Supertoughened Renewable PLA Reactive Multiphase Blends System: Phase Morphology and Performance
Abstract

Multiphase blends of poly(lactic acid) (PLA), ethylene-methyl acrylate-glycidyl methacrylate (EMA-GMA) terpolymer, and a series of renewable poly(ether-b-amide) elastomeric copolymer (PEBA) were fabricated through reactive melt blending in an effort to improve the toughness of the PLA. Supertoughened PLA blend showing impact strength of ∼500 J/m with partial break impact behavior was achieved at an optimized blending ratio of 70 wt % PLA, 20 wt % EMA-GMA, and 10 wt % PEBA. Miscibility and thermal behavior of the binary blends PLA/PEBA and PLA/EMA-GMA, and the multiphase blends were also investigated through differential scanning calorimetric (DSC) and dynamic mechanical analysis (DMA). Phase morphology and fracture surface morphology of the blends were studied through scanning electron microscopy (SEM) and atomic force microscopy (AFM) to understand the strong corelation between the morphology and its significant effect on imparting tremendous improvement in toughness. A unique “multiple stacked structure” with partial encapsulation of EMA-GMA and PEBA minor phases was observed for the PLA/EMA-GMA/PEBA (70/20/10) revealing the importance of particular blend composition in enhancing the toughness. Toughening mechanism behind the supertoughened PLA blends have been established by studying the impact fractured surface morphology at different zones of fracture. Synergistic effect of good interfacial adhesion and interfacial cavitations followed by massive shear yielding of the matrix was believed to contribute to the enormous toughening effect observed in these multiphase blends.
1 Introduction
2 Experimental Section
2.1 Materials
Scheme 1

2.2 Preparation of the Blends
2.3 Testing and Characterization
2.3.1 Impact Strength and Elongation
2.3.2 Dynamic Mechanical Analysis (DMA)
2.3.3 Differential Scanning Calorimetry (DSC)
2.3.4 Contact Angle Measurements
2.3.5 Scanning Electron Microscope (SEM)
2.3.6 Atomic Force Microscopy (AFM)
3 Results and Discussion
3.1 Tensile and Impact Properties
Figure 1

Figure 1. Tensile stress–strain curves of neat PLA, binary blend, and PLA/EMA-GMA/PEBA ternary blends.
Figure 2

Figure 2. Tensile properties of PLA/EMA-GMA/PEBA ternary blends as a function of the weight fraction: (A) Neat PLA; (B) PLA/PEBA(80/20); (C) PLA/EMA-GMA(80/20); (D) PLA/EMA-GMA/PEBA(70/10/20); (E)PLA/EMA-GMA/PEBA(70/15/15); (F) PLA/EMA-GMA/PEBA(70/20/10).
Figure 3

Figure 3. Notched Izod impact strength and percent elongation at break of PLA/EMA-GMA/PEBA ternary blends as a function of the weight fraction: (A) Neat PLA; (B) PLA/PEBA(80/20); (C) PLA/EMA-GMA(80/20); (D) PLA/EMA-GMA/PEBA(70/10/20); (E)PLA/EMA-GMA/PEBA(70/15/15); (F) PLA/EMA-GMA/PEBA(70/20/10).
Figure 4

Figure 4. Impact strength and elongation properties of the (a) PLA/EMA-GMA/PEBA (70/10/20) and (b) PLA/EMA-GMA/PEBA (70/20/10) with different grade PEBA: (A) Neat PLA, (B) Blend with Pebax 72R53, (C) Blend with Pebax 55R53, (D) Blend with Pebax 35R53.
3.2 Miscibility of the Blends
Figure 5

Figure 5. DMA traces of PLA blended with PEBA (Pebax 55R53) elastomer at various concentrations: (a) tan δ versus temperature; (b) storage modulus versus temperature curves.
3.3 Thermal and Crystallization Behaviors
Figure 6

Figure 6. DSC heating curves of the neat PLA and the blends after quenched: (a) neat PLA ;(b) PLA/EMA-GMA (80/20); (c) PLA/PEBA (80/20); (d) PLA/EMA-GMA/PEBA (70/10/20); (e) PLA/EMA-GMA/PEBA (70/20/10); (f) neat PEBA (Pebax Rnew 55R53).
Figure 7

Figure 7. DSC cooling curves of the neat PLA and the blends: (a) neat PLA; (b) PLA/EMA-GMA(80/20); (c) PLA/PEBA(80/20); (d) PLA/EMA-GMA/PEBA(70/10/20); (e) PLA/EMA-GMA/PEBA(70/20/10); (f) neat PEBA(Pebax Rnew 55R53).
| samples | Tg(PLA) (°C) | Tcc (°C) | Tc(PLA) (°C) | ΔHc(PLA) (J/g) | Tc(PEBA) (°C) | ΔHc(PEBA) (J/g) | Tm (°C) | ΔHm (J/g) |
|---|---|---|---|---|---|---|---|---|
| PLA | 62.0 | 98.6 | 95.6 | 15.8 | 168.2 | 45.3 | ||
| PLA/EMA-GMA(80/20) | 61.0 | 109.2 | 169.5 | 28.9 | ||||
| PLA/PEBA(80/20) | 61.2 | 102.9 | 92.1 | 3.6 | 146.7 | 0.6 | 168.5 | 38.0 |
| PLA/EMA-GMA/PEBA (70/10/20) | 61.8 | 108.5 | 88.6 | 6.0 | 146.4 | 0.3 | 169.4 | 32.4 |
| PLA/EMA-GMA/PEBA (70/20/10) | 61.3 | 109.3 | 88.5 | 3.5 | 169.5 | 26.3 | ||
| PEBA(Pebax 55R53) | 30.9 | 151.1 | 30.3 | 172.5 | 36.8 |
3.4 Impact Fractured Surface Morphology of the Blends
Figure 8

Figure 8. SEM images of impact-fracture surface of the binary blend and PLA/EMA-GMA/PEBA ternary blend with various weight compositions.
3.5 Phase Morphology of the Blend
Figure 9

Figure 9. SEM images of cryofractured surface of PLA/EMA-GMA/PEBA blend with various weight compositions.
Figure 10

Figure 10. Detail structure of the PLA/EMA-GMA/PEBA (70/20/10) blend with the SEM and AFM phase images: (A) SEM images of cryofractured surface (4000×), (B) AFM image, (C) SEM images of cryofractured surface after etched (10000×), and (D) the schematic structure.
λij is the spreading coefficient of i over j and αij is the interfacial tension between i and ij. For B to be encapsulated by C, λCB must be positive. In the case when both λCB and λBC are negative, B and C will tend to form separated phases. Here, the morphologies of the ternary blends were predicted using the spreading coefficient theory. Since there is no related interfacial tension data for each pairs of the PLA, EMA-GMA, and PEBA are available from the literatures, we have calculated the interfacial tension values based on the surface tension values measured by the contact angle. The contact angle and surface tension values for all the components of the blend can be referred in Support Information Table S1. Since the melt blending was carried out at essentially higher temperatures, the use of interfacial tension values calculated from surface tension values requires to be extrapolated to the processing temperature. To do that, a temperature coefficient of −0.06 mJ m–2 K–1 was used as adopted in many of the literatures. The interfacial values and spreading coefficient calculated for the polymer pairs are listed in Table 2.| interfacial tension, γij (mN/m) | ||||
|---|---|---|---|---|
| polymer pairs | using harmonic mean equation | using geometric mean equation | interfacial tension, γij (mN/m) at 190 C using geometric mean equation | spreading coefficient, λij |
| PLA/EMA-GMA (γab) | 3.61 | 1.84 | 5.91 | λbc = −7.53 |
| PLA/PEBA (γac) | 1.69 | 0.85 | 1.40 | λcb = 1.49 |
| EMA-GMA/PEBA (γbc) | 1.40 | 0.70 | 3.01 | λab = −4.30 |
3.6 Toughening Mechanism
Figure 11

Figure 11. AFM images of PLA/EMA-GMA/PEBA (70/20/10) ternary blend obtained under PeakForce QNM mode.
Figure 12

