Jing
Cui
a,
Zhe
Ma
a,
Li
Pan
*a,
Chun-Hua
An
c,
Jing
Liu
c,
Yu-Feng
Zhou
d and
Yue-Sheng
Li
*ab
aTianjin Key Laboratory of Composite and Functional Materials, School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China. E-mail: lilypan@tju.edu.cn; ysli@tju.edu.cn
bCollaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China
cState Key Laboratory of Precise Measurement Technology & Instruments, School of Precise Instruments & Optoelectronics Engineering, Tianjin 300072, China
dSchool of Materials Science & Engineering, Zhengzhou University, Zhengzhou 450002, China
First published on 15th January 2019
Self-healing materials typically suffer from poor mechanical performance in terms of practical applications. Herein, a self-healable copolymer with a gradient distribution of hard segments on ionic polymer chains is designed. By the optimization of the monomer sequences and physical cross-linking, the copolymer exhibits excellent mechanical properties with Young's modulus up to 286 MPa and toughness over 33 MJ m−3, which represents a significant improvement compared with traditional self-healing materials. Imidazolium in this copolymer not only generates strong dynamic ionic associations and imparts mending ability, but also provides ionic conductivity for potential device applications. Environment-insensitive self-healing in the presence of moisture, water and artificial sweat is achieved. Strain sensors with rapid response (<114 ms) and high durability (no performance decrease after 7000 cycles of tensile test) are fabricated using the gradient copolymers, opening an avenue for high-performance wearable devices using polymeric materials.
In an attempt to improve the mechanical properties of a self-healable polymer, we have previously tried tuning interaction intensities between the imidazolium and counter ions of a series of imidazolium-based norbornene polymerized ionic liquid (PIL) blends. Homopolymer of PILs with different counter ions (CH3SO3−, CF3SO3−, CF3(CF2)3SO3−, FSI−, and Tf2N−) were first synthesized via ring-opening metathesis polymerization, respectively, and then PIL blends with excellent mechanical performance and self-healing capability could be achieved simultaneously via varying the ratio of PILs with high/low glass transition (Tg) and/or counter ion.10 To construct a promising mechanically robust self-healing material in a simple synthesis pathway, a bottom-up design by controlling the compositions, monomer sequences and connections at the molecular level is of crucial importance.
In nature, self-healable materials with high mechanical strength and toughness play an important role in biological systems. For example, mussel byssus is used for attaching to rocks.11 Superior mechanical performance of mussel byssus is derived from the gradual collagen composition change along the fiber.12,13 This gradient structure results in a continuous alteration of elasticity modulus, minimizing interfacial stresses, and improving energy dissipation, thereby increasing mechanical toughness.12,14 For synthetic polymer materials, a gradient copolymer is a unique class in which chemical composition changes continuously along the copolymer chain.15–17 Therefore, inspired by the gradient structure of mussel byssus, we recently designed and synthesized a series of novel self-healing copolymers consisting of gradient distributed large sterically hindered hard segments and soft units suspended with imidazolium. The hard domains containing a stiff bulky bridged phenyl unit not only ensure the elasticity, but also contribute greatly to the modulus and stiffness of copolymers. Imidazolium cations and bis(trifluoromethylsulfonyl)amide (Tf2N−) anions are selected for dynamic supramolecular interaction to construct a reversible physically cross-linked network which can realize self-healing function. Meanwhile, ion sites only embed in soft segments, which are favorable to dynamic ionic association and endow the copolymer with more flexible interactions and healing ability. This elaborate molecular design provides tunable mechanical performance and environmentally tolerated self-healing properties. Besides, the above gradient copolymer can be directly used for flexible strain sensors, exhibiting fast response, high reproducibility and excellent stability.
