Crystallization Of PVDF Research Articles

Stabilizing Liquid Electrolytes in a Porous PVDF Matrix Incorporated with Star Polymers with Linear PEG Arms and CycloPEG Cores.

Porous membranes fabricated from poly(vinylidene fluoride) (PVDF) and a star polymer with linear poly(ethylene glycol) (PEG) arms and cycloPEG cores were fabricated via the phase-separation method. The porous gel polymer electrolytes (PGPEs) were obtained by immersing the porous membranes in the electrolyte solution. When the additive amount of star polymer was up to 20 wt %, the prepared membrane had the largest porosity and the pores were uniformly distributed in the membrane. The star polymer can not only decrease the crystallization of PVDF and enhance the absorption of liquid electrolyte but also offer ion conduction channels (cycloPEG cores). Therefore, the PGPE with 20 wt % star polymers exhibited competitive ionic conductivities of 1.27 mS cm-1 at 30 °C and 2.89 mS cm-1 at 80 °C. To stabilize the liquid electrolyte in the holes of porous membranes, a gelator was introduced in the liquid electrolyte to form gelled porous gel polymer electrolytes (GPGPEs), and the leakage of liquid electrolytes was thus remarkably reduced. The ionic conductivity of GPGPEs with 20 wt % star polymer and 1.5 wt % gelator was importantly improved at high temperatures (6.02 mS cm-1 at 80 °C). We systematically investigated the electrochemical performances of PGPEs without star polymer, PGPEs with star polymer, and GPGPEs with star polymer. The incorporation of star polymers with linear PEG arms and cycloPEG cores into the PGPEs and GPGPEs significantly improved the electrochemical performances of the lithium metal/LiFePO4 cell assembled with the PGPEs or GPGPEs.

Evident improvements in the rigidity, toughness, and electrical conductivity of PVDF/HDPE blend with selectively localized carbon nanotube

In this work, carbon nanotube (CNT) was used to fabricate poly(vinylidene fluoride) (PVDF)/high density polyethylene (HDPE) blend-based nanocomposites via a Haake mixer. Scanning electron microscopy confirmed that the CNT was mainly selectively located in the HDPE dispersed domains. Thermogravimetric analysis revealed that CNT addition improved the thermal stability of the blend (up to 61 °C increase at 3-phr CNT loading at 40 wt% loss) in air environment. Differential scanning calorimetry results revealed the enhanced nucleation of individual PVDF and HDPE upon crystallization in the composites; the presence of CNT inceased the stability of PVDF crystals. CNT addition increased the heat distortion temperature of the blend by up to 27 °C at 3-phr CNT loading. The complex viscosity and storage modulus increased due to the CNT pseudo-network formation in the reduce-sized HDPE phase of the composites. The rigidity of the blend was significantly improved after the addition of CNT. The impact strength of the blend increased by up to 66% after 2-phr CNT loading, and the electrical resistivity of the blend decreased by up to nine orders at 3-phr CNT loading due to the double percolation-like morphology formation.

Negative dielectric permittivity of PVDF nanocomposites induced by carbon nanofibers and polymer crystallization

AbstractNegative permittivity is a key characteristic of the distinctive metamaterials, a novel class of artificial materials with particular electromagnetic properties. Negative permittivity has been realized in metallic structures with special designs, but rarely achieved in polymer nanocomposites. Our recent studies discover that negative permittivity can be attained from randomly distributed carbon nanofiber (CNF) filled poly(vinylidene fluoride) (PVDF) composites over a wide frequency range, and the negative permittivity values are strongly influenced by CNF and PVDF crystalline structures. The effects of CNF on the crystallization of PVDF, and the resultant negative dielectric permittivity of CNF/PVDF composites influenced by crystallization of PVDF and CNF, are investigated. It is revealed that the introduction of CNF not only affects the dielectric permittivity directly, but also causes indirect effects to the dielectric permittivity through influencing the crystallization of PVDF. In particular, due to addition of more CNF, a α‐ to β‐phase transformation in PVDF is found to affect permittivity of the nanocomposites. Furthermore, the permittivity of CNF/PVDF composites are increased considerably (“more negative”) with more CNF, and is affected noticeably by crystalline structures of PVDF. The lowest negative permittivity achieved is −2,500 for the nanocomposite with 5 wt% CNF at 5 kHz.

