A theoretically reproduced phase diagram for vinylidene fluoride and trifluoroethylene copolymers

The phase diagram of ferroelectric copolymers of vinylidene fluoride and trifluoroethylene is reproduced theoretically using a simple model for ferroelectric polymers. The copolymerization ratio dependencies of the intramolecular interaction and the intermolecular interaction are induced to reproduce the phase diagram. These interactions have the following effects on the ferroelectric phase transition of the copolymers. The intermolecular interaction between vinylidene fluoride segments is dominant in the ferroelectric phase transition. The intramolecular interaction, discriminating between different chain conformations, gives the phase transition a variety of characters, including first and second order phase transitions. The copolymerization ratio dependence of the intermolecular interaction is also numerically estimated by summing the interaction energy between all atoms. Comparing these two results, we discuss the size of a segment carrying an elementary process of the phase transition.     

Dielectric properties and ferroelectric behavior of poly(vinylidene fluoride‐trifluoroethylene) 50/50 copolymer ultrathin films

Ultrathin films of poly(vinylidene fluoride‐trifluoroethylene) copolymer [P(VDF‐TrFE), with a content (mol %) ratio of 50/50 VDF/TrFE] were fabricated on silicon wafers covered with platinum by a spin‐coating technique, ranging in thickness from 20 nm to 1 μm. The effect of thickness on dielectric properties and polarization behavior was investigated. A critical thickness was found to be about 0.1 μm. An abrupt drop of dielectric constant was observed, although there is no significant change in dielectric loss at this thickness. Square and symmetric hysteresis loops were obtained in films thicker than 0.1 μm. However, for films thinner than 0.1 μm, fewer square hysteresis loops were observed. SEM and X‐ray results demonstrate that the effect of thickness on dielectric and ferroelectric properties could be explained by the changes of crystal structure in these films. In addition, the effects of irradiation on dielectric property and polarization response for ultrathin P(VDF‐TrFE) films were also presented. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2259–2266, 2001     

Temperature dependence of polarization fatigue in ferroelectric vinylidene fluoride and trifluoroethylene copolymer films

In this study, we report the temperature dependence of polarization fatigue in ferroelectric copolymer films. Studies on temperature effect show a non‐monotonic change of fatigue rate with increasing temperature. At temperature below ～ 90°C, fatigue endurance is weakened at higher temperature; while, at temperature above ～ 90°C, experimental data indicate that the higher the temperature, the lower the fatigue rate. X‐ray diffraction spectra reveal little changes of characteristic peak before and after polarization fatigue. On the basis of the hypothesis of charge‐injection‐induced fatigue, we propose a possible explanation of our experimental results. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Imaging of local vibratory and non-vibratory domains in ferroelectric P(VDF-TrFE) films

In this paper we studied the distribution of local piezoelectricity in P(VDF-TrFE) ferroelectric films, and observed the coexistence of vibratory and non-vibratory domains. In all such experiments, we could observe the coexistence of in-phase vibratory domains with non-vibratory ones, or opposite-phase vibratory domains with non-vibratory ones, but no coexistence of in-phase domains with opposite-phase ones could be obtained. The origin of vibratory and non-vibratory domains was also discussed.     

All‐polymer electromechanical systems consisting of electrostrictive poly(vinylidene fluoride‐trifluoroethylene) and conductive polyaniline

The low elastic modulus and the ability to withstand high strain without failure make the conducting polymer attractive for a wide range of acoustic applications based on high‐strain electroactive polymers. In this article, we examine the electric and electromechanical performance of all‐polymer electromechanical systems, fabricated by painting conductive polyaniline (PANI) doped with camphor sulfonic acid (HCSA) on both sides of electrostrictive Poly(vinylidene fluoride‐trifluoroethylene) (P(VDF‐TrFE)) copolymer films, and compare them with those from the same copolymers with gold electrodes. The all‐polymer composite films are flexible, with strong coherent interfaces between the electrostrictive polymer layer and the conductive polymer layer. The electric performance such as dielectric properties and polarization hysteresis loops from P(VDF‐TrFE)/PANI film is nearly identical to those of P(VDF‐TrFE)/gold films in a wide temperature (from −50 to 120°C), and frequency range (from 1 Hz to 1 MHz). The all‐polymer systems also show a similar or even larger electric field induced strain response than that of films with electrodes under identical measurement conditions. The results demonstrate that the polyaniline/HCSA is good candidate material as the electrodes for electroactive polymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 945–951, 2000     

