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1.
PLA and TPU were melt-blended to form shape memory bio-based blends with or without post-annealing effect. To the authors’ best knowledge, this is the first work to discuss the annealing effect on the PLA-based SMP blends. Annealed TPU showed regularly fractured surfaces unlike the macro-phase segregated domains for non-annealed TPU. After 3 h-annealing treatment, spherulites were observed for PLA, but not for TPU. The crystallinity of PLA increased, close to 3-fold increment, for annealed blends in comparison with non-annealed blends. The shape memory behaviors of PLA/TPU blends predeformed under three different predeformation temperatures (25, 80, 120 °C) were investigated. The annealing effect was helpful in enhancing the shape fixing ratio of the PLA/TPU (60/40) blend at high predeformation temperature of 120 °C in comparison with 25 °C. However, the suitable selection of the optimum predeformation temperature at 80 °C outweighed the annealing effect to attain the high shape fixing ratio, even in the case of non-annealed blends. The annealing effect often increased the perfection of crystal domains/interfaces and the larger crystal sizes, which would be detrimental to the molecular extensibility. The overall annealing effect on the shape recovery ratios were quite effective for both PLA/TPU blends of 80/20 and 60/40 without sacrificing the shape fixing ratios at the optimum predeformation temperature of 80 °C, attributing to the increased crystallinity of PLA and homogenized phase domains of TPU. Particularly, the annealing treatment did significantly increase the recovery ratio of the blends, more than 2-fold increment, especially for PLA/TPU (60/40) blend. At both lower or higher predeformation temperatures, the stress concentration between the increased crystalline domains and amorphous regions tended to dominate the annealing effect, leading to a negative contribution to the shape recovery processes.  相似文献   

2.
Blends of two biocompatible polymers: thermoplastic polyester‐urethane (TPU) and polylactic acid (PLA) were studied. The effect of the blending ratio on blend morphology and properties was examined by running a series of blends from 10 to 80 wt % of PLA. Increasing TPU concentration in the blends lowered the glass transition and melting point of PLA indicating that the components were compatible and partially miscible. The blends with 10–40 wt % PLA are hard, reinforced elastomers, while those with 60–80 wt % PLA are tough plastics. Cocontinuous morphology was suggested in samples with 40 and 50 wt % PLA. Inversion points between 30 and 40 wt % PLA (from globular phase is dispersed in the matrix to a cocontinuous morphology) and between 50 and 60 wt % PLA (a transition from cocontinuous to TPU dispersed in the PLA matrix) were observed. Elastomers with higher PLA content and intermediate morphology displayed a combination of high tensile strength, hardness, relatively high elongation and modulus. New materials have potential applications in the medical field. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41104.  相似文献   

3.
A series of thermoplastic polyurethane (TPU)/poly(lactic acid) (PLA) blends are studied in terms of morphological, thermal, and rheological properties by scanning electron microscopy, differential scanning calorimetry, and rheometry. Using supercritical CO2 batch foaming, the foamability of the blends is systematically investigated. It is found that the 80/20 (wt %/wt %) TPU/PLA blend (TPU80%) shows vastly enhanced foamability over a wide range of foaming conditions to produce foams with a myriad of cellular morphology. The foamability enhancement results from the improved cell nucleation and growth, and the changes in the polymer microstructure. Compared to elastic TPU foams, the TPU80% retain their shapes 3.4 times better. Mechanism for the enhanced stability is proposed and verified using Kohlrausch–Williams–Watts model. The materials developed in the study and the mechanistic understanding of the shape fixation process may facilitate the advancement of elastomeric foams in conventional use as well as in novel shape memory applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47416.  相似文献   

4.
In this study, shape memory is thermally induced in a series of graphene oxide (GO) filled poly(lactic acid)/thermoplastic polyurethane (PLA/TPU) blends, prepared via melt mixing process, and their shape recovery and shape fixity are measured, and the results are correlated with morphology, dynamic mechanical properties, crystallinity and creep recovery behavior. Morphological analysis by scanning and transmission electron microscopy reveals that the blends are immiscible, and GO platelets are mainly localized in the TPU phase of the blends, which lead to smaller and more elongated TPU droplets with improved interfacial adhesion being responsible for the improved shape recovery performance compared to the unfilled blend. A systematic enhancement found in storage and Young's modulus, tensile strength, creep resistance and creep recovery, and cold crystallinity as a result of GO inclusion are in agreement with the improved shape recovery, shape fixity and overall shape memory performance of the filled systems. The developed PLA/TPU/GO nanocomposites with highly improved mechanical properties can be utilized as a new class of environmentally friendly shape memory materials for a broad range of applications.  相似文献   