Figure 12. Schematic and impact surface graphs of the blends near the notch.
Conclusions
Supporting Information
Contact angle and surface tension values calculated for individual blend components are given in the Supporting Information, Table S1. This material is available free of charge via the Internet at http://pubs.acs.org.
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgment
The authors are grateful for the financial support from (1) the Ontario Ministry of Agriculture, Food, and Rural Affairs (OMAFRA)—New Directions and Alternative Renewable Fuels research program; (2) the Ontario Ministry of Economic Development and Innovation (MEDI), Ontario Research Fund—Research Excellence Round 4 program and (3) the Natural Sciences and Engineering Research Council (NSERC), Canada NCE AUTO21 program.
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This article references 56 other publications.
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- 20Noda, I.; Satkowski, M. M.; Dowrey, A. E.; Marcott, C. Polymer Alloys of Nodax Copolymers and Poly(Lactic Acid) Macromol. Biosci. 2004, 4, 269– 275[Crossref], [PubMed], [CAS], Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXjt1OrtLw%253D&md5=01aaf857a8ac221e6f3112cdd3479839Polymer alloys of Nodax copolymers and poly(lactic acid)Noda, Isao; Satkowski, Michael M.; Dowrey, Anthony E.; Marcott, CurtisMacromolecular Bioscience (2004), 4 (3), 269-275CODEN: MBAIBU; ISSN:1616-5187. (Wiley-VCH Verlag GmbH & Co. KGaA)Properties of polymer alloys comprising poly (lactic acid) and Nodax copolymers are investigated. Nodax is a family of bacterially produced polyhydroxyalkanoate (PHA) copolymers comprising 3-hydroxybutyrate (3HB) and other 3-hydroxyalkanoate (3HA) units with side groups greater than or equal to three carbon units. The incorporation of 3HA units with medium-chain-length (mcl) side groups effectively lowers the crystallinity and the melt temp., Tm, of this class of PHA copolymers, in a manner similar to that of alpha olefins controlling the properties of linear low d. polyethylene. The lower Tm makes the material easier to process, as the thermal decompn. temp. of PHAs is then relatively low. The reduced crystallinity provides the ductility and toughness required for many plastics applications. When a small amt. of ductile PHA is blended with poly(lactic acid) (PLA), a new type of polymer alloy with much improved properties is created. The toughness of PLA is substantially increased without a redn. in the optical clarity of the blend. The synergy between the two materials, both produced from renewable resources, is attributed to the retardation of crystn. of PHA copolymers finely dispersed in a PLA matrix as discrete domains.
- 21Shibata, M.; Inoue, Y.; Miyoshi, M. Mechanical Properties, Morphology, and Crystallization Behavior of Blends of Poly(l-Lactide) with Poly(Butylene Succinate-co-l-lactate) and Poly(butylene succinate) Polymer 2006, 47, 3557– 3564[Crossref], [CAS], Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XksFarsLc%253D&md5=06be101ccd7cb72ab593c5a41ea768fdMechanical properties, morphology, and crystallization behavior of blends of poly(L-lactide) with poly(butylene succinate-co-L-lactate) and poly(butylene succinate)Shibata, Mitsuhiro; Inoue, Yusuke; Miyoshi, MasanaoPolymer (2006), 47 (10), 3557-3564CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)The blends of poly(L-lactide) (PLLA) with poly(butylene succinate) (PBS) and poly(butylene succinate-co-L-lactate) (PBSL) contg. the lactate unit of ca. 3 mol% were prepd. by melt-mixing and subsequent injection molding, and their mech. properties, morphol., and crystn. behavior have been compared. Dynamic viscoelasticity and SEM measurements of the blends revealed that the extent of the compatibility of PBSL and PBS with PLLA is almost the same, and that the PBSL and PBS components in the blends with a low content of PBSL or PBS (5-20 wt%) are homogeneously dispersed as 0.1-0.4 μm particles. The tensile strength and modulus of the blends approx. followed the rule of mixts. over the whole compn. range except that those of PLLA/PBS 99/1 blend were exceptionally higher than those of pure PLLA. All the blends showed considerably higher elongation at break than pure PLLA, PBSL, and PBS. Differential scanning calorimetric anal. of the blends revealed that the isothermal and non-isothermal crystn. of the PLLA component is promoted by the addn. of a small amt. of PBSL, while the addn. of PBS was much less effective.
- 22Lu, J. M.; Qiu, Z. B.; Yang, W. T. Fully Biodegradable Blends of Poly(l-Lactide) and Poly(Ethylene Succinate): Miscibility, Crystallization, and Mechanical properties Polymer 2007, 48, 4196– 4204Google ScholarThere is no corresponding record for this reference.
- 23Ojijo, V.; Ray, S. S.; Sadiku, R. Toughening of Biodegradable Polylactide/Poly(Butylene Succinate-co-adipate) Blends via in Situ Reactive Compatibilization ACS Appl. Mater. Interfaces 2013, 5, 4266– 4276[ACS Full Text
], [CAS], Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXms1OqtLY%253D&md5=0def225e8fcf31c96067228b83c01060Toughening of Biodegradable Polylactide/Poly(butylene succinate-co-adipate) Blends via in Situ Reactive CompatibilizationOjijo, Vincent; Sinha-Ray, Suprakas; Sadiku, RotimiACS Applied Materials & Interfaces (2013), 5 (10), 4266-4276CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Polylactide and poly(butylene succinate-co-adipate) (PLA/PBSA) were melt-blended in the presence of tri-Ph phosphite (TPP). An increase in the torque during melt mixing was used to monitor the changes in viscosity as compatibilization of the blends occurred. Scanning electron micrographs showed not only a redn. in the dispersed-phase size with increased TPP content but also fibrillated links between the PLA and PBSA phases, signifying compatibilization. Moreover, optimization of parameters such as the mixing sequence and time, TPP content, and PBSA concn. revealed that blends contg. 30 and 10 wt % PBSA and 2 wt. % TPP, which were processed for 30 min, were optimal in terms of thermomech. properties. The impact strength increased from 6 kJ/m2 for PLA to 11 and 16 kJ/m2 for blends contg. 30 and 10 wt. % PBSA, resp., whereas the elongation-at-break increased from 6% for PLA to 20 and 37% for blends contg. 30 and 10 wt. % PBSA, resp. Upon compatibilization, the failure mode shifted from the brittle fracture of PLA to ductile deformation, effected by the debonding between the two phases. With improved phase adhesion, compatibilized blends not only were toughened but also did not significantly lose tensile strength and thermal stability. - 24Luzinov, I.; Pagnoulle, C.; Jerome, R. Ternary Polymer Blend with Core–Shell Dispersed Phases: Effect of the Core-forming Polymer on Phase Morphology and Mechanical Properties Polymer 2000, 41, 7099– 7109Google ScholarThere is no corresponding record for this reference.
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- 28Li, Y.; Shimizu, H. Compatibilization by Homopolymer: Significant Improvements in the Modulus and Tensile Strength of PPC/PMMA Blends by the Addition of a Small Amount of PVAc ACS Appl. Mater. Interfaces 2009, 1, 1650– 1655[ACS Full Text
], [CAS], Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXpsFSjtrg%253D&md5=c2c5e0f99e564925a6b57764e051a6dbCompatibilization by Homopolymer: Significant Improvements in the Modulus and Tensile Strength of PPC/PMMA Blends by the Addition of a Small Amount of PVAcLi, Yongjin; Shimizu, HiroshiACS Applied Materials & Interfaces (2009), 1 (8), 1650-1655CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Poly(propylene carbonate) (PPC), a polymer produced from CO2, was melt-mixed with 30 wt. % poly(Me methacrylate) (PMMA) with the aim of enhancing the phys. properties of PPC for practical use but keeping a relatively high CO2 fixing rate in the compd. The observation of a coarse phase structure with a large PMMA domain size and a large size distribution in the blend indicates the immiscibility between PPC and PMMA. The addn. of a small amt. of poly(vinyl acetate) (PVAc) not only shifts the glass transition temps. (Tg's) of both PPC and PMMA markedly but also significantly increases the modulus and tensile strength of the blend. The prepd. compd. with 5 per hundred parts of resin PVAc shows a 26 times higher elastic modulus and an approx. 3.8 Times higher tensile strength than pure PPC at room temp. The morphol. study indicates that the incorporation to PVAC not only induces the finer dispersion of PMMA in the PPC matrix but also results in the phase transformation from a sea-island to a co-continuous structure. - 29Li, L.; Yin, B.; Zhou, Y.; Gong, L.; Yang, M.; Xie, B.; Chen, C. Characterization of PA6/EPDM-g-MA/HDPE Ternary Blends: The Role of Core–Shell Structure Polymer 2012, 53, 3043– 3051Google ScholarThere is no corresponding record for this reference.
- 30Yin, B.; Li, L.; Zhou, Y.; Gong, L.; Yang, M.; Xie, B. Largely Improved Impact Toughness of PA6/EPDM-g-MA/HDPE Ternary Blends: The Role of Core–shell Particles Formed in Melt Processing on Preventing Micro-crack Propagation Polymer 2013, 54, 1938– 1947Google ScholarThere is no corresponding record for this reference.