P(VDF-TrFE)-layered silicate nanocomposites. Part 1. X-ray scattering and thermal analysis studies

X-ray scattering and thermal analyses were used to investigate the effects of organically modified layered silicates (OMS) on the paraelectric and ferroelectric phase transitions in poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)]/OMS nanocomposites. Nanocomposites comprising a 75/25 P(VDF-TrFE) random co-polymer with either Nanomer I.30TC or Lucentite STN OMS were prepared with compositions ranging from 2 to 25 wt% OMS. Wide-angle X-ray scattering (WAXS) studies show that the silicate gallery spacing increases modestly in the nanocomposites compared to the neat OMS powder, indicating a level of co-polymer intercalation. Thermogravimetric analysis indicates that thermal stability is improved in nanocomposites with higher OMS contents: they have substantial increase in weight remaining, both at 500 °C and at 1000 °C, compared to that predicted from the behavior of the neat co-polymer and OMS. Differential scanning calorimetry (DSC) and WAXS results show that thermal transitions in the nanocomposites depend on OMS content. Nanocomposites with 2% OMS exhibited a crystal nucleating effect, which results in significant increase in the amount of ferroelectric crystals formed during cooling. For greater OMS additions (10-25%), the amounts of para- and ferroelectric crystals are reduced. The larger OMS additions depress the melt-to-paraelectric transition temperature, while an increase in the paraelectric-to-ferroelectric transition temperature is observed for all compositions. Upon reheating, the ferroelectric phase transition shows significant hysteresis. We conclude that the addition of either Lucentite or Nanomer OMS to 75/25 P(VDF-TrFE) causes an increase in the temperature stability range for the ferroelectric phase.     

Crystallographic changes characterizing the Curie transition in three ferroelectric copolymers of vinylidene fluoride and trifluoroethylene: 1. As-crystallized samples

Copolymers of vinylidene fluoride/trifluoroethylene of molar composition $\text{65}\text{35}$, $\text{73}\text{27}$ and $\text{78}\text{22\%}$ respectively, are ferroelectric and undergo a Curie transition to the paraelectric state at high temperatures. In contrast to the irregular structure found earlier for the $\text{52}\text{48}\text{mol}\text{\%}$ copolymer, the structures of these three compositions in the low-temperature state are all well ordered and analogous to that of β-poly(vinylidene fluoride): they consist of molecular chains in a polar trans conformation whose order is improved with increasing vinylidene fluoride content, packed pseudo-hexagonally in unit cells whose dimensions decrease with increasing vinylidene fluoride content. In their paraelectric phase, the chains assume a partly disordered conformation consisting of irregular TG, T? and TT sequences and are packed on an expanded pseudo-hexagonal lattice. The Curie transitions were found to occur over a broad temperature range, encompassing ～30°C, and in the case of the $\text{78}\text{22}\text{mol}\text{\%}$ copolymer to extend into the melting region; they were also found to exhibit hysteresis by occurring at much lower temperatures upon cooling than upon heating.     