Inter‐spherulitic/inner‐spherulitic localization of PBSU during crystallization of PVDF in PVDF/PBSU blend

AbstractIn this work, the miscibility effect on the localization of poly(butylene succinate) (PBSU) during the crystallization of PVDF in their blend has been investigated. After annealed at 200 °C and 240 °C, homogeneous and phase‐separated structures can be obtained respectively, which was followed by isothermal crystallization at 141 °C. In the case of 200°C, PBSU tends to enrich in inner‐spherulitic regions because of the excellent miscibility of the blend and the higher growth rate of PVDF crystals. When the specimen was annealed at 240 °C, phase separation produces PVDF and PBSU domains. Upon cooling to 141 °C, one part of PBSU is miscible with , while the other part of it remains as phase‐separated domains due to the high viscosity and slow relaxation of them. The former accounts for the distribution of PBSU in inner‐spherulitic regions. In the latter, however, phase‐separated structures depress the diffusion of PVDF during its crystallization, leading to the lower magnitude of growth rate of spherulites. Both of them contribute to the localization of PBSU in inter‐spherulitic regions. The distribution of PBSU among PVDF spherulites has been validated by long periods, pore size, and mechanical performance of the porous PVDF membranes.

Relaxation dynamics of blends of PVDF and zwitterionic copolymer by dielectric relaxation spectroscopy

ABSTRACTRelaxation dynamics of PVDF blended with a random zwitterionic copolymer (r‐ZCP) of methyl methacrylate and zwitterionic sulfobetaine‐2‐vinylpyridine (PMMA‐r‐SB2VP) were investigated using dielectric relaxation spectroscopy. FTIR spectroscopy was used to determine the PVDF crystal phase of compression molded blends. Adding 25 wt% of r‐ZCP promoted the formation of the polar β and γ crystals over the nonpolar α phase. A structural model is proposed where the r‐ZCP biases the PVDF to form polar crystal phases. Boyd's model was used to calculate the room temperature dielectric constants and led to good agreement with our measurements. Dielectric spectra of neat r‐ZCP showed two relaxation peaks attributed to PMMA units, with no additional relaxations present from the zwitterions. Blends of PVDF with r‐ZCP were dominated by the αc relaxation associated with the crystalline phase of PVDF, which showed an Arrhenius temperature dependence. Analysis of the conductivity spectra shows a larger DC conductivity in the blends than in either r‐ZCP or homopolymer PVDF. Blends show an additional peak in the loss tangent, absent in the copolymer or PVDF attributed to space‐charge polarization. Higher DC conductivity and space‐charge polarization indicate that the combination of zwitterions and unique microstructure affects charge transport properties.

Hierarchically porous membranes with isolated-round-pores connected by narrow-nanopores: A novel solution for trade-off effect in separation

In this work, a concept of hierarchically porous membranes (HPMs) with isolated-round-pores connected by narrow-nanopores whose separation performance could be enhanced significantly is reported. On one hand, the simulation results provide the direct evidence that the existence of isolated-round-pores can shorten diffusion length and minimize diffusion barrier, which is the reason for the higher flux relative to the reference with only narrow-nanopores; on the other hand, HPMs have been fabricated successfully in ternary blend of PVDF/PMMA/PLLA. Due to the special miscibility in the blend, phase separation produces PLLA islands and PVDF/PMMA matrix. In the matrix, PMMA has been expelled out during the crystallization of PVDF, resulting in bi-continuous structures of them in nanometers. After the extraction with chloroform, the narrow-nanopores (from nano-continuous PMMA) connect the isolated-round-pores (from islands of PLLA) with each other, yielding interpenetrated micro-channels. During separation with HPMs, the selectivity is determined by porous structures in matrix. It has been further improved by the width of the anisotropic narrow pores, contributing to the high rejection ratio. The permeability has been enhanced remarkably via shorter diffusion length and lower diffusion barrier resulted from the isolated-round-pores. Our result provides a novel solution for trade-off effect between permeability and selectivity in separation.

