Ming Qiu Zhang - Extrinsic and Intrinsic Approaches to Self-Healing Polymers and Polymer Composites

1 Cover

2 Title Page Extrinsic and Intrinsic Approaches to Self‐Healing Polymers and Polymer Composites Ming Qiu Zhang and Min Zhi Rong Materials Science Institute, Zhongshan University Guangzhou, China

3 Copyright Page

4 Preface

5 1 Basics of Self‐Healing – State of the Art 1.1 Background 1.2 Intrinsic Self‐Healing 1.3 Extrinsic Self‐Healing 1.4 Insights for Future Work References

6 2 Extrinsic Self‐Healing via Addition Polymerization 2.1 Design and Selection of Healing System 2.2 Microencapsulation of Mercaptan and Epoxy by In‐Situ Polymerization 2.3 Filling Polymeric Tubes with Mercaptan and Epoxy 2.4 Characterization of Self‐Healing Functionality 2.5 Concluding Remarks References

7 3 Extrinsic Self‐Healing Via Cationic Polymerization 3.1 Thermosetting 3.2 Thermoplastics 3.3 Concluding Remarks References

8 4 Extrinsic Self‐Healing via Anionic Polymerization 4.1 Preparation of Epoxy‐Loaded Microcapsules and Latent Hardener 4.2 Self‐Healing Epoxy Materials with Embedded Epoxy‐Loaded Microcapsules and Latent Hardener 4.3 Self‐Healing Epoxy/Woven Glass Fabric Composites with Embedded Epoxy‐Loaded Microcapsules and Latent Hardener – Healing of Interlaminar Failure 4.4 Durability of Healing Ability 4.5 Self‐Healing Epoxy/Woven Glass Fabric Composites with Embedded Epoxy‐Loaded Microcapsules and Latent Hardener – Healing of Impact Damage 4.6 Concluding Remarks References

9 5 Extrinsic Self‐Healing Via Miscellaneous Reactions 5.1 Extrinsic Self‐Healing Via Nucleophilic Addition and Ring‐Opening Reactions 5.2 Extrinsic Self‐Healing Via Living Polymerization 5.3 Extrinsic Self‐Healing Via Free Radical Polymerization 5.4 Concluding Remarks References

10 6 Intrinsic Self‐Healing Via the Diels–Alder Reaction 6.1 Molecular Design and Synthesis 6.2 Blends of DGFA and FGE 6.3 Concluding Remarks References

11 7 Intrinsic Self‐Healing Via Synchronous Fission/Radical Recombinationof the C─ON Bond 7.1 Thermal Reversibility of Alkoxyamine in Polymer Solids 7.2 Self‐Healing Cross‐linked Polystyrene 7.3 Self‐Healing Epoxy 7.4 Self‐Healing Polymers Containing Alkoxyamine with Oxygen Insensitivity and Reduced Homolysis Temperature 7.5 Reversible Shape Memory Polyurethane Network with Intrinsic Self‐Healability of Wider Crack 7.6 Concluding Remarks References

12 8 Intrinsic Self‐Healing Via Exchange Reaction of the Disulfide Bond 8.1 Room‐Temperature Self‐Healable and Remoldable Cross‐Linked Polysulfide 8.2 Sunlight Driven Self‐Healing Cross‐Linked Polyurethane Containing the Disulfide Bond 8.3 Self‐Healing and Reclaiming of Vulcanized Rubber 8.4 Concluding Remarks References

13 Index

14 End User License Agreement

1 Chapter 1 Table 1.1 Typical intrinsic self‐healing polymers toward mechanical propert... Table 1.2 Typical intrinsic self‐healing polymers toward mechanical propert...

2 Chapter 2Table 2.1 Descriptions of the PMF‐walled microcapsules containing mercaptan...Table 2.2 Typical PMF‐walled microcapsules containing epoxy (DTP) prepared ...Table 2.3 Properties of epoxy resins.Table 2.4 Properties of mercaptan.Table 2.5 Description of the epoxy‐loaded microcapsules embedded in self‐he...Table 2.6 Description of the hardener‐loaded microcapsules embedded in self...Table 2.7 Curing kinetics (estimated from non‐isothermal DSC studies) and a...Table 2.8 Description of the microcapsules for making self‐healing epoxy ma...Table 2.9 Properties of the specimens of cured epoxy and its composites for...Table 2.10 Description of the epoxy‐loaded microcapsules for making self‐he...Table 2.11 Description of the hardener‐loaded microcapsules for making self...Table 2.12 Orthographic factorial design and results of four factors (capsu...Table 2.13 Non‐isothermal curing kinetics of the healing agent with and wit...Table 2.14 Relative outflow aof epoxy healing agent from PP tubes.