- 31Liu, H.; Chen, F.; Liu, B.; Estep, G.; Zhang, J. Super Toughened Poly(Lactic Acid) Ternary Blends by Simultaneous Dynamic Vulcanization and Interfacial Compatibilization Macromolecules 2010, 43, 6058– 6066[ACS Full Text
], [CAS], Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXotFKms7o%253D&md5=b811e85ff00ecf1d89184c627dcd85e3Super Toughened Poly(lactic acid) Ternary Blends by Simultaneous Dynamic Vulcanization and Interfacial CompatibilizationLiu, Hongzhi; Chen, Feng; Liu, Bo; Estep, Greg; Zhang, JinwenMacromolecules (Washington, DC, United States) (2010), 43 (14), 6058-6066CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)In this study, a poly(lactic acid) (PLA) ternary blend system consisting of PLA, an epoxy-contg. elastomer, and a zinc ionomer was introduced and studied in detail. Transmission electron microscopy revealed that the "salami"-like phase structure was formed in the ternary blends. While increase in blending temp. had little effects on the tensile properties of the resulting blends, it greatly changed the impact strength. For the blends prepd. at 240 °C by extrusion blending, the resulting PLA ternary blends displayed supertoughness with moderate levels of strength and modulus. It was found that the zinc ions catalyzed the crosslinking of epoxy-contg. elastomer and also promoted the reactive compatibilization at the interface of PLA and the elastomer. Both blending temp. and elastomer/ionomer ratio were found to play important roles in achieving supertoughness of the blends. The significant increase in notched impact strength was attributed to the effective interfacial compatibilization at elevated blending temps. - 32Liu, H.; Song, W.; Chen, F.; Guo, L.; Zhang, J. Interaction of Microstructure and Interfacial Adhesion on Impact Performance of Polylactide (PLA) Ternary Blends Macromolecules 2011, 44, 1513– 1522[ACS Full Text
], [CAS], Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXitVShtL8%253D&md5=5e41ea8f1dc5d9ab83181d183f0bad14Interaction of Microstructure and Interfacial Adhesion on Impact Performance of Polylactide (PLA) Ternary BlendsLiu, Hongzhi; Song, Wenjia; Chen, Feng; Guo, Li; Zhang, JinwenMacromolecules (Washington, DC, United States) (2011), 44 (6), 1513-1522CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)Polylactide (PLA) was blended with an ethylene/n-Bu acrylate/glycidyl methacrylate (EBA-GMA) terpolymer and a zinc ionomer of ethylene/methacrylic acid (EMAA-Zn) copolymer. The phase morphol. of the resulting ternary blends and its relationship with impact behaviors were studied systematically. Dynamic vulcanization of EBA-GMA in the presence of EMAA-Zn was investigated by torque rheol., and its cross-link level was evaluated by dynamic mech. anal. Reactive compatibilization between PLA and EBA-GMA was studied using Fourier transform IR spectroscopy. The dispersed domains in the ternary blends displayed a "salami"-like phase structure, in which the EMAA-Zn phase evolved from occluded subinclusions into continuous phase with decrease in the EBA-GMA/EMAA-Zn ratio. An optimum range of particle sizes of the dispersed domains for high impact toughness was identified. Also, the micromech. deformation process of these ternary blends was also investigated by observation of the impact-fractured surfaces using the electron microscope. It was suggested that the low cavitation resistance of dispersed particles in conjunction with suitable interfacial adhesion was responsible for the optimum impact toughness obsd. - 33Zhang, K.; Mohanty, A. K.; Misra, M. Fully Biodegradable and Biorenewable Ternary Blends from Polylactide, Poly(3-Hydroxybutyrate-co-hydroxyvalerate) and Poly(Butylene Succinate) with Balanced Properties ACS Appl. Mater. Interfaces 2012, 4, 3091– 3101[ACS Full Text
], [CAS], Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XntlOnsrY%253D&md5=324a233da2d1787fa7ee6d32b92c190aFully Biodegradable and Biorenewable Ternary Blends from Polylactide, Poly(3-hydroxybutyrate-co-hydroxyvalerate) and Poly(butylene succinate) with Balanced PropertiesZhang, Kunyu; Mohanty, Amar K.; Misra, ManjuACS Applied Materials & Interfaces (2012), 4 (6), 3091-3101CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)A ternary blend of entirely biodegradable polymers, namely polylactide (PLA), poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV), and poly(butylene succinate) (PBS), was first melt-compounded in an effort to prep. novel fully biodegradable materials with an excellent balance of properties. The miscibility, morphol., thermal behavior, mech. properties, and thermal resistance of the blends were studied. DMA anal. revealed that PHBV and PLA showed some limited miscibility with each other, but PBS is immiscible with PLA or PHBV. Minor phase-sepd. structure was obsd. from SEM for all the blends compn. except PHBV/PLA/PBS 60/30/10 blend, which formed a typical mixt. of core-shell morphol. The morphologies were verified by anal. of the spreading coeffs. Excellent stiffness-toughness balance was achieved by ternary blends of PLA, PHBV, and PBS. Significant enhancement of the toughness and flexibility of PLA was achieved by the incorporation of PBS and PHBV without sacrificing the strength apparently. Both the stiffness and toughness were improved for PHBV in the ternary blends with PHBV as matrix. The crystn. of the PLA and PBS were enhanced by presence of PHBV in the blends, while the crystn. of PHBV was confined by PLA and PBS phases. Moreover, the thermal resistances and melt flow properties of the materials were also studied by anal. of the heat deflection temp. (HDT) and melt flow index (MFI) value in the work. - 34Ravati, S.; Favis, B. D. Tunable Morphologies for Ternary Blends with Poly(Butylene Succinate): Partial and Complete Wetting Phenomena Polymer 2013, 54, 3271– 3281[Crossref], [CAS], Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXot1Cqt7w%253D&md5=e5aece5d0eb7c5310c92204990907fccTunable morphologies for ternary blends with poly(butylene succinate): Partial and complete wetting phenomenaRavati, Sepehr; Favis, Basil D.Polymer (2013), 54 (13), 3271-3281CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)Poly(butylene succinate) (PBS) is a promising polymer for the prodn. of bio-based and biodegradable materials. This study focuses on the development of novel tunable morphol. states based on ternary blends comprising PBS. The other biodegradable polymers are selected from a set of poly(lactic acid) (PLA), poly(butylene adipate-co-terephthalate) (PBAT), and polycaprolactone(PCL). Three completely different morphol. states are obsd. here for the ternary blends and are reported for the first time including: partial wetting for PBS/PLA/PCL in which PLA droplets self-assemble at the interface of PBS and PCL; complete wetting tri-continuous morphol. for PBS/PLA/PBAT; and a highly unusual state combining both partial and complete wetting cases for the PBS/PBAT/PCL blend. The dramatic variation of morphol. for these blends is possible due to very low interfacial tensions between the polymer pairs. Within these morphol. wetting states a significant variety of specific structures can be obtained through control of the relative compns. For example, for the partially wet xPBS/yPLA/50%PCL blend, changing the vol. fraction of PBS to PLA from φPBSφPLA = 10 to φPBS/φPLA = 0.1 results in a transformation from PLA droplets at the PBS/PCL interface to PBS droplets at the PLA/PCL interface. From the thermodn. standpoint, the obsd. partial and complete wetting cases are supported by Harkins theory. This work opens the door to a wide range of novel and stable PBS-based ternary blend structures comprising biodegradable polymers.
- 35Ravati, S.; Favis, B. D. Interfacial Coarsening of Ternary Polymer Blends with Partial and Complete Wetting Structures Polymer 2013, 54, 6739– 6751[Crossref], [CAS], Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhs1yrur7O&md5=3df9d3a8f2e5eee3aeab56fc6fbc7042Interfacial coarsening of ternary polymer blends with partial and complete wetting structuresRavati, Sepehr; Favis, Basil D.Polymer (2013), 54 (25), 6739-6751CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)The coarsening of polymer mixts. is an important route towards major morphol. modification in multiphase polymer systems. To date however the coarsening of ternary systems has not been significantly examd. In this study the phase coarsening mechanism via annealing for partial wetting, and complete wetting morphologies in ternary polymer blends is characterized. This is a route towards the examn. of interfacial coarsening in polymer blends since ternary partially wet systems involve the presence of interfacial droplets while completely wet ternary systems are comprised of a complete interfacial layer. A partial wetting type of morphol. is obtained for polybutylene succinate (PBS)/poly(lactic acid) (PLA)/polycaprolactone (PCL). Three different compns. for that system with compn. ratios of .vphi.(PBS/PLA) = 1.5; .vphi.(PBS/PLA) = 3; and .vphi.(PBS/PLA) = 10 are prepd. to show the effect of the concn. of the self-assembled PLA droplets located at the interface of PBS/PCL. As the concn. of PLA decreases, the growth rate of the PLA phase during the annealing process sharply decreases due to a significant increase of the "surface to vol. ratio" of the PLA droplets required in order to cover the interface. In this case, due to the short inter-droplet distances between PLA droplets at the interface, coalescence is controlled by the drainage time. This mechanism is confirmed by the observation of a linear relationship between the third power of droplet size and annealing time. For the 37.5%PBS/12.5%PLA/50%PCL blend, the conservation of interfacial-angles confirms that the annealing time has no effect on the angle values between phases, as predicted by Harkins spreading theory.The annealing process for complete wetting is studied at four compns. for an HDPE/PS/PCL blend where the PS phase is located as a continuous layer at the interface of co-continuous HDPE/PCL. In 33.3%HDPE/33.3%PS/33.3%PCL after 30 min of annealing, the PS phase thickness increases 49 times from 2.3 μm to 112 μm. Even for very low concns. of 3%PS, a high coarsening rate of 0.0039 μm/s is obsd. This sharp linear increase in PS phase size implies a capillary pressure mechanism and an impeded growth of Tomotika-like capillaries for all three phases that cause a confinement effect for coarsening of the middle PS phase.