The gradient copolymers were clearly characterized by 1H NMR where broad resonance signals in the range of 5.0–5.7 ppm are ascribed to olefinic protons in the ring-opened structure (Fig. S1–S8, ESI†). The molar ratios of BDI and HBM incorporated into the polymers agree well with the initial feed ratios by 1H NMR spectra analyses, indicating that the monomers were quantitatively converted into gradient copolymers. Furthermore, the two-dimensional nuclear Overhauser effect spectroscopy (NOESY) spectra of the gradient copolymers revealed spatial proximity (5 Å) among the protons of HBM and BDI units (Fig. S9, ESI†). This is different from that of a block copolymer analogue, which did not exhibit any signal or Overhauser data. According to the modified methodology developed by Matyjaszewski's group,20 we have successfully determined the molecular weights of the gradient copolymers by gel permeation chromatography (GPC) using N,N-dimethylformamide (DMF) containing 50 mM of LiBr as the eluent. High molecular weights (Mn = 89–98 × 103) and narrow molecular weight distributions (Mw/Mn < 1.4) are observed (Table S1, ESI†). As the HBM fraction is varied from 4.7 to 23 mol%, the glass transition temperature (Tg) increases from 27.9 to 63.0 °C according to dynamic mechanical analysis (Fig. S11 and Table S1, ESI†).
Gradient materials with a gradual change of composition do not possess a sharp interface as in block materials,21 as measured by small angle X-ray scattering (SAXS) and high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM). None of the gradient copolymers or the homopolymer (HP) exhibited any scattering peaks by SAXS measurement (Fig. 1c and Fig. S14a, ESI†). For the block copolymers, mcirophase separation was observed (HBM unit >4.7 mol%). When the content of HBM sequence increases from 11.1 through 20 to 23 mol%, the domain spacing (d = 2π/q) increases from 30 through 41.3 to 90.2 nm. These distinct structural differences between gradient and block copolymers were also confirmed by HAADF-STEM. The GCP-3 image presented the shallow contrast of the gradual phase interfaces, indicating the uniform distribution of hard and soft motifs (Fig. 1d). By contrast, distinct phase interfaces with an average spherical size of ∼35 nm were observed for BCP-3 (Fig. 1e). The roughness and morphology of the materials were also tested by atomic force microscopy (AFM). The root-mean-square roughness (RMS) is 3.1 nm for GCP-3 and 1.95 nm for BCP-3 (Fig. S13, ESI†). GCP-3 forms continuous films without phase separation. However, for the BCP-3 film, the HBM hard domain is dispersed in the continuous soft matrix.
In the polymer matrix, imdazolium with Tf2N− counterions aggregates to form multiplets or clusters, which can be reformed in a short relaxation period after crack damage and is responsible for the self-healing process. To identify the presence of such ionic aggregates, X-ray scattering measurement was carried out. All the ionic polymers exhibited three scattering peaks at the same position regardless of the monomer sequence distribution and HBM content (Fig. 1c and Fig. S14b, ESI†): the peaks at 12–15, 6–9 and 2–4 nm−1 were assigned to the amorphous phase, correlation between the anions and Bragg spacing between ionic aggregates of the ionic polymers, respectively.22–24 The relative broad scattering peaks at 2–4 nm−1 implied lower and looser ionic associations,25 which shortens the ionic relaxation time, thereby promoting the self-healing process.
The stretching speed-dependent mechanical behavior indicated that both the Young's modulus and fracture stress of GCP-1 increased with increasing stretching rate, while the stretchability decreased (Fig. 2c). At low deformation rates (1 and 10 mm mm−1 min−1), the dynamic dissociation and recombination of ionic groups are capable of transferring stress and dissipating energy, allowing ionic copolymers to have high elongation. This behavior is analogous to that of typical covalent cross-linked elastomers. When the stretching rate exceeds 50 mm mm−1 min−1, there is no sufficient time to reform ionic aggregates after their dissociation within the timescale of the tensile deformation. In this case, ionic aggregates serve as a strong cross-link to enhance fracture stress.31 Therefore, the polymeric network became stiff and a noticeable yield point was also observed.