The microstructure regulation, strengthening, toughening and hydrophilicity of polyamide6 in fabricating poly (vinylidene fluoride)-based flat membrane via the thermally induced phase separation technique

The poly (vinylidene fluoride) (PVDF)/polyamide6 (PA6) flat blend membrane was prepared via thermally induced phase separation (TIPS) process using water-soluble diluent mixture. The function of PA6 to induce the non-solvent induced phase separation (NIPS) was disclosed for the first time and the membrane formation mechanism about S-L phase separation of TIPS by combining the pore-forming effect of PA6 and restricting PVDF crystallization to form somewhat opened cellular pore was proposed. The effect of PA6 on the microstructure of upper surface and matrix was discussed. The hydrophilicity, permeability, anti-fouling capability and anti-fouling mechanism of the membrane were investigated. Interestingly, the morphology of PA6 within the matrix changed from the dispersed phase (particle or fiber) to the continuous phase (network fiber) with the addition of PA6, which in turn increased the breaking strength or breaking elongation and the corresponding mechanisms of strengthening and toughening were developed from the point of crystal particle, fiber and network fiber, respectively. Also, the introduction of PA6 reduced the shrinkage of the membrane, increased the porosity and hydrophilicity, improved the rejection to petroleum ether-in-water emulsion and Congo Red (CR), and enhanced the anti-fouling capacity. This work disclosed the functions of water-insoluble hydrophilic polymer to induce the mass-transfer, pore-forming effect by combining the S-L phase of TIPS and NIPS during the membrane formation process for the first time, presented sample and effective method to tailor the microstructure of membrane and enhance the mechanical property, permeability of membrane via the combination of TIPS and polymer blending for water treatment.

Effect of Illite on Crystallization of Poly(vinylidene fluoride)

Poly(vinylidene fluoride) (PVDF) was blended with cetyltrimethylammonium bromide (CTAB)-modified illite through a solvent-casting method. The effects of the content of modified illite and temperature on γ-phase PVDF crystallization were studied in detail. Unmodified illite does not affect the crystallization of PVDF. By contrast, modified illite can effectively boost the nucleation of the γ-phase due to the electrostatic interaction between PVDF and modified illite. For PVDF with low contents of modified illite, for example, 0.5 wt %, the ability to obtain the γ-phase is enhanced at 155 °C compared with neat PVDF. Increasing the crystallization temperature or the content of modified illite facilitates to form more γ-phase. Blending of 2.0% modified illite generates a pure γ-phase regardless of crystallization temperature. The technique to prepare pure γ-phase PVDF materials has a huge potential application in the fabrication of cheap pyro- or piezoelectric devices.

Dielectric relaxation, Li-ion transport, electrochemical, and structural behaviour of PEO/PVDF/LiClO4/TiO2/PC-based plasticized nanocomposite solid polymer electrolyte films

Abstract Poly(ethylene oxide) (PEO)/poly(vinylidene fluoride) (PVDF) (75/25 wt/wt%) host polymer blend matrix, lithium perchlorate (LiClO4) ionic dopant (25 wt%), titanium dioxide (TiO2) inorganic nanofiller (10 wt%), and propylene carbonate (PC) plasticizer (10–30 wt%) based different compositions electrolyte films were prepared. The morphological study reveals that the spherulite and fibril-like microstructures of the 75PEO/25PVDF–25 wt% LiClO4 primary electrolyte film turned highly complex having cracks, pores, and some crumpled fluffier structures when TiO2 and PC were added. X-ray diffractograms of these films confirm their semicrystalline structures having α-, β-, and γ-phase crystals of PVDF, and also the characteristic crystallites of PEO and TiO2 nanoparticles. Complex dielectric permittivity, dielectric loss tangent, ac electrical conductivity, impedance, and electric modulus spectra over the frequency range 20 Hz–1 MHz at 27 °C were reported and analyzed for confirmation of various polarization processes and relaxations in these heterogeneous electrolyte materials. It is found that the dc ionic conductivity of these materials is principally ruled by the ions coupled chain segmental dynamics which promotes the cations hopping mechanism. The results confirm that the electrolyte films containing 10 wt% TiO2 along with PC ≥ 20 wt% have dc ionic conductivity more than two times higher as compared to that of the primary electrolyte film. All these electrolyte films have considerable electrochemical performance and nearly unity value of total ion transference number. The fascinating ionic conduction and electrochemical properties confirm these flexible-type electrolytes as appealing materials for advances in all-solid-state lithium ion conducting devices.

Bioinspired Three-Dimensional Magnetoactive Scaffolds for Bone Tissue Engineering.