- 36Bitinis, N.; Verdejo, R.; Cassagnau, P.; Lopez-Manchado, M. A. Structure and properties of polylactide/natural rubber blends Mater. Chem. Phys. 2011, 129, 823– 831[Crossref], [CAS], Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXovFClsbs%253D&md5=57010d1a3d7d12f2196d4fdb2890d309Structure and properties of polylactide/natural rubber blendsBitinis, N.; Verdejo, R.; Cassagnau, P.; Lopez-Manchado, M. A.Materials Chemistry and Physics (2011), 129 (3), 823-831CODEN: MCHPDR; ISSN:0254-0584. (Elsevier B.V.)Polylactide, PLA, is a biodegradable thermoplastic polyester derived from biomass that has restricted packaging applications due to its high brittleness and poor crystn. behavior. Here, new formulations based on natural rubber-PLA blends have been developed. The processing windows, temp., time, and rotor rate, and the rubber content have been optimized in order to obtain a blend with useful properties. The rubber phase was uniformly dispersed in the continuous PLA matrix with a droplet size range from 1.1 to 2.0 μm. The ductility of PLA has been significantly improved by blending with natural rubber, NR. The elongation at break improved from 5% for neat PLA to 200% by adding 10% NR. In addn., the incorporation of NR not only increased the crystn. rate but also enhanced the crystn. ability of PLA. These materials are, therefore, very promising for industrial applications.
- 37Bitinis, N.; Sanz, A.; Nogales, A.; Verdejo, R.; Lopez-Manchado, M. A.; Ezquerra, T. A. Deformation Mechanisms in Polylactic Acid/Natural Rubber/Organoclay Bionanocomposites as Revealed by Synchrotron X-ray Scattering Soft Matter 2012, 8, 8990– 8997[Crossref], [CAS], Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtFOms7zL&md5=c2639941c1a0f9108055a2fa2f4fd532Deformation mechanisms in polylactic acid/natural rubber/organoclay bionanocomposites as revealed by synchrotron X-ray scatteringBitinis, Natacha; Sanz, Alejandro; Nogales, Aurora; Verdejo, Raquel; Lopez-Manchado, Miguel A.; Ezquerra, Tiberio A.Soft Matter (2012), 8 (34), 8990-8997CODEN: SMOABF; ISSN:1744-683X. (Royal Society of Chemistry)The micromech. deformation mechanisms of a polylactic acid (PLA)/natural rubber (NR) blend (PLA/NR 90/10 wt%) and its organoclay filled bionanocomposites have been investigated by small and wide angle X-ray scattering (SAXS-WAXS) under tensile conditions. The addn. of NR to a PLA matrix changed the brittle fracture of PLA to a ductile deformation through the debonding of the rubber droplets. Otherwise, the formation of cavities between PLA and NR was hampered by the nanoclays since they were mainly located at the polymer blend interface. In this case, the nanoclays acted as craze nucleation sites. At 1 wt% of filler concn., the crazes were able to fully develop in the blend and to evolve into stable microvoids, which kept growing and orienting in the tensile direction. These mechanisms also explained the progressive plastic deformation of the polymer chains and the preferential orientation of the nanoclay platelets.
- 38Bitinis, N.; Verdejo, R.; Maya, E. M.; Espuche, E.; Cassagnau, P.; Lopez-Manchado, M. A. Physicochemical Properties of Organoclay Filled Polylactic Acid/Natural Rubber Blend Bionanocomposites Compos. Sci. Technol. 2012, 72, 305– 313[Crossref], [CAS], Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XnvVSitA%253D%253D&md5=0eb7f9926fdcd7880a64450c26e29014Physicochemical properties of organoclay filled polylactic acid/natural rubber blend bionanocompositesBitinis, N.; Verdejo, R.; Maya, E. M.; Espuche, E.; Cassagnau, P.; Lopez-Manchado, M. A.Composites Science and Technology (2012), 72 (2), 305-313CODEN: CSTCEH; ISSN:0266-3538. (Elsevier Ltd.)A novel toughened polylactic acid (PLA) bionanocomposite with tuneable properties was successfully prepd. by melt mixing PLA with natural rubber and several montmorillonites (MMTs). The organoclays were preferentially located at the interface acting as compatibilizers between both polymer phases. This location resulted in a marked improvement of the phys. and mech. properties of the system. Moreover, these properties can be controlled as a function of the nanofiller nature and the mixing procedure used.
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- 42Eustache, R. P. In Handbook of Condensation Thermoplastic Elastomer; Fakirov, S., Eds; Wiley-VCH: Verlag GmbH & Co. KGaA: Weinheim, Germany, 2005; Chapter 10, pp 263– 280.Google ScholarThere is no corresponding record for this reference.
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- 44Han, L.; Han, C.; Dong, L. Effect of Crystallization on Microstructure and Mechanical Properties of Poly[(Ethylene Oxide)-block-(amide-12)]-toughened Poly(Lactic Acid) Blend Polym. Int. 2013, 62, 295– 303[Crossref], [CAS], Google Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XpsVOls7k%253D&md5=4ee6a430620f32ae10a804e6c1a668a6Effect of crystallization on microstructure and mechanical properties of poly[(ethylene oxide)-block-(amide-12)]-toughened poly(lactic acid) blendHan, Lijing; Han, Changyu; Dong, LisongPolymer International (2013), 62 (2), 295-303CODEN: PLYIEI; ISSN:0959-8103. (John Wiley & Sons Ltd.)The effect of crystn. on the microstructure and mech. properties of a poly[(ethylene oxide)-block-(amide-12)] (PEBA)-toughened poly(lactic acid) (PLA) blend was investigated. Annealing was used to govern the crystn. microstructure and hence the mech. properties of the blend. Crystn. resulted in the morphol. of the PLA component altering from a continuous amorphous phase to continuous cryst. phase. Moreover, as the crystn. of PLA proceeded, the degree of crystallinity, spherulite size and lamellar thickness increased, and the interlamellar and interspherulitic connections became weaker. These led to the large plastic deformation in the matrix during tension being suppressed, and cracks appeared easily under tensile load, which was favorable to fracture for the blend during tension and so a small elongation at break was obtained. However, the elongation at break for all the annealed specimens was higher than that for neat amorphous PLA, suggesting that PEBA still showed a toughening effect for PLA under annealing. Copyright © 2012 Society of Chem. Industry.
- 45Han, L.; Han, C.; Dong, L. Morphology and Properties of the Biosourced Poly(Lactic Acid)/Poly(Ethylene Oxide-b-amide-12) Blends Polym. Compos. 2013, 34, 122– 130[Crossref], [CAS], Google Scholar45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xhslymt77J&md5=e538dc60e34f823198d01cdb9e957b62Morphology and properties of the biosourced poly(lactic acid)/poly(ethylene oxide-b-amide-12) blendsHan, Lijing; Han, Changyu; Dong, LisongPolymer Composites (2013), 34 (1), 122-130CODEN: PCOMDI; ISSN:0272-8397. (John Wiley & Sons, Inc.)Biosourced poly(lactic acid) (PLA) blends with different content of poly(ethylene oxide-b-amide-12) (PEBA) were prepd. by melt compounding. The miscibility, phase structure, crystn. behavior, mech. properties, and toughening mechanism were investigated. The blend was an immiscible system with the PEBA domains evenly dispersed in the PLA matrix. The PEBA component suppressed the nonisothermal melt crystn. of PLA. With the addn. of PEBA, marked improvement in toughness of PLA was achieved. The max. for elongation at break and impact strength of the blend reached the level of 346% and 60.5 kJ/m2, resp. The phase morphol. evolution in the PLA/PEBA blends after tensile and impact tests was investigated, and the corresponding toughening mechanism was discussed. It was found that the PLA matrix demonstrates obvious shear yielding in the blend during the tensile and impact tests, which induced energy dissipation and therefore lead to improvement in toughness of the PLA/PEBA blends. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers.
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Abstract