Tuning the optical band gap of monolayer WSe2 in ferroelectric field-effect transistors

Ferroelectric field-effect transistors (FeFETs) hold great promises for application in modern semiconducting industry as memory or logic devices. Intensive studies have been done on improving the performance of FeFET, which mostly rely on the electrical polarization properties of ferroelectric gate. However, the influence of the piezoelectric effect of ferroelectric gate on the semiconducting channel has not been explored to a large extent. In this work, we use gate voltage-dependent photoluminescence (PL) spectroscopy to study the piezoelectric effect of P(VDF-TrFE) gate on monolayer WSe₂ channel in FeFETs. The PL peak of monolayer WSe₂ undergoes a blue shift or red shift when gate voltage is applied through the ferroelectric layer, while no peak shift is observed when gate voltage is applied through the SiO₂ layer. Raman spectroscopy measurements confirm the presence of in-plane strain in monolayer WSe₂. Qualitative theoretical analysis and discussion suggest that the piezoelectricity of monolayer WSe₂ and the P(VDF-TrFE) deformation caused by inverse piezoelectric effect are the main factors that cause strain in monolayer WSe₂. These results demonstrate that the band structure of two-dimensional channel, especially monolayer two-dimensional materials, can be modulated in FeFETs, which should not be neglected under large gate voltage in FeFETs.     

Crystallographic changes characterizing the Curie transition in three ferroelectric copolymers of vinylidene fluoride and trifluoroethylene: 2. Oriented or poled samples

The effects of uniaxial drawing or poling on the structural changes involved in the ferroelectric-to-paraelectric phase transition in copolymers of vinylidene fluoride and trifluoroethylene were examined and compared to the behaviour of as-crystallized films. The compositions studied were $\text{65}\text{35}$, $\text{73}\text{27}$ and $\text{78}\text{22}\text{mol}\text{\%}$ vinylidene fluoride/trifluoroethylene, all of which crystallize from the melt with a molecular conformation and packing analogous to those of the common piezoelectric β-phase of poly(vinylidene fluoride). Contrary to the previously described behaviour of a $\text{52}\text{48}\text{mol}\text{\%}$ copolymer, orientation did not induce any significant changes in the structure of these copolymers or in its variation with temperature, primarily because these already crystallize directly from the melt in well-ordered, compact unit cells. On the other hand, electrical poling caused the all-trans chains of the ferroelectric phase to be packed more compactly and to survive to higher temperatures, thus shifting the Curie transition closer to the melting points of these copolymers. As a result, competition from melting interfered with the later stages of this solid-state transformation in the $\text{73}\text{27}\text{mol}\text{\%}$ composition, and aborted it at a very early point in the $\text{78}\text{22}\text{mol}\text{\%}$ samples. The Curie temperature was found to exhibit hysteresis between heating and cooling parts of the thermal cycle, to extend over a broad range of temperatures, and to involve intramolecular changes to the same disordered conformation found in melt-crystallized samples. Our results have allowed reasonable implications to be made concerning the existence and nature of a Curie transition in the piezoelectric β-phase of poly(vinylidene fluoride).     

Solution‐derived ferroelectric vinylidene fluoride oligomer thin films with large polarization

Dense and uniform vinylidene fluoride (VDF) oligomer thin films with a highly polar β phase were prepared for the first time by a low‐cost and scalable solution casting approach, after treatments of substrate surface functionalization and hot‐pressing. Introducing hydrated salt in the precursor solution effectively promoted the ferroelectric β phase. The VDF oligomer thin films obtained with short molecular chains exhibited high crystallinity and high remnant polarization (91 mC m^?2), which is larger than both the polymer and copolymer counterpart films. The reasons for the observed low dielectric constant at low electric field, despite its larger polarization at high field, and the relatively high coercive field are discussed on the basis of the distinct structural characteristics of VDF oligomers. The low polar bulky end‐groups and difficulties in kink formation and propagation may result in the observed low dielectric constant at low electric field and the high coercive field. Copyright © 2011 Society of Chemical Industry     

Infrared spectra and ferro‐electricity of ultra‐thin films of vinylidene fluoride and trifluoroethylene copolymer

