Comparison between the efficiencies of two conductive networks formed in carbon black-filled ternary polymer blends by different hierarchical structures

Two different types of thermodynamically induced self-assembled hierarchical structures were formed in carbon black (CB)-filled POM/SAN/TPU and POM/SAN/PA6 ternary polymer blends when the minor third polymer components TPU and PA6, which have the highest affinity to CB among the three polymer components, were individually incorporated into CB-filled POM/SAN binary blend: TPU with imbedded CB forms the interphase, while PA6 with imbedded CB forms droplets inside the SAN phase. The efficiencies of the two types of conductive networks formed by these hierarchical structures are compared in terms of electrical percolation threshold. The percolation threshold of CB in POM/SAN (70/30) blend decreases by 59% and 54% when only 5 wt% of POM is replaced by TPU and PA6, respectively. The mechanisms of conductive network formation are different in the two cases and related to their blend morphology, one is double percolation in a tri-continuous blend and the other is triple percolation in a cocontinuous blend.     

Double percolation effect on the electrical conductivity of conductive particles filled polymer blends

Electrical conductivity of carbon black (CB) filled polymer blends which are incompatible with each other was studied as a function of the polymer's blend ratio. Transmission electron microscope (TEM) analysis shows that CB distributes unevenly in each component of a polymer blend. TEM photographs of phase structure of solvent extracted HDPE/PMMA blend and solvent extraction experiments of PMMA/PP blend detect the blend ratio at which the structural continuity of filler rich phase is formed. The electrical conductivity of polymer blends is found to be determined by two factors. One is the concentration of CB in the filler rich phase and the other is the structural continuity of this phase. This double percolation affects the conductivity of conductive particle filled polymer blends.     

Erosion‐dependant continuity development in high viscosity ratio blends of very low interfacial tension

This work studies continuity development and cocontinuity in high viscosity ratio EPDM/PP blends. A very low interfacial tension (0.3 mN/m) between the blend components together with high viscosity ratios (11 and 17) result in a variety of unusual morphological features, including isolated nanometer diameter fibers, very large particles, partially coalesced particles, and numerous particles interconnected by fibers. This unique combination of morphologies leads the blend to a novel and stable cocontinuous structure of partially coalesced particles and particles interconnected by fibers. Compared with low to medium viscosity ratio EPDM/PP blends, these cocontinuous networks demonstrate early percolation thresholds, rapid continuity development, and attain cocontinuity at lower compositions of minor phase. The slow surface erosion of the high viscosity EPDM phase during melt blending is shown to be responsible for the generation of these unusual morphological structures. Typically the timescale for erosion phenomena are so small that they have defied study in the mixing environment itself and typical blend morphology studies almost always examine the final steady‐state morphology obtained after several minutes of mixing. The combination of very low interfacial tension and very high viscosity ratios of these EPDM/PP systems provide a unique opportunity to examine erosion phenomena persisting over longer time scales during melt mixing. We propose a new concentration‐dependant erosion mechanism that is based on particle collision–coalescence–separation dynamics. The proposed conceptual mechanism is shown to dramatically accelerate the erosion process and maintain cocontinuity over prolonged periods of mixing. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1919–1929, 2006     

Electrical properties and conductive mechanisms of immiscible polypropylene/Novolac blends filled with carbon black

Carbon black (CB)-filled immisicible thermoplastic/thermosetting polymer blends consisting of polypropylene (PP) and Novolac resin were reported in this paper. The PP/Novolac/CB blends with varied compositions and different processing sequences were prepared by melt-mixing method. The CB distribution, conductive mechanism and the relationship between morphology and electrical properties of the PP/Novolac/CB blends were investigated. Scanning electron microscopy (SEM), optical microscopy and extraction experiment results showed that in PP/Novolac blends CB particles preferentially localized in the Novolac phase, indicating CB has a good affinity with Novolac resin. The incorporation of CB changed the spherical particles of the dispersed Novolac phase into elongated structure. With increasing Novolac content, the elongation deformation of Novolac phase became more obvious and eventually the blends developed into co-continuous structure, which form double percolation and decrease the percolation threshold. When CB was initially blended with PP and followed by the addition of Novolac resin, the partial migration of CB from PP to the Novolac phase was possibly occurred. The addition of Novolac to PP evidently increases the storage modulus G′, loss modulus G″ and complex viscosity η^∗. The addition of CB to PP/Novolac blends further increase η^∗, and it increases with increasing CB loading, which was related to the change of composite morphology.     