Scheme 1
Scheme 1. Illustration of the Chemical Structure of the Three Polymers UsedFigure 1

Figure 1. Tensile stress–strain curves of neat PLA, binary blend, and PLA/EMA-GMA/PEBA ternary blends.
Figure 2

Figure 2. Tensile properties of PLA/EMA-GMA/PEBA ternary blends as a function of the weight fraction: (A) Neat PLA; (B) PLA/PEBA(80/20); (C) PLA/EMA-GMA(80/20); (D) PLA/EMA-GMA/PEBA(70/10/20); (E)PLA/EMA-GMA/PEBA(70/15/15); (F) PLA/EMA-GMA/PEBA(70/20/10).
Figure 3

Figure 3. Notched Izod impact strength and percent elongation at break of PLA/EMA-GMA/PEBA ternary blends as a function of the weight fraction: (A) Neat PLA; (B) PLA/PEBA(80/20); (C) PLA/EMA-GMA(80/20); (D) PLA/EMA-GMA/PEBA(70/10/20); (E)PLA/EMA-GMA/PEBA(70/15/15); (F) PLA/EMA-GMA/PEBA(70/20/10).
Figure 4

Figure 4. Impact strength and elongation properties of the (a) PLA/EMA-GMA/PEBA (70/10/20) and (b) PLA/EMA-GMA/PEBA (70/20/10) with different grade PEBA: (A) Neat PLA, (B) Blend with Pebax 72R53, (C) Blend with Pebax 55R53, (D) Blend with Pebax 35R53.
Figure 5

Figure 5. DMA traces of PLA blended with PEBA (Pebax 55R53) elastomer at various concentrations: (a) tan δ versus temperature; (b) storage modulus versus temperature curves.
Figure 6

Figure 6. DSC heating curves of the neat PLA and the blends after quenched: (a) neat PLA ;(b) PLA/EMA-GMA (80/20); (c) PLA/PEBA (80/20); (d) PLA/EMA-GMA/PEBA (70/10/20); (e) PLA/EMA-GMA/PEBA (70/20/10); (f) neat PEBA (Pebax Rnew 55R53).
Figure 7

Figure 7. DSC cooling curves of the neat PLA and the blends: (a) neat PLA; (b) PLA/EMA-GMA(80/20); (c) PLA/PEBA(80/20); (d) PLA/EMA-GMA/PEBA(70/10/20); (e) PLA/EMA-GMA/PEBA(70/20/10); (f) neat PEBA(Pebax Rnew 55R53).
Figure 8

Figure 8. SEM images of impact-fracture surface of the binary blend and PLA/EMA-GMA/PEBA ternary blend with various weight compositions.
Figure 9

Figure 9. SEM images of cryofractured surface of PLA/EMA-GMA/PEBA blend with various weight compositions.
Figure 10

Figure 10. Detail structure of the PLA/EMA-GMA/PEBA (70/20/10) blend with the SEM and AFM phase images: (A) SEM images of cryofractured surface (4000×), (B) AFM image, (C) SEM images of cryofractured surface after etched (10000×), and (D) the schematic structure.
Figure 11

Figure 11. AFM images of PLA/EMA-GMA/PEBA (70/20/10) ternary blend obtained under PeakForce QNM mode.
Figure 12