Bone tissue repair strategies are gaining increasing relevance due to the growing incidence of bone disorders worldwide. Biochemical stimulation is the most commonly used strategy for cell regeneration, while the application of physical cues, including magnetic, mechanical, or electrical fields, is a promising, however, scarcely investigated field. This work reports on novel magnetoactive three-dimensional (3D) porous scaffolds suitable for effective proliferation of osteoblasts in a biomimetic microenvironment. This physically active microenvironment is developed through the bone-mimicking structure of the scaffold combined with the physical stimuli provided by a magnetic custom-made bioreactor on a magnetoresponsive scaffold. Scaffolds are obtained through the development of nanocomposites comprised of a piezoelectric polymer, poly(vinylidene fluoride) (PVDF), and magnetostrictive particles of CoFe2O4, using a solvent casting method guided by the overlapping of nylon template structures with three different fiber diameter sizes (60, 80, and 120 μm), thus generating 3D scaffolds with different pore sizes. The magnetoactive composites show a structure very similar to trabecular bone with pore sizes that range from 5 to 20 μm, owing to the inherent process of crystallization of PVDF with the nanoparticles (NPs), interconnected with bigger pores, formed after removing the nylon templates. It is found that the materials crystallize in the electroactive β-phase of PVDF and promote the proliferation of preosteoblasts through the application of magnetic stimuli. This phenomenon is attributed to both local magnetomechanical and magnetoelectric response of the scaffolds, which induce a proper cellular mechano- and electro-transduction process.

Influence of Cation and Anion Type on the Formation of the Electroactive β-Phase and Thermal and Dynamic Mechanical Properties of Poly(vinylidene fluoride)/Ionic Liquids Blends

Films based on poly(vinylidene fluoride) (PVDF) blended with ionic liquids (ILs) comprising different cations and anions were developed to investigate the IL influence on the resulting PVDF crystal...

Highly Sensitive Humidity Sensor Based on Ionic Liquid–Polymer Composites

Polymer composites comprising the ionic liquid (IL) [Bmim][FeCl4] and poly(vinylidene fluoride) (PVDF) have been developed for humidity sensing applications. Different IL contents (5, 10, and 20 wt %) were incorporated into the PVDF matrix and the morphological, physical–chemical and electrical properties of the composites evaluated, together with their humidity sensitivity response. Higher IL contents (20 wt %) induce a porous morphology in the composites. Further, IL incorporation leads to the crystallization of PVDF in the electroactive β phase, which content increases with the incorporation of IL into the polymer. The thermal stability of the composites decreases with increasing IL content. The humidity sensing response of the composites was evaluated with relative humidity variations from 35 to 90%. It is shown that all composites exhibit a linear resistance variation with the relative humidity, the sensitivity to humidity variations increasing linearly with the IL content. The developed materials show a strong potentiality for printable humidity sensors.

Hydrophobic SiO2 nanoparticle‐induced polyvinylidene fluoride crystal phase inversion to enhance permeability of thin film composite membrane

ABSTRACTThin film composite (TFC) membrane can get rid of small molecular contaminants and salts with a very high efficiency, thus exhibiting promising potential for addressing the emerging problem of a clean water shortage. In this work, a new type of TFC membrane was prepared by interfacial polymerization of two monomers (MPD and TMC) on surface of SiO2/polyvinylidene fluoride (PVDF) substrate. The maximum flux of 3.16 L m−2 h−1 Bar−1 was achieved for the optimized hydrophobic SiO2 nanoparticles well dispersed in PVDF substrate, which is 2.6 times higher than that of 1.21 L m−2 h−1 Bar−1 for the commercial cellulose triacetate reverse osmosis membrane. The improved performance of TFC membrane could be attributed to the higher compaction resistance of SiO2/PVDF substrate. Further analysis revealed that PVDF crystal phase inversion induced by superhydrophobic SiO2 nanoparticles obviously enhanced the intramolecular and intermolecular hydrogen bonds between PVDF polymer molecules. Additionally, the narrower finger‐like pore size and thicker pore wall of SiO2/PVDF substrate also played significant roles in enhancing the compaction resistance of PVDF membrane. This work also provides a proof‐of‐concept demonstration of high permeability substrates for effective flux enhancement of TFC membranes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 48204.