Volume‐exclusion effects in polyethylene blends filled with carbon black,graphite, or carbon fiber

Conductive polymer composites possessing a low percolation‐threshold concentration as a result of double percolation of a conductive filler and its host phase in an immiscible polymer blend afford a desirable alternative to conventional composites. In this work, blends of high‐density polyethylene (HDPE) and ultrahigh molecular weight polyethylene (UHMWPE) were used to produce ternary composites containing either carbon black (CB), graphite (G), or carbon fiber (CF). Blend composition had a synergistic effect on electrical conductivity, with pronounced conductivity maxima observed at about 70–80 wt % UHMWPE in the CB and G composites. A much broader maximum occurred at about 25 wt % UHMWPE in composites prepared with CF. Optical and electron microscopies were used to ascertain the extent to which the polymers, and hence filler particles, are segregated. Differential scanning calorimetry of the composites confirmed that the constituent polymers are indistinguishable in terms of their thermal signatures and virtually unaffected by the presence of any of the fillers examined here. Dynamic mechanical analysis revealed that CF imparts the greatest stiffness and thermal stability to the composites. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1013–1023, 2002     

Conductivity of Poly(methyl methacrylate)/Polystyrene/Carbon Black and Poly(ethyl methacrylate)/Polystyrene/Carbon Black Ternary Composite Films

Poly(methyl methacrylate)(PMMA)/polystyrene(PS)/carbon black(CB)and poly(ethyl methacrylate)(PEMA)/PS/CB ternary composite films were obtained using solution casting technique to investigate double percolation effect.In both PMMA/PS/CB and PEMA/PS/CB ternary composite films,the CB particles prefer to locate into PS phase based on the results of calculating wetting coefficient,which is also confirmed by SEM images.The conductivity of the films was investigated,and the percolation threshold(￠c)of both ternary composite films with different polymer blend ratios was determined by fitting the McLachlan GEM equation.Conductivity of PMMA/PS/CB ternary composite films showed a typical double percolation effect.However,due to the double emulsion structure of PEMA/PS polymer blends,the PEMA/PS/CB ternary composite films(PEMA/PS=50/50)showed a higher￠c,even CB only located in PS phase,which conflicts with the double percolation effect.A schematic diagram combined with SEM images was proposed to explain this phenomenon.     

Simultaneous enhancement of electrical conductivity and impact strength via formation of carbon black‐filler network in PP/EPDM Blends

The electrical conductivity and impact strength of polypropylene(PP)/EPDM/carbon black ternary composites were investigated in this paper. Two processing methods were employed to prepare these ternary composites. One was called one‐step processing method, in which the elastomer and the filler directly melt blended with PP matrix. Another one was called two‐step processing method, in which the elastomer and the filler were mixed first, and then melt blended with pure PP. To get an optimal phase morphology that favors the electrical conductivity and impact strength, controlling the distribution of CB in PP/EPDM blend was a crucial factor. Thus the interfacial tension and the work of adhesion were first calculated based on the measurement of contact angle, and the results showed that CB tended to be accumulated around EPDM phases to form filler‐network structure. Expectably, the filler‐network structure was observed in PP/EPDM/CB(80/20/3) composite prepared by two‐step processing method. The formation of this filler‐network structure decreased the percolation threshold of CB particles in polymer matrix, and the electrical conductivity as well as Izod impact strength of the composite increased dramatically. This work provided a new way to prepare polymer composites with both improved conductivity and impact strength. Copyright © 2009 John Wiley & Sons, Ltd.     