Figure 12. Schematic and impact surface graphs of the blends near the notch.
References
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- 7Liu, H.; J. Zhang, J. Research Progress in Toughening Modification of Poly (lactic acid) J. Polym. Sci., Part B: Polym. Phys. 2011, 49, 1051– 1083[Crossref], [CAS], Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXmslenurc%253D&md5=db682a433e533412c56ef7236cd728dbResearch progress in toughening modification of poly(lactic acid)Liu, Hongzhi; Zhang, JinwenJournal of Polymer Science, Part B: Polymer Physics (2011), 49 (15), 1051-1083CODEN: JPBPEM; ISSN:0887-6266. (John Wiley & Sons, Inc.)A review. Renewable poly(lactic acid) (PLA) exhibits high strength and stiffness. PLA is fully biodegradable and has received great interest. However, the inherent brittleness of PLA largely impedes its wide applications. In this article, the recent progress in PLA toughening using various routes including plasticization, copolymn., and melt blending with flexible polymers, was reviewed in detail. PLA toughening, particularly modification of impact toughness through melt blending, was emphasized in this review. Reactive blending was shown to be esp. effective in achieving high impact strength. The relationship between compn., morphol., and mech. properties were summarized. Toughening mechanisms were also discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011.
- 8Kfoury, G.; Raquez, J.; Hassouna, F.; Odent, J.; Toniazzo, V.; Ruch, D.; Dubois, P. Recent Advances in High Performance Poly(Lactide): From “Green” Plasticization to Super-tough Materials via (Reactive) Compounding Front. Chem. 2013, 1, 1– 45
- 9Jiang, L.; Wolcott, M. P.; Zhang, J. Study of Biodegradable Polylactide/Poly(Butylenes Adipate-co-terephthalate) Blends Biomacromolecules 2006, 7, 199– 207
- 10Anderson, K. S.; Lim, S. H.; Hillmyer, M. A. Toughening of Polylactide by Melt Blending with Linear Low-Density Polyethylene J. Appl. Polym. Sci. 2003, 89, 3757– 3768[Crossref], [CAS], Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXmsFGqsrs%253D&md5=aba199cfc813e784f463557c77a4e4bfToughening of poly-lactide by melt blending with linear low-density polyethyleneAnderson, Kelly S.; Lim, Shawn H.; Hillmyer, Marc A.Journal of Applied Polymer Science (2003), 89 (14), 3757-3768CODEN: JAPNAB; ISSN:0021-8995. (John Wiley & Sons, Inc.)Melt blending of poly-lactide and linear low-d. polyethylene (LLDPE) was performed in an effort to toughen poly-lactide. In addn., two model poly-lactide-polyethylene (PLLA-PE) block copolymers were investigated as compatibilizers. The LLDPE particle size and the impact resistance of binary and ternary blends were measured to det. the extent of compatibilization. For the amorphous poly-lactide (PLA), toughening was achieved only when a PLLA-PE block copolymer was used as a compatibilizer. For the semicryst. poly-lactide (PLLA), toughening was achieved in the absence of block copolymer. To decrease the variability in the impact resistance of the PLLA/LLDPE binary blend, as little as 0.5 wt % of a PLLA-PE block copolymer was effective. The differences that were seen between the PLA and PLLA binary blends were investigated with adhesion testing. The semicryst. PLLA did show significantly better adhesion to the LLDPE. We propose that tacticity effects on the entanglement mol. wt. or miscibility of poly-lactide allow for the improved adhesion between the PLLA and LLDPE.
- 11Anderson, K. S.; Hillmyer, M. A. The Influence of Block Copolymer Microstructure on the Toughness of Compatibilized Polylactide/Polyethylene Blends Polymer 2004, 45, 8809– 8823[Crossref], [CAS], Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXhtVWgtrnJ&md5=9b00a7bac5db64def8edc6fa358fb7eaThe influence of block copolymer microstructure on the toughness of compatibilized polylactide/polyethylene blendsAnderson, Kelly S.; Hillmyer, Marc A.Polymer (2004), 45 (26), 8809-8823CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)Poly(L-lactide) (PLLA) was melt blended with two linear-low-d. polyethylenes, i.e., Engage 8100 and Engage 8540, and a high-d. polyethylene, i.e., Dowlex IP40, in an effort to increase the impact strength of the PLLA. A series of molecularly distinct polylactide-polyethylene block copolymers were used as compatibilizers. The influence of the copolymer structure on the matrix/dispersed phase interfacial adhesion was correlated with the mech. properties of the PLLA composites. When a rubbery ethylene-1-octene copolymer with a low modulus was used as the dispersed phase (e.g., Engage 8100), the block copolymer that gave the strongest interfacial adhesion was necessary to achieve the most significant improvement in toughening. With the high-d. polyethylene the block copolymer that gave the weakest interfacial adhesion resulted in the greatest improvement in impact strength. For the rubbery copolymer with intermediate stiffness (e.g., Engage 8540), an intermediate degree of adhesion was necessary to obtain the largest increase in the impact properties. The impact properties of the composites were highly dependent on the dispersed phase properties.
- 12Lin, Y.; Zhang, K. Y.; Dong, Z. M.; Dong, L. S.; Li, Y. S. Study of Hydrogen-Bonded Blend of Polylactide with Biodegradable Hyperbranched Poly(Ester Amide) Macromolecules 2007, 40, 6257– 6267[ACS Full Text
], [CAS], Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXnvFOluro%253D&md5=7017893f9d6eff2c1bebc62199416f35Study of Hydrogen-Bonded Blend of Polylactide with Biodegradable Hyperbranched Poly(ester amide)Lin, Ying; Zhang, Kun-Yu; Dong, Zhong-Min; Dong, Li-Song; Li, Yue-ShengMacromolecules (Washington, DC, United States) (2007), 40 (17), 6257-6267CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)Polylactide (PLA) was melt blended with a biodegradable hyperbranched poly(ester amide) (HBP) to enhance its flexibility and toughness without sacrificing comprehensive performance. The advantage of using HBP was due to its unique spherical shape, low melt viscosity, and abundant functional end groups together with its easy access. Rheol. measurement showed that blending PLA with as little as 2.5% HBP resulted in a 40% redn. of melt viscosity. The glass transition temp. (Tg) of PLA in the blends decreased slightly with the increase of HBP content, indicating partial miscibility which resulted from intermol. interactions via H-bonding. The H-bonding involving C:O of PLA with OH and NH of HBP was evidenced by FTIR anal. for the first time. The HBP component, as a heterogeneous nucleating agent, accelerated the crystn. rate of PLA. Remarkably, with the increase of HBP content, the elongation at break of PLA blends dramatically increased without severe loss in tensile strength, even the tensile strength increased within 10% content of HBP. The stress-strain curves and the SEM photos of impact-fractured surface showed the material changed from brittle to ductile failure with the addn. of HBP. Reasonable interfacial adhesion via H-bonding and finely dispersed particulate structure of HBP in PLA were proposed to be responsible for the improved mech. properties. - 13Li, Y. J.; Shimizu, H. Toughening of Polylactide by Melt Blending with a Biodegradable Poly(Ether)urethane Elastomer Macromol. Biosci. 2007, 7, 921– 928[Crossref], [PubMed], [CAS], Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXotlCit7g%253D&md5=8c8f62c38e311a5f9332646198165f3bToughening of polylactide by melt blending with a biodegradable poly(ether)urethane elastomerLi, Yongjin; Shimizu, HiroshiMacromolecular Bioscience (2007), 7 (7), 921-928CODEN: MBAIBU; ISSN:1616-5187. (Wiley-VCH Verlag GmbH & Co. KGaA)Melt blending of polylactide (PLA) and a biodegradable poly(ether)urethane (PU) elastomer was performed in an effort to toughen the polylactide without compromising its biodegradability and biocompatibility. The miscibility, phase morphol., mech. properties, and toughening mechanism of the blend were investigated. The blend was found by dynamic mech. anal. to be a partially miscible system with shifted glass transition temps. The PU elastomer was dispersed in the PLA matrix with a domain size of sub-micrometer scale. The addn. of PU elastomer not only accelerated the crystn. speed, but also decreased the crystallinity of the PLA. With an increase in PU content, the blend shows decreased tensile strength and modulus; however, the elongation at break and the impact strength were significantly increased, indicating the toughening effects of the PU elastomer on the PLA. The brittle fracture of neat PLA was gradually transformed into ductile fracture by the addn. of PU elastomer. It was found that the PLA matrix demonstrates large area, plastic deformation (shear yielding) in the blend upon being subjected the tensile and impact tests, which is an important energy-dissipation process and leads to a toughened, biodegradable polymer blend.
- 14Bhardwaj, R.; Mohanty, A. K. Modification of Brittle Polylactide by Novel Hyperbranched Polymer-Based Nanostructures Biomacromolecules 2007, 8, 2476– 2484
- 15Hashima, K.; Nishitsuji, S.; Inoue, T. Structure-Properties of Super-Tough PLA Alloy with Excellent Heat Resistance Polymer 2010, 51, 3934– 3939[Crossref], [CAS], Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXpvFegs7s%253D&md5=e89511f7db21a88992cd0569e28e3f2cStructure-properties of super-tough PLA alloy with excellent heat resistanceHashima, Kazuhiro; Nishitsuji, Shotaro; Inoue, TakashiPolymer (2010), 51 (17), 3934-3939CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)Poly(lactic acid) (PLA) was toughed by blending hydrogenated styrene-butadiene-styrene block copolymer (SEBS) with the aid of reactive compatibilizer, poly(ethylene-co-glycidyl methacrylate) (EGMA). The high temp. property and thermal aging resistance were improved by further incorporating polycarbonate (PC), the ductile polymer with high glass transition temp. On the basis of transmission electron microscopy, differential scanning calorimetry, and dynamic mech. anal., the outstanding toughness and aging resistance of the 4 component alloy; e.g., PLA/PC/SEBS/EGMA = 40/40/5/5 (wt. ratio), seems to come from the neg. pressure effect of SEBS that dilates the plastic matrix consisting of PLA and PC to enhance the local segment motions.