A great amount of ionic physical cross-linking and the gradual change in composition permit gradient copolymers to dissipate stress from all directions. In Fig. 2d, inhomogeneous deformation of GCP-1 film without any fracture was observed after the sample was poked by a metal cylindrical cut-off knife. Surprisingly, the sample could withstand repeated jabbing (Movie S1, ESI†). Besides, the gradient copolymers were also proved to be notch-insensitive. We cut out a notch in the center of GCP-1 and subsequently stretched the sample, a dramatically blunted notch was presented, and the notched sample could be stretched up to a critical strain of 1050% at a deformation rate of 100 mm mm−1 min−1, demonstrating exceptional toughness of the specimen (Fig. 2e and Movie S2, ESI†).
The gradient copolymers are highly fatigue resistant. After the first loading–unloading cycle, GCP-1 exhibited prominent yielding and hysteresis, indicating a large amount of energy dissipation through ionic disassociations (Fig. 2f). The emergence of a significant residual strain after unloading suggested a plastic deformation of the sample. The residual strain disappeared and the hysteresis ratio almost completely recovered after 3 h of waiting time. Heating at 50 °C greatly promoted self-recovery of the copolymers because of the accelerated dynamic ionic rearrangement and diffusion of polymeric segments. Full mechanical recovery demonstrated that the deformation was caused by disassociation of ionic aggregates and no breaking of main chains occurred. The waiting time-dependent hysteresis ratio, estimated from the hysteresis area change and the residual strain, is shown in Fig. 2g. During unloading, the mechanical recovery involves elastic contraction of the main chain and rearrangement of temporarily reformed ionic aggregates, which are competing with each other. When the deformation exceeds 110%, elastic contraction is dominant leading to a quick mechanical recovery, whereas at a small deformation (<110%), the reformed ionic bonds need time to re-organize, which slows down the recovery of the main chain to its equilibrium state. A complete recovery was observed at a larger loading strain of 1000% (Fig. S15, ESI†), approaching the fracture strain of 1150–1200%. This result suggests that there is no chain sliding until fracture because of strong ionic supramolecular interactions between copolymer chains.
To comprehend the detailed healing process, all the cut specimens have been kept in contact for various durations, followed by tensile tests. The stress–strain curves of the repaired samples overlapped with that of the original uncut one (Fig. S18, ESI†), indicating that as the contact time extended, the fracture stress and fracture strain were continuously repaired; however, the Young's modulus and yield stress have already been completely restored after the healed strain exceeded the yield strain. In sharp contrast, most of the previously reported self-healing materials could not reach their original Young's modulus or yield stress unless complete recovery was achieved.33–36 A probable explanation is that ionic aggregates rapidly re-form once the cut samples are contacted, and the interface interactions dominated by ionic associations are strong enough to resist the plastically yielding deformation. Compared to GCP-1 with BCP-1, the self-healing efficiency of the gradient copolymer was superior to that of the block ones (Fig. S18, ESI†). It was speculated that the absence of ionic groups in the self-assembled HBM domain of the block copolymers impedes their self-repair.
The occurrence of healing is explained by the rearrangement of ionic aggregates and the interdiffusion of polymer chains over the surface of the crack. At low HBM content (<5.4%), self-healing of the gradient copolymers was achieved at room temperature in the absence of any external stimuli including plasticizer, solvent or healing agent. As the content of HBM further increased, the rigidity of the polymer chain enhanced but the mobility of the chain decreased. As a result, ion hopping, i.e. ions on the polymer chain hopping from one aggregation to another was restricted, the repair process accordingly slowed down. Higher repair temperature is required to speed up the healing of samples. As observed, GCP-3 took over 40 h to recover its fracture strain to around 90% at 50 °C (Fig. 3d). At 60 °C, a comparable recovery took much less time of about 10 h. Further raising the healing temperature to 70 °C, complete recovery was achieved within only 3 h. The healing process of GCP-3 is remarkably accelerated approximately 13 times just through elevating the temperature by 20 °C. GCP-4 with the highest mechanical strength also possessed excellent self-healing performance. The complete recovery period was shortened from 18 to 4 h through elevating the temperature by 20 °C (from 70 to 90 °C) (Fig. S18, ESI†). The relaxation time (τ) of GCP-1 for the flow transition was evaluated in the range of 107 seconds (∼months), much longer than its complete repair time (∼6 h) at 25 °C (Fig. 3f). This dramatic contrast indicated that high healing efficiency of gradient copolymers is ascribed to the rapid and dynamic ionic associations rather than the flow relaxation of primary chains.