Calorimetric investigation of the interaction of carbon nanotubes with polystyrene

A simple, scalable procedure that does not require covalent modification of the filler or specialized high shear mixers is described for preparing well‐dispersed carbon nanotube composites. Excellent particle dispersions of multiple‐walled carbon nanotubes (NTs) and carbon black (CB) in polystyrene (PS) are obtained by coating the particles with a <2‐nm layer of PS adsorbed from dilute solution, prior to incorporation in the composite. Improved mechanical properties of composites containing coated particles, especially NT, are demonstrated by dynamic mechanical analysis at low frequency and low amplitude. Formation of a partially immobilized region of polymer surrounding the particles is quantified using flow microcalorimetry with ethyl acetate or methyl ethyl ketone vapor to measure the increase in solvation enthalpy in this region. This calorimetric method is applied to both composites and compacted powder mixtures of NT or CB with PS. The response of integral heat of vapor sorption as a function of particle loading in powder mixtures is similar to percolation curves reported for mechanical and electrical properties of composites. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1821–1834, 2006     

Ethylene–acrylic acid copolymer induced electrical conductivity improvements and dynamic rheological behavior changes of polypropylene/carbon black composites

The experimental data reveal that the addition of ethylene–acrylic acid copolymer (EAA) into carbon black (CB)/polypropylene (PP) composites can improve the electrical conductivity of CB/PP composites by two to six orders of magnitude at a comparatively low CB content (φ), and when φ = 2.5 vol %, 60/40 of PP/EAA is an optimum for electrical conductivity improvement. The dynamic rheological data show that with increasing φ there are apparent rheological percolations for CB/PP composites. A modified Kerner–Nielson equation can be used to describe the correlation between electrical percolation and dynamic viscoelastic percolation. The addition of EAA into CB/PP composites leads to apparent changes in dynamic rheological behaviors. When φ = 2.5 vol %, a rheological percolation appears in CB/PP/EAA (CPE) composites with increasing EAA content. The similar rheological behaviors correspond to the similar morphological structures for CPE composites with φ = 5.0 vol %. The appearance of bumps in the van‐Gurp–Palmen plots corresponds to the formation of network structure in CB/PP and CPE composites, and the more perfect the networks, the higher the amplitude of the bumps. All data indicate that the van‐Gurp–Palmen plot is sensitive to the formation of filler particle networks or cocontinuous phase which spans the whole composite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1762–1771, 2009     

Relationship between electrical resistivity and particle dispersion state for carbon black filled poly (ethylene-<Emphasis Type="Italic">co</Emphasis>-vinyl acetate)/poly (<Emphasis Type="SmallCaps">L</Emphasis>-lactic acid) blend

It is known that the electrical volume resistivity of insulating polymers filled with conductive fillers suddenly decreases at a certain content of filler. This phenomenon is called percolation. Therefore, it is known that controlling resistivity in the semi-conductive region for carbon black (CB) filled composites is very difficult. When poly (ethylene-co-vinyl acetate) (EVA) is used as a matrix, the percolation curve becomes gradual because CB particles disperse well in EVA. In this study, the relationship between the dispersion state of CB particles and electrical resistivity for EVA/poly (L-lactic acid) (PLLA) filled with CB composite was investigated. The apparent phase separation was seen in the SEM photograph. It was predicted that the CB particles located into the EVA phase in the light of thermodynamical consideration, which was estimated from the wetting coefficient between polymer matrix and CB particles. The total surface area per unit mass of dispersed CB particles in the polymer blend matrix was estimated from small-angle X-ray scattering and the volume resistivity decreased with increasing CB content. The values of the surface area of CB particles in CB filled EVA/PLLA (25/75 wt%) and EVA/PLLA (50/50 wt%) polymer blends showed a value similar to that of the CB filled EVA single polymer matrix. In electrical volume resistivity measurement, moreover, the slopes of percolation curves of EVA/PLLA (25/75 wt%) and EVA/PLLA (50/50 wt%) filled with CB composite are similar to that of EVA single polymer filled with CB composite. As a result, it was found that CB particles selectively locate in the EVA phase, and then the particle forms conductive networks similar to the networks in the case of EVA single polymer used as a matrix.     