3 Chapter 3Table 3.1 Creation of an orthographic factorial design of five factors and f...Table 3.2 Pyrolytic characteristics of epoxy, epoxy‐containing microcapsules...Table 3.3 Results analysis of the orthographic factorial design for microcap...Table 3.4 Recipes for preparing hollow microcapsules in emulsion via UV‐irra...Table 3.5 Three‐dimensional solubility parameters of MMA and EPON 828‐epoxy ...Table 3.6 Surface free energies of the hollow microcapsules.Table 3.7 Estimation of (C 2H 5) 2O·BF 3/epoxy weight ratio of released healant ...Table 3.8 Estimated average thickness of the bled healing agent delivered to...

4 Chapter 4Table 4.1 Porosity of self‐healing woven glass fabric/epoxy composites.Table 4.2 Dependence of healing efficiency of self‐healing woven glass fabri...Table 4.3 Effect of storage time on healing efficiency of self‐healing woven...Table 4.4 Linear shrinkage rates of TEPA cured epoxy resin a.Table 4.5 Specifications of the epoxy‐loaded microcapsules.Table 4.6 Healing efficiencies of the composite laminates.

5 Chapter 5Table 5.1 Descriptions of PMF‐walled microcapsules containing GMA prepared u...Table 5.2 Control tests showing the solvent effect of GMA a.

6 Chapter 6Table 6.1 Curing kinetic parameters of stoichiometric DGFA/MHHPA obtained fr...Table 6.2 Quantification of endothermic peaks of cured DGFA polymer measured...Table 6.3 Mechanical properties of cured epoxy.Table 6.4 Quantification of endothermic peaks of cured FGE polymer measured ...Table 6.5 Healing efficiency of cured FGE.Table 6.6 Molar compositions of cured DGFA/FGE blends.Table 6.7 Thermal reversibility of DA reaction in the cured blends of DGFA a...Table 6.8 Healing efficiency of the DF10 specimen.Table 6.9 Healing efficiency of the DF91 specimen.Table 6.10 Healing efficiency of the DF82 specimen.Table 6.11 Healing efficiency of of DF73 specimen.Table 6.12 Healing efficiency of the DF64 specimen.Table 6.13 Mechanical properties of the cured blends of DGFA and FGE.

7 Chapter 7Table 7.1 Molecular weight between crosslinks, M c, of the cured epoxies esti...Table 7.2 Healing efficiencies of 828/diEP measured during three successive ...Table 7.3 DSC characterization of the polyurethanes.

8 Chapter 8Table 8.1 Disulfide exchanges of linear polymers containing disulfide bonds....Table 8.2 Compositions of the rubbers studied in this work.

1 Chapter 1 Figure 1.1 Cohesive failures beside plated through holes on copper clad lami... Scheme 1.1 Flow chart of the key stages for thermosetting composite repair.... Figure 1.2 Typical repair processes of thermosetting composites represented ... Scheme 1.2 Fusion bonding techniques. Figure 1.3 Blood clotting in an injured vessel. Figure 1.4 Number of research papers on self‐healing polymers and polymer co... Figure 1.5 Connectivity transition difference for the reversible addition (t... Scheme 1.3 Thermally reversible cross‐linking based on Diels–Alder reaction.... Figure 1.6 Cross‐linked polymers constructed with dynamic‐covalent boronic e... Scheme 1.4 Strategy for constructing a dynamic hydrogel with an environmenta... Figure 1.7 (a) Scheme illustrating the welding of two pieces of epoxy resin ... Figure 1.8 (a) Chemical structure of the cross‐linked polyurethane (P1). (b)... Figure 1.9 Chemical structure of a PDMS functionalized with 2,6‐pyridinedica... Figure 1.10 (a) Chemical structure of PU‐b‐P(D‐r‐U)‐b‐PU and (b) its microph... Figure 1.11 Schematic diagram of repair concept for polymer matrix composite... Figure 1.12 Vascular hierarchy. (a) 1D straight channels; (b) 2D segregated ... Figure 1.13 Typical extrinsic self‐healing systems based on microcapsules. (... Figure 1.14 Schematic drawing of the formation of microcapsules by in‐situ p... Scheme 1.5 Ring‐opening metathesis polymerization of DCPD. Scheme 1.6 Schematic illustration of polycondensation between HOPDMS and PDE... Figure 1.15 Performance map of self‐healing structural composites. Maximum h... Figure 1.16 Schematic drawing of a cross‐linked polyurethane containing a re... Figure 1.17 Cartoon depicting the ultrasound‐induced mechanochemical scissio... Figure 1.18 Schematic drawing of the mechanochemically initiated reversible ...