β-Cyclodextrin functionalized coaxially electrospun poly(vinylidene fluoride) @ polystyrene membranes with higher mechanical performance for efficient removal of phenolphthalein

Core-shell structured fibers of poly (vinylidene fluoride) and polystyrene (PVDF@PS) were coaxially electrospun from two kinds of polymer solutions. The presence of PVDF as a core component greatly enhanced the mechanical properties of PVDF@PS fiber membranes due to the crystallization of PVDF, and the tensile strength as well as the elongation at break were 12.3 and 28.2 times higher than that of individual PS respectively. Then β-cyclodextrin (β-CD) molecules were attached onto the surface of PVDF@PS fibers using polydopamine (PDA) as an intermediate layer, achieving the functionalization of fiber membranes (PVDF@PS/PDA/β-CD). In comparison with other adsorbents containing β-CD, the as-prepared membranes exhibited an efficient adsorption capability of 19.24 mg/g for phenolphthalein (php) by the formation of inclusion complexes with β-CD and the interaction of hydrogen bond with PDA to some extent. Moreover, the membranes could be regenerated easily and retained about 86% of adsorption efficiency after five cycles. These results demonstrated the promise of PVDF@PS/PDA/β-CD membranes for removal of organic compound from aqueous media.

Impact of surface-modified molybdenum disulphide on crystallization, thermal and mechanical properties of polyvinylidene fluoride

Polymer nanocomposite based on layered structure such as graphene, MoS2, MoO3 and WS2 has become an active field of research due to their exceptional thermal, mechanical and electrical properties. Achieving uniform dispersion of layered nanostructures within the polymer matrix is challenging because of the agglomeration of nanostructures which occurs due to the Van der Waals attraction and the cohesive nature between the two phases. In this work, we report the preparation of PVDF-modified MoS2 nanocomposites by the solvent blending method. The XRD results reveal the interaction of the negatively charged surface of MoS2 sheets and the positive CH2 group of PVDF through the predomination of β-phase. Morphological observation through SEM suggests the MoS2 induced formation of nanofibres in the composite. Enhancement in the thermal stability of the nanocomposite is observed and is possibly due to the heat barrier by the exfoliated MoS2 which in turn supports the tortuous effect. The DSC of the PVDF-modified MoS2 composite indicates the domination of β-phase and the hindrance to crystallization of PVDF. Improvement in the mechanical strength of the composites was also noticed on higher filler concentration.

Synergistic Effect of Hydrogen Bonds and Diffusion on the β-Crystallization of Poly(vinylidene fluoride) On Poly(methyl methacrylate) Interface

The PVDF thin film was prepared on PMMA sublayer. Compared to the PVDF on Si wafer, the PMMA layer shows great influence on the crystallization of PVDF under quenching thermal treatment. When the PMMA layer is thinner than 90 nm, mixture of α- and β-crystals form. Pure β-crystals are obtained when the PMMA layer is around 90 nm. With further thickening of the PMMA layer, pure β-crystals always form but with a decreased crystallinity. The nanodomains and needlelike morphology of β-crystals is observed. Moreover the formation mechanism of β-phase on PMMA interface is clarified. The hydrogen bonds at PVDF and PMMA interface is formed adopting the perpendicular orientation, which serve as the key role to induce β-PVDF. The amount of β-PVDF is not only determined by the interaction of PMMA and PVDF at interface, but also the diffusion extent of PMMA into the PVDF layer.

Effect of Interfacial Interaction on the Conformational Variation of Poly(vinylidene fluoride) (PVDF) Chains in PVDF/Graphene Oxide (GO) Nanocomposite Fibers and Corresponding Mechanical Properties.

Poly(vinylidene fluoride) (PVDF)/graphene oxide (GO) nanocomposite fibers were dry-jet wet spun at the GO concentrations of 0, 1, and 2 wt % with respect to the polymer. The as-spun fibers were drawn in the draw ratio (DR) range of 2-6.5, and the correlation between the PVDF chain conformation and the mechanical properties of the fibers upon drawing has been studied by two-dimensional correlation spectroscopy of Fourier-transformed infrared, wide-angle X-ray diffraction, differential scanning calorimetry, and tensile testing. The PVDF/GO nanocomposite fibers exhibited that the mobile PVDF crystals due to the conformational defects and kinks were nucleated because of the polar interaction between PVDF chains and functional groups of GO, whereas the control PVDF fiber showed the conventional conversion of crystal polymorphs (α and γ phases to β phase). As a result, the nanocomposite fiber showed dramatically improved toughness (enhanced by 1123% at a DR of 2 and 120% at a DR of 6.5) as compared to that of the control fiber. Furthermore, the tensile strength and modulus of the PVDF/GO (2 wt %) fiber were 394 MPa and 4.6 GPa, respectively, whereas those of the control PVDF fiber were 295 MPa and 3.9 GPa, respectively.

