A combined fracture mechanical – rheological study to separate the contributions of hydrogen bonds and disulphide linkages to the healing of poly(urea-urethane) networks

Grande, Antonio Mattia; Bijleveld, Johan; Garcia, Santiago J.; Zwaag, Sybrand van der

doi:10.1016/j.polymer.2016.05.004

Cited by 82 publications

(57 citation statements)

References 44 publications

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“…To further understand the self‐healing behavior from a rheological perspective, frequency sweep and step‐strain experiments were conducted on the TPUs at 25 and 60 °C . The TPUs appeared to be elastic solids at 25 °C, with G′ displaying a higher modulus than G″ in the frequency sweep graph (Figure S13, Supporting Information).…”

Section: Estimated Uts Elongation At Break Toughness and Recovery mentioning

confidence: 99%

Superior Toughness and Fast Self‐Healing at Room Temperature Engineered by Transparent Elastomers

et al. 2017

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To realize a robust, transparent, and easily processable polymer that is intrinsically selfhealable at room temperature, the following three material design criteria were established: (1) a readily processable and physically tunable base material, (2) a dynamic covalent bond that is operable at room temperature, and (3) optimal self-healing efficiency and mechanical properties.Thermoplastic polyurethane (TPU) is a thermoprocessable elastomer that is widely used as a protective film in the automotive and electronic industries. TPU was selected as the base material to satisfy the first criterion because its chemical structure can be fine-tuned to generate the desired transparency and mechanical properties. [4] Urethane structures containing polytetramethylene ether glycol (PTMEG) have been utilized to prepare shape memory effectassisted self-healing materials. [5] To satisfy the second criterion, an aromatic disulfide bond was selected as the chemical operator. [6] Intrinsic self-healing is chemically driven by noncovalent bonds such as hydrogen bonds, [3c-e,5c,7] metal-ligand, [8] host-guest interactions, [2e,9] or reversible (dynamic) covalent bonds [10] such as Diels-Alder, [11] radical recombination, [12] urea chemistry, [13] olefin metathesis, [14] polysiloxanes, [15] boronic esters, [16] acylhydrazones, [17] and other reactions. [18] Among these, disulfide metathesis has attracted significant attention since it can be activated at moderate temperatures (60-90 °C) and without external stimuli. [5d,19] In particular, an aromatic disulfide-based poly(urea-urethane) shows efficient room-temperature self-healing because aromatic disulfides undergo more efficient metathesis than aliphatic disulfides. [6e,f,20] The third criterion was addressed by optimizing the mechanical properties and self-healing efficiency of TPU through the design of a hard segment of the polymer containing the chemical operator, i.e., an aromatic disulfide moiety. Generally, TPUs with tightly packed hard segments have better mechanical properties but lower self-healing efficiency because the restricted chain mobility hinders disulfide metathesis. [5d,21] Loosely packed hard segments produce the opposite effect. Room-temperature self-healable cross-linked poly(urea-urethane) has an undesirable ultimate tensile strength (UTS) of ≈0.8 MPa with a toughness of ≈13 MJ m −3 . [6e] Other disulfide-containing TPUs have UTS values greater than 10 MPa, but they must be heated above 80 °C to initiate self-healing. [5d] The most important properties of self-healing polymers are efficient recovery at room temperature and prolonged durability. However, these two characteristics are contradictory, making it difficult to optimize them simultaneously. Herein, a transparent and easily processable thermoplastic polyurethane (TPU) with the highest reported tensile strength and toughness (6.8 MPa and 26.9 MJ m −3 , respectively) is prepared. This TPU is superior to reported contemporary roomtemperature self-healable materials and conveniently heals w...

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Section: Estimated Uts Elongation At Break Toughness and Recovery mentioning

confidence: 99%

Superior Toughness and Fast Self‐Healing at Room Temperature Engineered by Transparent Elastomers

et al. 2017

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“…However, other effects can not be discarded. In addition, the different behavior of PPGAPDS and PPGAPDM systems suggests that the hydogen bonds allowed the reparation in the first stages while, in the case of PPGAPDS samples, the disulfide metathesis reaction is responsible for the acquisition of the final structural integrity [21,38,41]. In addition to the evaluation of the healing time, the influence of consecutive damage-healing cycles on the healing efficiency of the process was also studied.…”

Section: Evaluation Of the Healing Propertiesmentioning

confidence: 99%

Autonomic healable waterborne organic-inorganic polyurethane hybrids based on aromatic disulfide moieties

Aguirresarobe¹,

Martin²,

Fernández‐Berridi³

et al. 2017

Express Polym. Lett.

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Abstract. Aromatic disulfide dynamic structures were incorporated as chain extenders in waterborne organic-inorganic polyurethane hybrids in order to provide autonomic healable characteristics. The synthesis was carried out following the acetone process methodology and the influence of the introduction of the healing agents in the polymer dispersion stability was analyzed. After the crosslinking process at room temperature, organic-inorganic hybrid films, which presented autonomic healing characteristics, were obtained. These features were evaluated by means of stress-strain tests and the films showed repetitive healing abilities. Thus, the optimum healing time at room temperature (25°C) as well as the influence of different parameters in the healing efficiency, such the aromatic disulfide concentration or the physical properties of the polymer matrix were analyzed.

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“…first proposed a self‐healing mechanism of exchange reactions for aromatic disulfides facilitated by quadrupole hydrogen bonds. Garcia et al . separated and computed self‐healing contributions for hydrogen bonds and disulfide bonds interactions using the rheology and mechanics.…”

Section: Resultsmentioning

confidence: 99%

Room‐Temperature Self‐Healing and Reprocessable Waterborne Polyurethane with Dynamically Exchangeable Disulfide Bonds

et al. 2020

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Recently, covalent adaptable networks (CANs) based on dynamic exchange reactions have been synthesized, and the research on these materials has been mainly focused on the self-healing behavior and reprocessing properties of CANs. Disulfide bonds can be considered to be a type of dynamic reversible covalent bonds, and exchange reactions of disulfide bonds proceed easily at mild temperatures, which endow materials containing disulfide bonds with self-healing properties and the reprocessability under suitable conditions. Herein, we synthesized a type of waterborne polyurethane (WPU) CAN incorporated with disulfide bonds. A reasonable structural design was used in conjunction with a self-healing kinetic analysis to predict that the highest performing CWPU-8 sample could repair a microcrack at room temperature, which was verified by optical microscopy observations combined with self-healing mechanics. The most important feature of this material is its reprocessing property, which was investigated by rheology tests. These assessments demonstrate that the selfhealing behavior and the reprocessability are closely related to exchange reactions of disulfide bonds, and the structureproperty relationship provides deep insights into the CANs chemistry.[a] Dr. Figure 11. Characterization of the reprocessability: (a) original sample; (b) crushed sample; (c) hot pressing scenario; (d) reprocessed sample; and (e) tensile mechanical curves for reprocessing sample 4 times ChemistrySelect Full Papers

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A combined fracture mechanical – rheological study to separate the contributions of hydrogen bonds and disulphide linkages to the healing of poly(urea-urethane) networks

Cited by 82 publications

References 44 publications

Superior Toughness and Fast Self‐Healing at Room Temperature Engineered by Transparent Elastomers

Superior Toughness and Fast Self‐Healing at Room Temperature Engineered by Transparent Elastomers

Autonomic healable waterborne organic-inorganic polyurethane hybrids based on aromatic disulfide moieties

Room‐Temperature Self‐Healing and Reprocessable Waterborne Polyurethane with Dynamically Exchangeable Disulfide Bonds

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