Positive‐temperature‐coefficient/negative‐temperature‐coefficient effect of low‐density polyethylene filled with a mixture of carbon black and carbon fiber

Low‐density polyethylene (LDPE) filled with carbon black (CB) and carbon fiber (CF) composites were prepared by a conventional melt‐mixing method. The effects of a mixture of CB and CF on the positive‐temperature‐coefficient (PTC) effect and the negative‐temperature‐coefficient (NTC) effect, as well as the percolation threshold, were examined in detail. A synergy effect between CB and CF occurred, in that continuous conductive pathways formed within the CB/CF‐filled composite. The percolation threshold was moved to a reduced filler content with the addition of CF to an LDPE/CB composite. A model was proposed to explain the difference in the PTC behavior of composites containing CB and CF and composites containing only CB or CF. In addition, the NTC effect was weakened with a mixture of CB and CF, and a relatively small radiation dose was required to eliminate the NTC phenomenon in LDPE/CB/CF composites. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3094–3101, 2003     

The outstanding ability of nanosilica to stabilize dispersions of Nylon 6 droplets in a polypropylene matrix

The effectiveness of hydrophobically modified nanosilica (NS) as interfacial modifying agent for immiscible polymer blends is evaluated. Blends of polypropylene (PP) with 20% of polyamide 6 (PA) and 5% hydrophobic NS were prepared by melt mixing. Compression molded sheets and extruded films were evaluated by scanning electron microscopy, transmission electron microscopy, tensile testing, and rheological measurements. Hydrophobic NS particles strongly reduce the polydispersity and droplet size of the dispersed phase, as a result of their preferential location at the interface. NS promotes outstanding stability of blend dispersion regardless of the processing or post‐processing technique employed. The viscoelastic terminal zone shows a plateau for PP/PA/NS, which corresponds to a suspension‐like behavior. Under large amplitude oscillatory shear, the increment in the non‐linearity parameter Q evidences the interactions between NS and blend components. Therefore, NS is an excellent morphological stabilizer that prevents coalescence, but cannot promote interfacial adhesion between immiscible PP and PA phases. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1567–1579     

Thermoelectric behavior (PTC) of carbon black‐containing TPX/UHMWPE and TPX/XL‐UHMWPE blends

This article describes the structure and electrical performance of positive‐temperature‐coefficient/negative‐temperature‐coefficient (PTC/NTC) effects of the following three‐component blends: poly(4‐methyl pentene‐1)/ultra‐high molecular weight polyethylene/carbon black (TPX/UHMWPE/CB), poly(4‐methyl pentene‐1)/crosslinked‐ultra‐high molecular weight polyethylene/carbon black (TPX/XL‐UHMWPE/CB), and γ‐irradiated, compression‐molded plaques of these blends. CB particles are preferentially attracted to the UHMWPE and XL‐UHMWPE particles, which constitute the dispersed phase within the TPX matrix, but practically cannot or can only very slightly penetrate them because of their extremely high viscosity. Thus, CB particles initially form conductive networks on the UHMWPE phase; this is followed by distribution in the TPX matrix, electrically connecting the CB‐covered UHMWPE particles. This unusual CB distribution results in a reduced percolation threshold of all blends. A double‐PTC effect is exhibited by the XL‐UHMWPE‐containing samples. Irradiation of compression‐molded plaques improves their thermoelectric behavior by amplifying the PTC effect and reducing the NTC effect. A schematic model of the double‐PTC effect is suggested, describing the morphological changes of 70TPX/30XL‐UHMWPE/CB blends at different stages of heating with respect to their thermoelectric behavior. Irradiation of TPX/UHMWPE/CB plaques converts these systems into high‐intensity PTC materials free of the NTC effect. © 2001 John Wiley & Sons, Inc. J Polym Sci B Part B: Polym Phys 39: 1415–1428, 2001     

Temperature-resistivity characteristics of a segregated conductive CB/PP/UHMWPE composite

A carbon black (CB)/polypropylene (PP)/ultrahigh-molecular-weight polyethylene (UHMWPE) composite with a segregated structure was fabricated by using binary polymer granules as matrices. In preparation, an ethanol-assisted dispersion method was employed to disperse CB particles on the surface of the two polymer granules. The segregated conductive network was then constructed by hot compaction based on the volume exclusion effect of the polymer matrices. The conductive composite shows an ultralow percolation threshold of 0.34 vol.%. In temperature-resistivity test, a double positive temperature coefficient (PTC) effect was observed. In addition, the negative temperature coefficient (NTC) effect was eliminated significantly. These interesting temperature-resistivity behaviors were ascribed to the introduction of the binary polymer matrices and the mobility limitation of CB particles located at the PP/UHMWPE interface. These characteristics were probed by in situ morphology observation in heating process. The present paper provides a novel route for preparing conductive composites with an ultralow percolation threshold, a wider PTC region, and a zero NTC effect.     