Graphene Nanoplatelet-Reinforced Poly(vinylidene fluoride)/High Density Polyethylene Blend-Based Nanocomposites with Enhanced Thermal and Electrical Properties.

In this study, a graphene nanoplatelet (GNP) was used as a reinforcing filler to prepare poly(vinylidene fluoride) (PVDF)/high density polyethylene (HDPE) blend-based nanocomposites through a melt mixing method. Scanning electron microscopy confirmed that the GNP was mainly distributed within the PVDF matrix phase. X-ray diffraction analysis showed that PVDF and HDPE retained their crystal structure in the blend and composites. Thermogravimetric analysis showed that the addition of GNP enhanced the thermal stability of the blend, which was more evident in a nitrogen environment than in an air environment. Differential scanning calorimetry results showed that GNP facilitated the nucleation of PVDF and HDPE in the composites upon crystallization. The activation energy for non-isothermal crystallization of PVDF increased with increasing GNP loading in the composites. The Avrami n values ranged from 1.9–3.8 for isothermal crystallization of PVDF in different samples. The Young’s and flexural moduli of the blend improved by more than 20% at 2 phr GNP loading in the composites. The measured rheological properties confirmed the formation of a pseudo-network structure of GNP-PVDF in the composites. The electrical resistivity of the blend reduced by three orders at a 3-phr GNP loading. The PVDF/HDPE blend and composites showed interesting application prospects for electromechanical devices and capacitors.

Nano-porous shape memory membrane: Fabrication based on double bicontinuous structures in ternary blend and pore-size manipulation by macroscopic deformation

Nano-pore size is the key factor to determine the performance of porous membrane in various applications. The programmable and continuous manipulation of it remains as a great challenge. In this work, nano-porous shape memory polymer (SMP) membrane has been fabricated successfully in ternary blend of PVDF, PBSU and random copolymer (BMG) based on the special interface interaction and complicated phase behaviors among them. On one hand, phase separation takes place, producing bicontinuous structures with the characteristic size of microns including BMG rich phase and PVDF/PBSU mixed phase. The former provides shape memory effect in which cross-linked points and network play the roles of shape fixed phase and recovery phase respectively; on the other hand, exclusion of PBSU during crystallization of PVDF contributes to bicontinuous structures in nanoscale. The removal of PBSU based on double bicontinuous structures results in the interconnected nano-pores. The obtained nano-porous PVDF/BMG composite membranes possess not only shape memory performance, but also the interpenetrated channels. The pore size has been manipulated successfully by means of biaxial tension based on the proportional deformation in macro- and micro-scales. Our results provide a new strategy for the fabrication of nano-porous SMPs and the manipulation of pore size in them.

Multilayered assembly of poly(vinylidene fluoride) and poly(methyl methacrylate) for achieving multi-shape memory effects

The alternately-organized poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) multilayer materials were prepared through layer-multiplying coextrusion. With the multiplication of layers, the thickness of each layer was reduced in proportion and the layer interfaces were enriched generating a broader and more continuous thermal transition temperature (Ttrans) from PVDF to PMMA layers as mapped by in-situ thermal analysis. The low-Ttrans side originated from the glass transition of PMMA, whereas the high-Ttrans side was dominated by the melting of PVDF crystals based on the heating curves of DMA and DSC. The dielectric spectroscopy and 2D-SAXS were performed and demonstrated that the compositional diffusion not only broadened the relaxation distribution of amorphous chains, but also strengthened the interaction between amorphous and crystalline domains. Therefore, a unique multilayer network, where the crystals in PVDF layers acting as physical networks connected the neighboring amorphous layers, was fabricated and its potential application in obtaining multi-shape memory effect (MSME) was disclosed for the first time. The results exhibited that the 1024-layer specimen owned a better triple- and quadruple-shape memory capacity than conventional blend which possessed the same compositions and a similar Ttrans range. The latter one even failed to successively memorize more than two temporary shapes. A possible mechanism was proposed through polarized IR and creeping-recovery measurements. Higher phase continuity which benefited for the stress transfer was revealed to play a significant role in strengthening the shape-fixing and -recovering ability during each shape-memory progress. Accordingly, a new physically-compounding strategy was addressed to achieve outstanding MSME for meeting complex demands in smart applications.