5.
Shape memory polymer nanocomposites based on thermoplastic polyurethane (TPU)/polylactic acid (PLA) blends filled with pristine multi-walled carbon nanotubes (MWCNTs) and modified MWCNTs─COOH were fabricated by direct melt blending technique and investigated for its morphology, mechanical, thermal, electrical, and shape memory properties. Morphological characterizations by using transmission electron microscope (TEM) and field emission scanning electron microscope (FESEM) revealed better dispersion of MWCNTs─COOH in the polymer blend, which is attributed to the improved interfacial interactions between the polymer blends and MWCNTs-COOH. Loading of the MWCNTs-COOH in the TPU/PLA blends resulted in the significant improvements in the mechanical properties such as tensile strength and elastic modulus and these effects are more pronounced on increasing the MWCNTs─COOH loading amount, when compared to the pristine MWCNTs filled system. Thermal analysis showed that the glass transition temperature of the blends increases slightly with increasing loading of both pristine and modified MWCNTs in the system. The resistance of nanocomposites decreased from 2 × 1012 Ω to 3.2 × 1010 Ω after adding 3% MWCNTs─COOH. The shape memory performance tests showed that the enhancement of shape recovery by 252% could be achieved at 3% MWCNTs loading, when compared to that of TPU/PLA blends.  相似文献   

6.
In this work, the compatibility of blends of plasticized poly(vinyl chloride) (p‐PVC) and thermoplastic polyurethane (TPU) was investigated using a dynamic mechanical analyzer and scanning electron microscopy. Two kinds of TPU with different ratios of hard to soft segments, i.e., TPU90 and TPU70 were compared. p‐PVC/TPU90 and p‐PVC/TPU70 blends with variable weight ratios (100/0, 90/10, 80/20, 70/30, 60/40, 50/50, 0/100) were prepared by melt blending. PVC was plasticized with 40 phr of dioctyl phthalate. It was found that TPU with a lower hard segment (i.e., TPU70) is more compatible with plasticized PVC than TPU with a higher hard segment (i.e., TPU90) in over the composition ranges examined. It was concluded that the compatibility of plasticized PVC and TPU are dependent on the ratio of hard to soft segments in TPU. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 415–422, 1999  相似文献   

7.
In this study, poly(l ‐lactide) (PLA) is melt‐blended with thermoplastic polyurethane (TPU) to modify the brittleness of PLA. An aliphatic ester‐based TPU was selected in order to have an ester sensitivity for degradation and an inherent biocompatibility. Using this compatible TPU, there was no need to apply problematic compatibilizers, so the main positive properties of PLA such as biocompatibility and degradability were not challenged. The detected microstructure of PLA/TPU blends showed that when the TPU content was lower than 25 wt %, the structure appeared as sea‐islands, but when the TPU content was increased, the morphology was converted to a cocontinuous microstructure. A higher interfacial surface area in the blend with 25 wt % TPU (PLA25) resulted in a higher toughness and abrasion resistance. The various analyses confirmed interactions and successful coupling of two phases and confirmed that melt‐blending of PLA with the aliphatic ester‐based TPU is a convenient, cost‐effective, and efficient method to conquer the brittleness of PLA. The prepared blends are general‐purpose plastics, but PLA25 showed an optimum mechanical strength, toughness, and biocompatibility suitable for a wide range of applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43104.  相似文献   