The structures of ultra‐thin films of vinylidene fluoride and trifluoroethylene copolymer were characterized using Fourier transform infrared reflection absorption spectroscopy (FTIR‐RAS), FTIR transmission spectroscopy (FTIR‐TRS), atomic force microscopy, and wide‐angle X‐ray diffraction. The ferro‐electricity was determined from polarization charge (a displacement (D)–electric field (E) hysteresis). FTIR‐RAS and FTIR‐TRS measurements showed that the molecular chains of polymers (crystal c‐axis) near the substrate tended to align parallel to the substrate. However, thermal annealing of the sample films at temperatures above 145 °C caused a marked change in molecular alignment of the polymer chains (crystal c‐axis) from parallel to normal to the substrate, and, further, caused a conformation change from trans to partially gauche forms. Copyright © 2007 Society of Chemical Industry     

Structure, phase transition and electric properties of poly(vinylidene fluoride-trifluoroethylene) copolymer studied with density functional theory

The geometry, energy, internal rotation, vibrational spectra, dipole moments and molecular polarizabilities of poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) of α- and β-chain models were studied with density functional theory at B3PW91/6-31G(d) level and compared with those of the poly(vinylidene fluoride) (PVDF) homopolymer. The chain length and the trifluoroethylene (TrFE) concentration were examined to discuss the copolymer chain stabilities, chain conformations and electric properties. The asymmetrical internal-rotation potential energy curve shows that the angles for the g and g′ conformations in the α-chain (tg and tg′) models are 53° and −70°, respectively, and the β-chain (ttt) conformation is a slightly distorted all-trans plane with dihedral angle at 177°. The energy differences, E_β − E_α(g) and E_β − E_α(g′), between the β- and the α-conformation are 2.1 and 7.8 kJ/mol, respectively. These values are smaller than that in PVDF (8.4 kJ/mol), suggesting that the β-conformation in the copolymer will be more stable than in PVDF. The energy barriers for β → α(g) and β → α(g′) transitions are 16.2 and 5.8 kJ/mol, respectively. The former is almost twice of the energy barrier in PVDF by 8.2 kJ/mol and the latter is slightly smaller (by 2.4 kJ/mol) than that in PVDF. The respective energy barriers for α(g) → β and α(g′) → β transitions are 18.3 and 13.6 kJ/mol compared with the value 16.3 kJ/mol in PVDF. The asymmetrical energy barriers may be one of the reasons for the copolymers with 0.5-0.6 (mole fraction) VDF exhibiting complicated phase transition behavior. The conformation of α-chain P(VDF-TrFE) exhibits from a helical (containing higher TrFE) to a nearly beeline (containing lower TrFE). This behavior is different from that in the PVDF and the nearly beeline conformation might be responsible for the increasing crystallizability. The helical might also be associated with the complicated phase transition behavior and the larger lattice strain in the P(VDF-TrFE)s with higher TrFE concentration. The energy difference per monomer unit between the β- and α-chain decreases with increasing TrFE content. The ideal β-chain is curved with a radius of about 30 Å, which is similar to that in PVDF. The chain curvature and the TrFE content will affect the dipole moment contribution per monomer. The chain length and TrFE content will not significantly affect the mean polarizability. The calculations indicated that there are some additional characteristic vibrational modes that may be used in identification of the α- or β-phase P(VDF-TrFE)s with different TrFE contents.     

聚偏氟乙烯-b-聚乙烯基吡咯烷酮嵌段共聚物的制备和结构

以C₆F₁₃I为链转移剂,通过碘转移乳液聚合制得碘封端的聚偏氟乙烯（PVDF-I）,再以PVDF-I为大分子链转移剂进行N-乙烯基吡咯烷酮碘转移溶液聚合,得到聚偏氟乙烯-b-聚乙烯基吡咯烷酮（PVDF-b-PVP）两亲性嵌段共聚物;采用NMR、IR、XRD、DSC和AFM等对PVDF-b-PVP嵌段共聚物的分子和相态结构进行了表征。发现PVP能有效嵌入PVDF与末端碘之间,PVDF嵌段PVP后,PVDF分子链的有序度明显降低,产生γ晶型PVDF,同时结晶温度和结晶度降低。PVDF-b-PVP嵌段共聚物表现微相分离结构,相分离尺寸约20 nm,其亲水性也优于PVDF均聚物。     