- 16Oyama, H. T. Super-Tough Poly(Lactic Acid) Materials: Reactive Blending with Ethylene Copolymer Polymer 2009, 50, 747– 751Google ScholarThere is no corresponding record for this reference.
- 17Zhang, K.; Ran, X.; Wang, X.; Han, C.; Han, L.; Wen, X.; Zhuang, Y.; Dong, L. Improvement in Toughness and Crystallization of Poly(l-Lactic Acid) by Melt Blending with Poly(Epichlorohydrin-co-ethylene oxide) Polym. Eng. Sci. 2011, 51, 2370– 2380[Crossref], [CAS], Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsVektr3J&md5=750c786638fe1be0ad5cfdbeddf18c51Improvement in toughness and crystallization of poly(L-lactic acid) by melt blending with poly(epichlorohydrin-co-ethylene oxide)Zhang, Kunyu; Ran, Xianghai; Wang, Xuemei; Han, Changyu; Han, Lijing; Wen, Xin; Zhuang, Yugang; Dong, LisongPolymer Engineering & Science (2011), 51 (12), 2370-2380CODEN: PYESAZ; ISSN:0032-3888. (John Wiley & Sons, Inc.)Melt blending of poly(lactic acid) (PLA) and poly(epichlorohydrin-co-ethylene oxide) copolymers (ECO) was performed to improve the toughness and crystn. of PLA. Thermal and SEM anal. indicated that PLA and ECO were not thermodynamically miscible but compatible to some extent. The addn. of a small amt. of ECO accelerated the crystn. rate and increased the final crystallinity of PLA in the blends. Significant enhancement in toughness and flexibility of PLA were achieved by the incorporation of the ECO elastomer. When 20 wt% ECO added, the impact strength increased from 5 kJ/m2 of neat PLA to 63.9 kJ/m2, and the elongation at break increased from 5% to above 160%. The failure mode changed from brittle fracture of neat PLA to ductile fracture of the blend. Rheol. measurement showed that the melt elasticity and viscosity of the blend increased with the concn. of ECO. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.
- 18Broz1, M. E.; VanderHart, D. L.; Washburn, N. R. Structure and Mechanical Properties of Poly(d,l-Lactic Acid)/Poly(ε-Caprolactone) Blends Biomaterials 2003, 24, 4181– 4190Google ScholarThere is no corresponding record for this reference.
- 19Robertson, M. L.; Chang, K.; Gramlich, W. M.; Hillmyer, M. A. Toughening of Polylactide with Polymerized Soybean Oil Macromolecules 2010, 43, 1807– 1814
- 20Noda, I.; Satkowski, M. M.; Dowrey, A. E.; Marcott, C. Polymer Alloys of Nodax Copolymers and Poly(Lactic Acid) Macromol. Biosci. 2004, 4, 269– 275[Crossref], [PubMed], [CAS], Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXjt1OrtLw%253D&md5=01aaf857a8ac221e6f3112cdd3479839Polymer alloys of Nodax copolymers and poly(lactic acid)Noda, Isao; Satkowski, Michael M.; Dowrey, Anthony E.; Marcott, CurtisMacromolecular Bioscience (2004), 4 (3), 269-275CODEN: MBAIBU; ISSN:1616-5187. (Wiley-VCH Verlag GmbH & Co. KGaA)Properties of polymer alloys comprising poly (lactic acid) and Nodax copolymers are investigated. Nodax is a family of bacterially produced polyhydroxyalkanoate (PHA) copolymers comprising 3-hydroxybutyrate (3HB) and other 3-hydroxyalkanoate (3HA) units with side groups greater than or equal to three carbon units. The incorporation of 3HA units with medium-chain-length (mcl) side groups effectively lowers the crystallinity and the melt temp., Tm, of this class of PHA copolymers, in a manner similar to that of alpha olefins controlling the properties of linear low d. polyethylene. The lower Tm makes the material easier to process, as the thermal decompn. temp. of PHAs is then relatively low. The reduced crystallinity provides the ductility and toughness required for many plastics applications. When a small amt. of ductile PHA is blended with poly(lactic acid) (PLA), a new type of polymer alloy with much improved properties is created. The toughness of PLA is substantially increased without a redn. in the optical clarity of the blend. The synergy between the two materials, both produced from renewable resources, is attributed to the retardation of crystn. of PHA copolymers finely dispersed in a PLA matrix as discrete domains.
- 21Shibata, M.; Inoue, Y.; Miyoshi, M. Mechanical Properties, Morphology, and Crystallization Behavior of Blends of Poly(l-Lactide) with Poly(Butylene Succinate-co-l-lactate) and Poly(butylene succinate) Polymer 2006, 47, 3557– 3564[Crossref], [CAS], Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XksFarsLc%253D&md5=06be101ccd7cb72ab593c5a41ea768fdMechanical properties, morphology, and crystallization behavior of blends of poly(L-lactide) with poly(butylene succinate-co-L-lactate) and poly(butylene succinate)Shibata, Mitsuhiro; Inoue, Yusuke; Miyoshi, MasanaoPolymer (2006), 47 (10), 3557-3564CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)The blends of poly(L-lactide) (PLLA) with poly(butylene succinate) (PBS) and poly(butylene succinate-co-L-lactate) (PBSL) contg. the lactate unit of ca. 3 mol% were prepd. by melt-mixing and subsequent injection molding, and their mech. properties, morphol., and crystn. behavior have been compared. Dynamic viscoelasticity and SEM measurements of the blends revealed that the extent of the compatibility of PBSL and PBS with PLLA is almost the same, and that the PBSL and PBS components in the blends with a low content of PBSL or PBS (5-20 wt%) are homogeneously dispersed as 0.1-0.4 μm particles. The tensile strength and modulus of the blends approx. followed the rule of mixts. over the whole compn. range except that those of PLLA/PBS 99/1 blend were exceptionally higher than those of pure PLLA. All the blends showed considerably higher elongation at break than pure PLLA, PBSL, and PBS. Differential scanning calorimetric anal. of the blends revealed that the isothermal and non-isothermal crystn. of the PLLA component is promoted by the addn. of a small amt. of PBSL, while the addn. of PBS was much less effective.
- 22Lu, J. M.; Qiu, Z. B.; Yang, W. T. Fully Biodegradable Blends of Poly(l-Lactide) and Poly(Ethylene Succinate): Miscibility, Crystallization, and Mechanical properties Polymer 2007, 48, 4196– 4204Google ScholarThere is no corresponding record for this reference.
- 23Ojijo, V.; Ray, S. S.; Sadiku, R. Toughening of Biodegradable Polylactide/Poly(Butylene Succinate-co-adipate) Blends via in Situ Reactive Compatibilization ACS Appl. Mater. Interfaces 2013, 5, 4266– 4276[ACS Full Text
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- 28Li, Y.; Shimizu, H. Compatibilization by Homopolymer: Significant Improvements in the Modulus and Tensile Strength of PPC/PMMA Blends by the Addition of a Small Amount of PVAc ACS Appl. Mater. Interfaces 2009, 1, 1650– 1655[ACS Full Text
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- 31Liu, H.; Chen, F.; Liu, B.; Estep, G.; Zhang, J. Super Toughened Poly(Lactic Acid) Ternary Blends by Simultaneous Dynamic Vulcanization and Interfacial Compatibilization Macromolecules 2010, 43, 6058– 6066[ACS Full Text
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], [CAS], Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XntlOnsrY%253D&md5=324a233da2d1787fa7ee6d32b92c190aFully Biodegradable and Biorenewable Ternary Blends from Polylactide, Poly(3-hydroxybutyrate-co-hydroxyvalerate) and Poly(butylene succinate) with Balanced PropertiesZhang, Kunyu; Mohanty, Amar K.; Misra, ManjuACS Applied Materials & Interfaces (2012), 4 (6), 3091-3101CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)A ternary blend of entirely biodegradable polymers, namely polylactide (PLA), poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV), and poly(butylene succinate) (PBS), was first melt-compounded in an effort to prep. novel fully biodegradable materials with an excellent balance of properties. The miscibility, morphol., thermal behavior, mech. properties, and thermal resistance of the blends were studied. DMA anal. revealed that PHBV and PLA showed some limited miscibility with each other, but PBS is immiscible with PLA or PHBV. Minor phase-sepd. structure was obsd. from SEM for all the blends compn. except PHBV/PLA/PBS 60/30/10 blend, which formed a typical mixt. of core-shell morphol. The morphologies were verified by anal. of the spreading coeffs. Excellent stiffness-toughness balance was achieved by ternary blends of PLA, PHBV, and PBS. Significant enhancement of the toughness and flexibility of PLA was achieved by the incorporation of PBS and PHBV without sacrificing the strength apparently. Both the stiffness and toughness were improved for PHBV in the ternary blends with PHBV as matrix. The crystn. of the PLA and PBS were enhanced by presence of PHBV in the blends, while the crystn. of PHBV was confined by PLA and PBS phases. Moreover, the thermal resistances and melt flow properties of the materials were also studied by anal. of the heat deflection temp. (HDT) and melt flow index (MFI) value in the work. - 34Ravati, S.; Favis, B. D. Tunable Morphologies for Ternary Blends with Poly(Butylene Succinate): Partial and Complete Wetting Phenomena Polymer 2013, 54, 3271– 3281[Crossref], [CAS], Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXot1Cqt7w%253D&md5=e5aece5d0eb7c5310c92204990907fccTunable morphologies for ternary blends with poly(butylene succinate): Partial and complete