8.
Viscoelastic, interfacial properties, and morphological data were employed to predict the thermal and mechanical properties of compatibilized poly(lactic acid) (PLA)/thermoplastic polyurethane (TPU) blends. The combination of interfacial thickness measured by contact angle and entanglement density determined by dynamical mechanical analysis analyze data was employed to evaluate the mechanical behavior of PLA/TPU blends with and without ethylene-butyl acrylate-glycidyl methacrylate (EBG) compatibilization agent. The PLA/TPU blend (70/30 wt %) was prepared in a Haake internal mixer at 190 °C and compatibilized with different contents of EBG. The evaluation of the interfacial properties revealed an increase in the interfacial layer thickness of the PLA/TPU blend with EBG. The scanning electronic microscopy images showed a drastic reduction in the size of the dispersed phase by increasing the compatibilizer agent EBG content in the blend. The compatibilization of the PLA/TPU blends improved both the Izod impact strength and yield stress by 38 and 33%, respectively, in comparison with neat PLA/TPU blend. The addition of EBG into PLA/TPU blends significantly increased the entanglement density and the PLA toughening but resulted in a decrease of PLA deformation at break. The PLA and TPU glass transitions were affected by the EBG, suggesting that the PLA and TPU domains were partially miscible. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48926.  相似文献   

9.
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  相似文献   

10.
Ternary blends of poly(lactic acid) (PLA), polycaprolactone (PCL) and cellulose acetate butyrate (CAB) were fabricated into the form of electrospun nanofibres targeted for skin tissue scaffolds. The effects of blend ratio and molecular mass of PCL (PCL1 and PCL2) on morphology, miscibility, crystallinity, thermal properties, surface hydrophilicity and cell culture of the nanofibres were investigated. Blends with high PLA loading (80/10/10 PLA/PCL/CAB) gave fibres with a smooth surface, owing to the enhanced miscibility between the polymer chains from the presence of CAB, which acts as compatibilizer. In contrast, blends with high PCL loading were immiscible, which led to beads during the electrospinning process. The increased molecular mass of PCL2 produced smoother fibres than low‐molecular‐mass PCL1. The XRD patterns of blends of PLA/PCL1/CAB and PLA/PCL2/CAB were similar to one another, in which the high‐crystallinity peaks of PCL seen for 20/70/10 blends were very small for 50/40/10 blends and much less prevalent for 80/10/10 blends. Better fibre formation (80/10/10 > 50/40/10 > 20/70/10) with less crystallinity occurs in well‐formed fibres. Selected blends of PLA/PCL/CAB promoted growth of NIH/3T3 fibroblast cells, demonstrating that our novel biocompatible ternary blend nanofibrous scaffolds have potential in skin tissue repair applications. In addition, this work helps in the design and understanding of the factors that control the properties of nanofibrous PLA/PCL/CAB scaffolds. © 2017 Society of Chemical Industry  相似文献   

11.
The objective of the study is preparation of shape memory blend of polycarbonate (PC) and thermoplastic polyurethane (TPU). Polycarbonate is blended with three types of TPUs and subsequently mechanical, thermal, morphological, and shape memory properties of the PC/TPU blends are studied. When TPU content in the blend is higher than 40% (by weight), the glass transition temperature related to PC is not shown in the differential scanning calorimetry thermogram, indicating loss of PC properties. The 60/40 optimized blend of PC/TPUs exhibits maximum increment of about 1100% in elongation and 43% decrement in tensile strength. The shape recovery of the optimized blend obtained by addition of 40% (by weight) of TPUs in PC polymer is found to be 65% and shape fixity is 97%. These results suggest that the blend of PC/TPU may be utilized for various applications where shape memory property is required including strategic applications.  相似文献   

12.
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.  相似文献   

13.
To explore a potential method for improving the toughness of a polylactide (PLA), we used a thermoplastic polyurethane (TPU) elastomer with a high strength and toughness and biocompatibility to prepare PLA/TPU blends suitable for a wide range of applications of PLA as general‐purpose plastics. The structure and properties of the PLA/TPU blends were studied in terms of the mechanical and morphological properties. The results indicate that an obvious yield and neck formation was observed for the PLA/TPU blends; this indicated the transition of PLA from brittle fracture to ductile fracture. The elongation at break and notched impact strength for the PLA/20 wt %TPU blend reached 350% and 25 KJ/m2, respectively, without an obvious drop in the tensile strength. The blends were partially miscible systems because of the hydrogen bonding between the molecules of PLA and TPU. Spherical particles of TPU dispersed homogeneously in the PLA matrix, and the fracture surface presented much roughness. With increasing TPU content, the blends exhibited increasing tough failure. The J‐integral value of the PLA/TPU blend was much higher than that of the neat PLA; this indicated that the toughened blends had increasing crack initiation resistance and crack propagation resistance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