Viscoelastic properties of ionic polymer composites reinforced by soy protein isolate

Both linear and nonlinear viscoelastic properties of ionic polymer composites reinforced by soy protein isolate (SPI) were studied. Viscoelastic properties were related to the aggregate structure of fillers. The aggregate structure of SPI is consisted of submicron size of globule protein particles that form an open aggregate structure. SPI and carbon black (CB) aggregates characterized by scanning electron microscope and particle size analyzer indicate that CB aggregates have a smaller primary particle and aggregate size than SPI aggregates, but the SPI composites have a slightly greater elastic modulus in the linear viscoelastic region than the CB composites. The composite containing 3–40 wt % of SPI has a transition in the shear elastic modulus between 6 and 8 vol % filler, indicating a percolation threshold. CB composites also showed a modulus transition at <6 vol %. The change of fractional free volume with filler concentration as estimated from WLF fit of frequency shift factor also supports the existence of a percolation threshold. Nonlinear viscoelastic properties of filler, matrix, and composites suggested that the filler‐immobilized rubber network generated a G′ maximum in the modulus‐strain curves and the SPI formed a stronger filler network than the CB in these composites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3503–3518, 2005     

On the structure and electrical conductivity of polyaniline/polystyrene blends prepared by an aqueous‐dispersion blending method

This article describes electrically conductive polymer blends containing polyaniline‐dodecyl benzene sulfonic acid (PANI‐DBSA) dispersed in a polystyrene (PS) matrix or in crosslinked polystyrene (XPS). Melt blending of previously mixed, coagulated, and dried aqueous dispersions of PANI‐DBSA and PS latices lead to high conductivities at extremely low PANI‐DBSA concentrations (∼0.5 wt % PANI‐DBSA). In these blends, the very small size of the PANI‐DBSA particles and the surface properties (with surfactants used) of both the PANI and polymer particles play a major role in the PANI‐DBSA particle structuring process. The PANI‐DBSA behavior is characteristic of a unique colloidal polymeric filler with an extremely high surface area and a strong interaction with the matrix, evidenced by a significantly higher glass‐transition temperature of the matrix. The effect of the shear level on the conductivity and morphology of the PS/PANI‐DBSA blends was studied by the production of capillary rheometer filaments at various shear rates. An outstanding result was found for XPS/PANI‐DBSA blends prepared by the blending of aqueous XPS and PANI‐DBSA dispersions. Some of these blends were insulating at low shear levels; however, above a certain shear level, smooth surface filaments were generated, with dramatically increased and stable conductivities. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 611–621, 2001     

Phase morphology development in PP/PA6 blends induced by a maleated thermoplastic elastomer

The effects of maleated thermoplastic elastomer (TPEg) on morphological development of polypropylene (PP)/polyamide 6 (PA6) blends with a fixed PA6 content (30 wt %) were investigated. For purpose of comparison, nonmaleated thermoplastic elastomer (TPE) was also added to the above binary blends. A comparative study of FTIR spectroscopy in above both ternary blends confirmed the formation of in situ graft copolymer in the PP/PA6/TPEg blend. Dynamic mechanical analysis (DMA) indicated that un‐like TPE, the incorporation of TPEg remarkably affected both intensity and position of loss peaks of blend components. Scanning electron microscopy (SEM) demonstrated that PP/PA6/TPE blends still exhibited poor interfacial adhesion between the dispersed phase and matrix. However, the use of TPEg induced a finer dispersion and promoted interfacial adhesion. Transmission electron microscopy (TEM) for PP/PA6/TPEg blends showed that a core‐shell structure consisting of PA6 particles encapsulated by an interlayer was formed in PP matrix. With the concentration of TPEg increasing, the dispersed core‐shell particles morphology was found to transform from discrete acorn‐type particles to agglomerate with increasing degree of encapsulation. The modified Harkin's equation was applied to illustrate the evolution of morphology with TPEg concentration. “Droplet‐sandwiched experiments” further confirmed the encapsulation morphology in PP/PA6/TPEg blends. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1050–1061, 2006     

Nanostructured carbon black filled polypropylene/polystyrene blends containing styrene-butadiene-styrene copolymer: Influence of morphology on electrical resistivity