Miscibility and morphology of poly(vinylidene fluoride)/poly[(vinylidene fluoride)‐ran‐trifluorethylene] blends

This study presents an investigation of the effect of the different crystalline phases of each blend component on miscibility when blending poly(vinylidene fluoride) (PVDF) and its copolymer poly[(vinylidene fluoride)‐ran‐trifluorethylene] [P(VDF–TrFE)] containing 72 mol % of VDF. It was found that, when both components crystallized in their ferroelectric phase, the PVDF showed a strong effect on the crystallinity and phase‐transition temperature of the copolymer, indicating partial miscibility in the crystalline state. On the other hand, immiscibility was observed when both components, after melting, were crystallized in their paraelectric phase. In this case, however, a decrease in crystallization temperatures suggested a strong interaction between monomers in the liquid state. Blend morphologies indicated that, in spite of the lack of miscibility in the crystalline state, there is at least miscibility between PVDF and P(VDF–TrFE) in the liquid state, and that a very intimate mixture of the two phases on the lamellar level can be maintained upon crystallization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1362–1369, 2002     

Evolution of morphology,ferroelectric, and mechanical properties in poly(vinylidene fluoride)–poly(vinylidene fluoride‐trifluoroethylene) blends

Considering the complementary properties of poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride‐trifluoroethylene) [P(VDF‐TrFE)], it appears that their blends have the potential to be promising candidates for device applications. We report the evolution of morphology, ferroelectric, and mechanical properties (modulus and hardness) and their dependence on preparation temperature for PVDF–P(VDF‐TrFE) blends. From ferroelectric hysteresis measurements it was found that P(VDF‐TrFE) rich blends treated at higher temperature show significant values of remanent polarization. Remanent polarization values show a fourfold increase in these P(VDF‐TrFE) rich blends treated at higher temperature. Interestingly, blends prepared from high temperature showed greater value of remanent polarization even though they were found to consist of smaller amount of electroactive phase as compared to their low temperature treated counterpart. Nanoindentation experiments revealed that high temperature treatment improves the modulus of blends by at least 100%. This report attempts to tie these findings to the morphology and crystallinity of these blends. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45955.     

Spatially‐confined crystallization of poly(vinylidene fluoride)

Nanometre‐sized poly(vinylidene fluoride) (PVDF) particle domains in a confined space were obtained by blending PVDF with excess poly(methyl methacrylate) (PMMA). When these particles were small enough they showed β‐form structure, which was different from the structure of bigger particles or PVDF bulk. However, the β‐form was thermodynamically metastable because it could eventually be transformed to a more stable phase by annealing at a certain temperature. Larger particle domains were of identical phase to the bulk, indicating that small size favours the formation of the β‐form. © 2000 Society of Chemical Industry     

Annealing effect on poly(vinylidene fluoride/trifluoroethylene) (70/30) copolymer thin films above the melting point

To further understand crystallization behaviors above the melting temperature (T_m), the morphologies and structure of ferroelectric poly(vinylidene fluoride/trifluoroethylene) [P(VDF–TrFE); 70/30] copolymer films at different temperatures were studied by atomic force microscopy, differential scanning calorimetry, and X‐ray diffraction (XRD). We found that there was a structural change in the P(VDF–TrFE) copolymer film above T_m, which corresponded to the transition from tightly arrayed grains to fiberlike crystals. For the samples annealed above T_m, heat treatment reduced the density of gauche defects and caused a better arrangement of the crystalline phase. So those samples were in the ferroelectric phase without gauche defects, with one sharp diffraction peak reflected in the XRD curves. It was helpful to further make clear the thermal behaviors from the melts of the P(VDF–TrFE) copolymers and discuss their application under higher temperatures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Annealing effect upon chain orientation, crystalline morphology, and polarizability of ultra-thin P(VDF-TrFE) film for nonvolatile polymer memory device