14.
The morphology and helium‐barrier properties of thermoplastic polyurethane (TPU)/ethylene‐vinyl alcohol (EVOH) blends with and without dicumyl peroxide (DCP) were investigated by melting blending. A lamellar dispersion of EVOH with good helium‐barrier properties was observed in the TPU matrix with DCP. The evolution of the morphology of the blends is mainly related to the variation of the viscosity ratio between the dispersed phase and the matrix phase. Compared with pure TPU, lamellar morphology increased the helium‐barrier properties of the TPU/EVOH (60/40) blend by as much as 10‐fold. We also explored the effects of composition, DCP content, and blending sequence on the morphology and helium‐barrier properties of the TPU/EVOH blends. The morphology of the blends ranged from a droplet‐matrix to a lamellar structure. We determined the optimum amount of DCP to improve the helium barrier of the blends. The helium‐barrier properties of the blends prepared by direct blending were superior to those of the blends prepared by two‐segment blending, and the blends prepared by direct blending exhibited a well‐developed lamellar morphology. We compared the permeability of the samples with the theoretical results to explain the relationship between morphology and helium‐barrier properties. POLYM. ENG. SCI., 56:922–931, 2016. © 2016 Society of Plastics Engineers  相似文献   

15.
This study aims to compare thermal, mechanical, and shape memory behavior of polylactic acid (PLA) blended with different structures of styrene-butadiene-styrene block copolymer (SBS), namely linear SBS (L-SBS), and radial SBS (R-SBS). The amount of L-SBS and R-SBS added was varied between 10 and 70 wt%, and the blending process was carried out using an internal mixer at 180°C before the shaping process by the compression molding. An improvement in the degree of crystallinity was observed across the entire composition range with less pronounced transition temperature change. Tensile strength and modulus of PLA/L-SBS blends were higher than PLA/R-SBS blends across all composition ranges. The results also revealed that the shape fixing ratio (Rf) and recovery ratio (Rr) of PLA/L-SBS were higher than PLA/R-SBS, with PLA70/SBS30 showed the best shape memory behavior. The morphology characteristics of the blend were also examined with the scanning electron microscope.  相似文献   

16.
A new thermoplastic polyurethane (TPU) was prepared from polylactide-b-poly(ethylene glycol)-b-polylactide (soft segment) and 2,4-toluene diisocyanate (hard segment). Then, TPU in various proportions (i.e., 50, 70, and 90 wt%) was blended with poly(ethylene-alt-maleic anhydride) (PEMA) to form samples coded as TPU/PEMA50, TPU/PEMA70, and TPU/PEMA90. The TPU and PEMA blend at ratio of 50:50 was reinforced by various graphene nanoplatelets (GNPs) contents. Three novel strategies were opted in this research, including design of novel thermoplastic polyurethane, blend of TPU with poly(ethylene-alt-maleic anhydride), and fabrication of graphene nanoplatelet-based nanocomposites. Hydrogen bonding between blend component and GNPs directed the formation of regular nanostructure. Consequently, unique self-assembled flower-shaped morphology was observed in blends as well as hybrid materials using the scanning electron microscopy technique. Physical interlinking between blend components and nanofiller was also responsible for rise in tensile modulus (39.3 MPa) and Young’s modulus (4.04 GPa) of the TPU/PEMA/GNP 5 hybrid compared with the neat blend. The crystallization property was studied by the X-ray diffraction analysis and differential scanning calorimetry. The melting temperature of about 70 °C was preferred for the shape recovery studies. The results from heat-induced shape recovery were compared with those of electroactive shape memory effects. Electrical conductivity was increased to 0.18 S cm?1 using 5 wt% GNP nanofiller, which was dependent on the applied temperature, as well. The original shape of TPU/PEMA/GNP 5 sample was almost 95 % recovered using heat-induced shape memory effect, while 98 % recovery was observed in an electric field of 40 V. Electroactive shape memory results were found to be better than those induced by heat stimulation effect.  相似文献   