Microwave radiation is also an effective way to enhance recovery efficiency of gradient copolymers. The diffusion of the molecules between two sides of the crack is stimulated by microwaves, which will create connection points that restore the continuity of the material.37 The time for complete healing by microwaves was shortened to 30 s for HP. Even for GCP-4, a complete recovery could be achieved within 150 s (Fig. S17, ESI†). After 50 s of microwave irradiation, the GCP-1 specimen possessed a steady interface capable of sustaining various mechanical forces, including bending, stretching up to a maximum extension and loading up to 0.785 kg, which is more than 4200 times of its own weight (Fig. 3c).
For self-healing materials based on hydrogen bonding interaction, both formation of co-facial interaction partners and combination with water in the environment will destroy the bridges of hydrogen bonding across the fracture interfaces, resulting in the degradation of self-healing capability.34,35 However, the gradient copolymers presented very tenacious mending performance, and their self-healing ability was not significantly affected by moisture or even water (Fig. 3e). Furthermore, because of the hydrophobicity of the counterion (Tf2N−), the repair of the GCP-1 sample in water could be repeated lots of times (Movie S3, ESI†). Besides, the healing process of the separated GCP-1 samples was further tested in artificial sweat. After immersing in artificial sweat for 6 h, the healing efficiency of fracture strain still reached up to 87.5%, very close to the result of healing in air (∼93%).
The relative current of the sample showed a downward step-like trend during a step-by-step loading–unloading cycle because of the increase in resistance of the stretched conductor (Fig. 4b). The key performance parameters of recently reported strain sensors are compared in Table S5 (ESI†). The response time of the sensor to strain (from 0 to 10%) was only 114 ms, which is comparable to that of human skin (∼100 ms),42 indicating that the sensor can immediately monitor the applied strain without evident hysteresis. In contrast, the current showed an increase with the raise of compressive strain (Fig. 4c). This observation implied the formation of ion transport channels during compression. The gauge factor (GF), a representative parameter for accessing strain sensitivity, was measured to be 3.0 within 5% compressive strain, 1.0 for 5–20%, and 0.6 for compressive strain exceeding 20%, demonstrating the high sensitivity of the soft sensor in a wide sensing range. Fig. 4d presents the variation of current during cyclical stretching from ε = 0% to ε = 5% with a frequency of 1.5 Hz for 7000 cycles. The current changed periodically, implying reproducible and reliable performance of the sensor.
The ionic sensor was fixed on a finger by conductive tapes as a wearable device to detect the joint motion in real-time. When the finger was bent, an increase of current was observed (Fig. 4e). This phenomenon is different from those of the previously reported strain sensors.43–47 The motion of a bending finger involves two opposite movements: the side of the sample attached to the finger is contracted while the other side is stretched. When contraction is dominant, current increases. Furthermore, as the finger bent to different angles from 30 through 45 to 90°, the vibration amplitude of the current was obviously enhanced, exhibiting excellent reliable and highly sensitive sensing response to the bent finger. Similarly, we could monitor the muscle movement of a bent wrist through the changes in current for a long time by attaching the ionic copolymer sensor onto the wrist (Fig. 4f), implying the reproducibility of the strain sensor. Different from the hydrogels, no small molecular component escapes from the matrix of the gradient copolymer during usage, and the strain sensor is able to be used under extra-dry or humid conditions where traditional conductive hydrogel sensors fail to work properly. For example, the sensor responded stably to cyclic mechanical bending motion in a wide humidity range from 10 to 80% (Fig. 4g).
Footnote |
† Electronic supplementary information (ESI) available: Synthetic materials and instruments, synthetic methods, reactivity ratio measurements, NMR, NOESY, DMA, TGA, XRD, mechanical properties, self-healing performance and ion conductivity. See DOI: 10.1039/c8qm00592c |
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