blending masterbatch process using a Brabender mixer. In order to improve the interfacial adhesion and achieve diverse desired properties of the composites, nanosilica surface silylation by means of two silane coupling agents: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (AEAPTMS) and 3-methacryloxypropyltrimethoxysilane (MPTMS) was explored. The composites were also compatibilized using three compatibilizers: methyl methacrylate grafted PP (MMA-g-PP), glycidylmethacrylate grafted PP (GMA-g-PP) and maleic anhydride grafted PP (MAH-g-PP). The properties of the blends and the composites were examined using tensile and Izod impact tests, differential scanning calorimetry (DSC), thermogravimetric analysis (ATG) and scanning electron microscopy (SEM). According to the mechanical property evaluations, the incorporation of nano-SiO₂ particles into PP/EPR blend improved the tensile strength and Young’s modulus of the composites. The elongation and Izod impact strength were adversely affected. A significant improvement in the mechanical properties was obtained for the composites with AEAPTMS-SiO₂ and MAH-g-PP. The DSC results indicated that the incorporation of the modified silica and MAH-g-PP increased the crystallinity of the composites. However, no significant variation in the crystallinity was observed as a result of the addition of MMA-g-PP and GMA-g-PP. The TGA results revealed that the composites exhibit a higher thermal stability than that of the neat matrix. SEM micrographs of the fractured surfaces revealed a two-phase morphology with EPR nodules being dispersed in the PP matrix. SEM also indicated that the incorporation of MAH-g-PP into PP/EPR composites contributes to a better dispersion of the EPR phase and nano-SiO₂ particles in the polymer matrix.     

Biopolymer blends based on polylactic acid and polyhydroxy butyrate‐co‐valerate: Effect of clay on mechanical and thermal properties

Biodegradable polymer blends consisting of polylactic acid (PLA) and polyhydroxy butyrate‐co‐valerate (PHBV) have been prepared by melt mixing in a twin screw extruder and followed by injection molding technique. Cereplast PLA containing starch as an additive was used to make the blends. The effects of three different types of clay (montmorillonite, bentonite, and chemically modified bentonite) on the mechanical and thermal properties of the blends were studied. The ratio of PLA and PHBV (w/w) was maintained at 70:30 while the weight of clay was fixed at 1%. The addition of clay was found to result in a slight increase in tensile strength and modulus. Viscoelastic studies revealed that the damping property of the blends decreased with the addition of clay. This was attributed to the decreased segmental motion in the molecular chains. The morphology of the blends has been investigated by environmental scanning electron microscopy and a homogenous surface was observed for the blend containing montmorillonite. POLYM. COMPOS., 36:2042–2050, 2015. © 2014 Society of Plastics Engineer