17.
There are many studies devoted to conquer the strength–ductility trade‐off dilemma of polylactic acid (PLA) by flexible elastomer blending, like thermoplastic polyurethane (TPU), but little is known about the effects of the fused deposition modeling (FDM) process on the in situ morphology evolution of the elastomers. In this work, the effects of the three successive drawing processes in FDM on the morphology evolution of the dispersed TPU in the PLA matrix, and the toughening behavior of FDM‐printed PLA/microfibrillar‐TPU blends, are systematically studied. The results manifest that the average length of the TPU microfibrils can be turned precisely from 67.24 to 103.72 µm. The in situ microfibrillation process can remarkably improve the PLA crystallization capability and interfacial interaction. More interestingly, the inevitable decrease of impact strength of FDM‐printed part induced by the voids is compensated by the network‐like TPU microfibrils formed during the layer‐by‐layer printing. These inspiring findings suggest that the in situ fibrillation process can conquer the inherent weaknesses of both FDM process and PLA materials, providing facile and efficient method for fabricating high toughness PLA parts.  相似文献   

18.
Styrene–butadiene impact resin (SBC) was chosen as the toughening agent to improve the tensile toughness of polylactide (PLA). Epoxidized SBC (ESBC) with different epoxidation degree were prepared by epoxidation using in situ peroxoformic acid method and a series of PLA/SBC(ESBC) blends were prepared by melt blending. The elongation at break of the PLA/ESBC blends was greatly improved, which was reflected in the slight decrease in the tensile strength and tensile modulus. Moreover, the tensile strength and tensile modulus were not significantly affected by the epoxidation degree of ESBC. For example, the incorporation of ESBC28.8% (30 wt %) to PLA caused an obvious increment of elongation at break from 3.5% of pure PLA to 305.0%, while the tensile modulus and tensile strength decreased to 80 and 78% of pure PLA, respectively. Scanning electron microscopy observations of cryo‐fractured surface morphology and particle size analysis demonstrated that the compatibility of the PLA/ESBC blends was improved significantly compared to PLA/SBC blend. PLA/ESBC(70/30) blends exhibited shear‐thinning behavior over the range of the studied shear rate. With an increase in shear rate, the non‐Newtonian index of the blends decreased gradually. Furthermore, the flow behavior of PLA/ESBC(70/30) blends was more sensitive to the shear rate than pure PLA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46058.  相似文献   

19.
Bio‐based blends of commercially available polyester based bio thermoplastic polyurethane (TPU) and castor oil based polyamide 11 (PA11) of different ratios are prepared by melt processing. The blends properties such as shape memory behavior through unconstrained and constrained recovery, interfacial interaction, morphology, dynamic mechanical, rheological, and mechanical behavior are studied. A strong interface between the two polymeric phases due to hydrogen bonding observed through morphology indicates that TPU and PA11 are well compatible. The complex viscosity of blends ranges between that of neat PA11 and TPU. Thermal analysis shows that higher the TPU content lower the melting point (Tm ) corresponding to PA11 and the crystallization temperature (Tc ) remains unaltered. Adding TPU to PA11 ductility and impact strength of the blends increases significantly with the small reduction in their tensile strength. Shape memory behavior investigation reveals that, blends recover almost 95% of the applied deformation when heated at zero load and they recovered a stress of 1.8–3.2 MPa in constrained recovery during three consecutive thermomechanical cycles. The reported results on bioalloys promotes the usage in multidisciplinary field of intelligent devices, such as ergonomic grips and sports shields. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44794.  相似文献   

20.
Blends of two semicrystalline polymers, poly(L ‐lactic acid) (PLLA) and poly‐p‐dioxanone (PPD) have been prepared by solvent casting in different compositions. Thermal, morphological, and mechanical properties of the blends were studied using modulated differential scanning calorimetry, wide‐angle X‐ray diffractometry, scanning electron microscopy (SEM), polarizing light microscopy (PLM), and tensile tests. Thermal analysis showed two glass transition temperatures nearly constant and equal to the values of the homopolymers and constant values of melting temperature (Tm) for all blend compositions, suggesting that both polymers are immiscible. The PLM and SEM observations validated these results, and showed the different morphology obtained by changing the composition of the blend. The blends 40/60, 50/50, and 60/40 presented a clearly macroseparated system, while the 20/80 and 80/20 blends presented better homogeneity, probably due to the low amount of one component in the other. It was found by PLM that PPD is able to crystallize according to a spherulitic morphology when its content is above 40%. Under this content, the crystallization of PPD is hardly observed. The blend 20/80 is more flexible, and tough material and neck formation during elongation is also observed, due to PPD, which may act as a plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 2744–2755, 2003  相似文献   

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