wetting phenomenaRavati, Sepehr; Favis, Basil D.Polymer (2013), 54 (13), 3271-3281CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)Poly(butylene succinate) (PBS) is a promising polymer for the prodn. of bio-based and biodegradable materials. This study focuses on the development of novel tunable morphol. states based on ternary blends comprising PBS. The other biodegradable polymers are selected from a set of poly(lactic acid) (PLA), poly(butylene adipate-co-terephthalate) (PBAT), and polycaprolactone(PCL). Three completely different morphol. states are obsd. here for the ternary blends and are reported for the first time including: partial wetting for PBS/PLA/PCL in which PLA droplets self-assemble at the interface of PBS and PCL; complete wetting tri-continuous morphol. for PBS/PLA/PBAT; and a highly unusual state combining both partial and complete wetting cases for the PBS/PBAT/PCL blend. The dramatic variation of morphol. for these blends is possible due to very low interfacial tensions between the polymer pairs. Within these morphol. wetting states a significant variety of specific structures can be obtained through control of the relative compns. For example, for the partially wet xPBS/yPLA/50%PCL blend, changing the vol. fraction of PBS to PLA from φPBSφPLA = 10 to φPBS/φPLA = 0.1 results in a transformation from PLA droplets at the PBS/PCL interface to PBS droplets at the PLA/PCL interface. From the thermodn. standpoint, the obsd. partial and complete wetting cases are supported by Harkins theory. This work opens the door to a wide range of novel and stable PBS-based ternary blend structures comprising biodegradable polymers.
- 35Ravati, S.; Favis, B. D. Interfacial Coarsening of Ternary Polymer Blends with Partial and Complete Wetting Structures Polymer 2013, 54, 6739– 6751[Crossref], [CAS], Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhs1yrur7O&md5=3df9d3a8f2e5eee3aeab56fc6fbc7042Interfacial coarsening of ternary polymer blends with partial and complete wetting structuresRavati, Sepehr; Favis, Basil D.Polymer (2013), 54 (25), 6739-6751CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)The coarsening of polymer mixts. is an important route towards major morphol. modification in multiphase polymer systems. To date however the coarsening of ternary systems has not been significantly examd. In this study the phase coarsening mechanism via annealing for partial wetting, and complete wetting morphologies in ternary polymer blends is characterized. This is a route towards the examn. of interfacial coarsening in polymer blends since ternary partially wet systems involve the presence of interfacial droplets while completely wet ternary systems are comprised of a complete interfacial layer. A partial wetting type of morphol. is obtained for polybutylene succinate (PBS)/poly(lactic acid) (PLA)/polycaprolactone (PCL). Three different compns. for that system with compn. ratios of .vphi.(PBS/PLA) = 1.5; .vphi.(PBS/PLA) = 3; and .vphi.(PBS/PLA) = 10 are prepd. to show the effect of the concn. of the self-assembled PLA droplets located at the interface of PBS/PCL. As the concn. of PLA decreases, the growth rate of the PLA phase during the annealing process sharply decreases due to a significant increase of the "surface to vol. ratio" of the PLA droplets required in order to cover the interface. In this case, due to the short inter-droplet distances between PLA droplets at the interface, coalescence is controlled by the drainage time. This mechanism is confirmed by the observation of a linear relationship between the third power of droplet size and annealing time. For the 37.5%PBS/12.5%PLA/50%PCL blend, the conservation of interfacial-angles confirms that the annealing time has no effect on the angle values between phases, as predicted by Harkins spreading theory.The annealing process for complete wetting is studied at four compns. for an HDPE/PS/PCL blend where the PS phase is located as a continuous layer at the interface of co-continuous HDPE/PCL. In 33.3%HDPE/33.3%PS/33.3%PCL after 30 min of annealing, the PS phase thickness increases 49 times from 2.3 μm to 112 μm. Even for very low concns. of 3%PS, a high coarsening rate of 0.0039 μm/s is obsd. This sharp linear increase in PS phase size implies a capillary pressure mechanism and an impeded growth of Tomotika-like capillaries for all three phases that cause a confinement effect for coarsening of the middle PS phase.
- 36Bitinis, N.; Verdejo, R.; Cassagnau, P.; Lopez-Manchado, M. A. Structure and properties of polylactide/natural rubber blends Mater. Chem. Phys. 2011, 129, 823– 831[Crossref], [CAS], Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXovFClsbs%253D&md5=57010d1a3d7d12f2196d4fdb2890d309Structure and properties of polylactide/natural rubber blendsBitinis, N.; Verdejo, R.; Cassagnau, P.; Lopez-Manchado, M. A.Materials Chemistry and Physics (2011), 129 (3), 823-831CODEN: MCHPDR; ISSN:0254-0584. (Elsevier B.V.)Polylactide, PLA, is a biodegradable thermoplastic polyester derived from biomass that has restricted packaging applications due to its high brittleness and poor crystn. behavior. Here, new formulations based on natural rubber-PLA blends have been developed. The processing windows, temp., time, and rotor rate, and the rubber content have been optimized in order to obtain a blend with useful properties. The rubber phase was uniformly dispersed in the continuous PLA matrix with a droplet size range from 1.1 to 2.0 μm. The ductility of PLA has been significantly improved by blending with natural rubber, NR. The elongation at break improved from 5% for neat PLA to 200% by adding 10% NR. In addn., the incorporation of NR not only increased the crystn. rate but also enhanced the crystn. ability of PLA. These materials are, therefore, very promising for industrial applications.
- 37Bitinis, N.; Sanz, A.; Nogales, A.; Verdejo, R.; Lopez-Manchado, M. A.; Ezquerra, T. A. Deformation Mechanisms in Polylactic Acid/Natural Rubber/Organoclay Bionanocomposites as Revealed by Synchrotron X-ray Scattering Soft Matter 2012, 8, 8990– 8997[Crossref], [CAS], Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtFOms7zL&md5=c2639941c1a0f9108055a2fa2f4fd532Deformation mechanisms in polylactic acid/natural rubber/organoclay bionanocomposites as revealed by synchrotron X-ray scatteringBitinis, Natacha; Sanz, Alejandro; Nogales, Aurora; Verdejo, Raquel; Lopez-Manchado, Miguel A.; Ezquerra, Tiberio A.Soft Matter (2012), 8 (34), 8990-8997CODEN: SMOABF; ISSN:1744-683X. (Royal Society of Chemistry)The micromech. deformation mechanisms of a polylactic acid (PLA)/natural rubber (NR) blend (PLA/NR 90/10 wt%) and its organoclay filled bionanocomposites have been investigated by small and wide angle X-ray scattering (SAXS-WAXS) under tensile conditions. The addn. of NR to a PLA matrix changed the brittle fracture of PLA to a ductile deformation through the debonding of the rubber droplets. Otherwise, the formation of cavities between PLA and NR was hampered by the nanoclays since they were mainly located at the polymer blend interface. In this case, the nanoclays acted as craze nucleation sites. At 1 wt% of filler concn., the crazes were able to fully develop in the blend and to evolve into stable microvoids, which kept growing and orienting in the tensile direction. These mechanisms also explained the progressive plastic deformation of the polymer chains and the preferential orientation of the nanoclay platelets.
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- 45Han, L.; Han, C.; Dong, L. Morphology and Properties of the Biosourced Poly(Lactic Acid)/Poly(Ethylene Oxide-b-amide-12) Blends Polym. Compos. 2013, 34, 122– 130[Crossref], [CAS], Google Scholar45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xhslymt77J&md5=e538dc60e34f823198d01cdb9e957b62Morphology and properties of the biosourced poly(lactic acid)/poly(ethylene oxide-b-amide-12) blendsHan, Lijing; Han, Changyu; Dong, LisongPolymer Composites (2013), 34 (1), 122-130CODEN: PCOMDI; ISSN:0272-8397. (John Wiley & Sons, Inc.)Biosourced poly(lactic acid) (PLA) blends with different content of poly(ethylene oxide-b-amide-12) (PEBA) were prepd. by melt compounding. The miscibility, phase structure, crystn. behavior, mech. properties, and toughening mechanism were investigated. The blend was an immiscible system with the PEBA domains evenly dispersed in the PLA matrix. The PEBA component suppressed the nonisothermal melt crystn. of PLA. With the addn. of PEBA, marked improvement in toughness of PLA was achieved. The max. for elongation at break and impact strength of the blend reached the level of 346% and 60.5 kJ/m2, resp. The phase morphol. evolution in the PLA/PEBA blends after tensile and impact tests was investigated, and the corresponding toughening mechanism was discussed. It was found that the PLA matrix demonstrates obvious shear yielding in the blend during the tensile and impact tests, which induced energy dissipation and therefore lead to improvement in toughness of the PLA/PEBA blends. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers.
- 46Dong, W.; Jiang, F.; Zhao, L.; You, J.; Cao, X.; Li, Y. PLLA Microalloys Versus PLLA Nanoalloys: Preparation, Morphologies, and Properties ACS Appl. Mater. Interfaces 2012, 4, 3667– 3675[ACS Full Text
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Supporting Information
Supporting Information
ARTICLE SECTIONSContact angle and surface tension values calculated for individual blend components are given in the Supporting Information, Table S1. This material is available free of charge via the Internet at http://pubs.acs.org.
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