The ferroelectric behavior of spin-cast ultra-thin P(VDF-TrFE) (72-28) film is highly influenced by sample preparation methods including thermal annealing. The effect of sample preparation methods on the surface morphology, chain and dipole orientation, ferroelectric properties, and nonvolatile memory characteristics were studied using FTIR-grazing incident reflection absorption spectroscopy (GIRAS), grazing incident wide angle X-ray diffraction (GIWAXD), atomic force microscope (AFM), dynamic contact electrostatic force microscope (DC-EFM), and polarization-electric field (P-E) hysteresis measurements to find the feasibility of applying the ultra-thin P(VDF-TrFE) film to scanning probe microscopy (SPM)-based storage device or low-cost nonvolatile ferroelectric polymer random access memory (NvFePoRAM) device. From the collective analysis of GIRAS, GIWAXD, and AFM data, annealing the as-cast sample at temperature (ca. 120 °C) above Curie transition, but below its melting transition temperature was found to be the most suitable condition to fabricate the NvFePoRAM and/or SPM-based storage device with a memory density of about 30 GB/in². DC-EFM technique was successfully used to characterize the nonvolatile memory properties by ‘writing and erasing’ the data bit through applying a dc bias voltage much larger than coercive voltage with different polarities and then reading the data bit by applying a high frequency ac voltage of only 2 V to the ‘written or erased’ area.     

Modelling of chain twist boundaries in poly(vinylidene fluoride) as a mechanism for ferroelectric polarization

It is assumed that the process of ferroelectric polarization of the beta phase of poly(vinylidene fluoride) (PVF₂) in response to the action of the external electric field in direction perpendicular to the molecular axis and to the film, involves movement of the chain twist boundaries. These boundaries, at which every chain is twisted by 180 degrees, separate domains of opposite polarization. The energy barriers that are surmounted as the boundary was advanced one repeat unit were calculated and compared with the energy gained by reversing the polarization of an unfavourably oriented repeat unit in an electric field that produces polarization in PVF₂. It is suggested that the movement of chain twist boundaries, in contradistinction to previously postulated models in which only one chain is twisted at a time, provides a model for the poling of PVF₂ that is feasible energetically and kinetically. Theoretical modelling, analogous to that for Bloch wall that separates domains in magnetic materials, suggest that the process of polarization might be described either as a diffusion process or as the propagation of a soliton along the chains.     

Preparation and physicochemical performances of poly[(vinylidene fluoride)‐co‐hexafluoropropylene]‐based composite polymer electrolytes doped with modified carbon nanotubes

Modified carbon nanotubes (m‐CNTs) were successfully prepared by the interactions between nitric and sulfuric acids and CNTs, which was confirmed using Fourier transform infrared spectroscopy. Poly[(vinylidene fluoride)‐co‐hexafluoropropylene]‐based composite polymer electrolyte (CPE) membranes doped with various amounts of m‐CNTs were prepared by phase inversion method. The desired CPEs were obtained by soaking the liquid electrolytes for 30 min. The physicochemical and electrochemical properties of the CPE membranes were investigated using scanning electron microscopy, X‐ray diffraction, thermogravimetry, electrochemical impedance spectroscopy and linear sweep voltammetry. The results show that the CPE membranes doped with 2.2 wt% m‐CNTs possess the smoothest surface and the highest decomposition temperature about 450 °C. Obviously, adding an appropriate amount of m‐CNTs into the polymer matrix can decrease the crystallinity and enhance the ionic conductivity; the temperature dependence of ionic conductivity follows the Arrhenius relation and the ionic conductivity at room temperature is up to 4.9 mS cm^?1. The interfacial resistance can reach a stable value of about 415 Ω cm^?2 after 10 days storage. The excellent rate and cycle performances with an electrochemical working window up to 5.4 V ensure that the CPEs doped with 2.2 wt% m‐CNTs can be considered as potential candidates as polymer electrolyte for lithium ion batteries. © 2013 Society of Chemical Industry