This paper is part of a comprehensive study on using selective localization of carbon black (CB) at the interface of immiscible polymer blends in order to reduce the percolation threshold concentration and enhance the conductivity of the blends. CB was successfully localized at the interface of polypropylene/polystyrene (PP/PS) blend by introducing styrene-butadiene-styrene (SBS) tri-block copolymer to the blend. In CB-PP/PS/SBS blends, CB has higher affinity for the polybutadiene (PBD) section of the SBS copolymer, whereas in CB-PP/PS blends, CB prefers the PS phase. PP/PS interface is one of the preferred locations for the SBS copolymer in the (PP/PS) blend; at which the PBD section of the SBS copolymer forms a few nanometers thick layer able to accommodate the CB nano-particles. The influence of SBS addition on the morphology and electrical properties of various PP/PS blends filled with 1 vol% CB were studied. SBS influence on the conductivity of PP/PS blends was found to be a function of the PP/PS volume ratio and SBS loading. The most dramatic increase in conductivity was found in the (60/40) and (70/30) PP/PS blends upon the addition of 5 vol% SBS. 5 vol% SBS was found to be the optimum loading for most blends. Using 10 vol% of SBS was reported to deteriorate electrical conductivity of the conductive co-continuous PP/PS blends. For all blends studied, SBS addition was found to compatibilize the blends. Finer morphologies were obtained by increasing SBS loading.     

Preparation of Polylactide/Poly(ether)urethane Blends with Excellent Electro-actuated Shape Memory via Incorporating Carbon Black and Carbon Nanotubes Hybrids Fillers

In this work, hybrid conductive fillers of carbon black(CB) and carbon nanotubes(CNTs) were introduced into polylactide(PLA)/thermoplastic poly(ether)urethane(TPU) blend(70/30 by weight) to tune the phase morphology and realize rapid electrically actuated shape memory effect(SME). Particularly, the dispersion of conductive fillers, the phase morphology, the electrical conductivities and the shape memory properties of the composites containing CB or CB/CNTs were comparatively investigated. The results suggested that both CB and CNTs were selectively localized in TPU phase, and induced the morphological change from the sea-island structure to the co-continuous structure. The presence of CNTs resulted in a denser CB/CNTs network, which enhanced the continuity of TPU phase.Because the formed continuous TPU phase provided stronger recovery driving force, the PLA/TPU/CB/CNTs composites showed better shape recovery properties compared with the PLA/TPU/CB composites at the same CB content. Moreover, the CB and CNTs exerted a synergistic effect on enhancing the electrical conductivities of the composites. As a result, the prepared composites exhibited excellent electrically actuated SME and the shape recovery speed was also greatly enhanced. This work demonstrated a promising strategy to achieve rapid electrically actuated SME via the addition of hybrid nanoparticles with self-networking ability in binary PLA/TPU blends over a much larger composition range.     

Preparation of Polylactide/Poly(ether)urethane Blends with Excellent Electro-actuated Shape Memory <Emphasis Type="Italic">via</Emphasis> Incorporating Carbon Black and Carbon Nanotubes Hybrids Fillers

In this work, hybrid conductive fillers of carbon black (CB) and carbon nanotubes (CNTs) were introduced into polylactide (PLA)/thermoplastic poly(ether)urethane (TPU) blend (70/30 by weight) to tune the phase morphology and realize rapid electrically actuated shape memory effect (SME). Particularly, the dispersion of conductive fillers, the phase morphology, the electrical conductivities and the shape memory properties of the composites containing CB or CB/CNTs were comparatively investigated. The results suggested that both CB and CNTs were selectively localized in TPU phase, and induced the morphological change from the sea-island structure to the co-continuous structure. The presence of CNTs resulted in a denser CB/CNTs network, which enhanced the continuity of TPU phase. Because the formed continuous TPU phase provided stronger recovery driving force, the PLA/TPU/CB/CNTs composites showed better shape recovery properties compared with the PLA/TPU/CB composites at the same CB content. Moreover, the CB and CNTs exerted a synergistic effect on enhancing the electrical conductivities of the composites. As a result, the prepared composites exhibited excellent electrically actuated SME and the shape recovery speed was also greatly enhanced. This work demonstrated a promising strategy to achieve rapid electrically actuated SME via the addition of hybrid nanoparticles with self-networking ability in binary PLA/TPU blends over a much larger composition range.