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

temperatures at 1% weight loss of melamine...Figure 5.28 SEM images of (a, c, e) styrene‐loaded microcapsules and (b, d, ...Figure 5.29 FTIR spectra of (a) styrene‐ and (b) BPO‐loaded microcapsules in...Figure 5.30 DSC heating curves of the polymerization of styrene initiated wi...Figure 5.31 Healing efficiency of self‐healing epoxy composites containing s...Figure 5.32 Healing efficiency of control unfilled epoxy specimens that were...

      6 Chapter 6Scheme 6.1 Molecular structure of DGFA.Scheme 6.2 (a) Molecular structure of cured DGFA and (b) schematic drawing h...Scheme 6.3 Molecular structure of FGE.Scheme 6.4 Molecular structure of cured FGE.Scheme 6.5 DGFA synthesized by a two‐step route.Figure 6.1 FTIR spectra of (a) raw DGFA and (b) its purified version.Figure 6.2 ¹H‐NMR spectrum of DGFA.Figure 6.3 ¹³C‐NMR spectrum of DGFA.Figure 6.4 DSC heating traces of the mixture of DGFA and MHHPA at stoichiome...Scheme 6.6 DA and retro‐DA reactions between DGFA and DPMBMI.Figure 6.5 FTIR spectra of (a) mixture of DGFA and DPMBMI, and (b) mixture o...Figure 6.6 ¹H‐NMR spectra of the mixture of DGFA and DPMBMI kept at 70 °C fo...Figure 6.7 DSC heating trace of the mixture of DGFA and DPMBMI. Heating rate...Figure 6.8 ¹H‐NMR spectra of (a) the adduct of DGFA and DPMBMI and (b) the r...Figure 6.9 ¹³C‐NMR spectra of (a) the adduct of DGFA and DPMBMI and (b) the ...Figure 6.10 FTIR spectrum of DGFA/MHHPA/DPMBMI cross‐linked polymer.Figure 6.11 DSC heating traces of DGFA/MHHPA/DPMBMI cross‐linked polymer (he...Figure 6.12 DSC heating traces of DGFA/MHHPA/DPMBMI cross‐linked polymer (he...Figure 6.13 DMA spectra of DGFA/MHHPA/DPMBMI cross‐linked polymer. (A) As‐ma...Figure 6.14 Visual inspection of thermal remendability of cured DGFA polymer...Scheme 6.7 FGE synthesized by a two‐step route.Figure 6.15 FTIR spectra of (a) raw FGE and (b) its purified version.Figure 6.16 ¹H‐NMR spectrum of FGE.Figure 6.17 13C‐NMR spectrum of FGE.Figure 6.18 DSC heating trace of the mixture of FGE and DPMBMI. Heating rate...Figure 6.19 FTIR spectra of (a) the mixture of FGE and DPMBMI and (b) the ad...Figure 6.20 ¹H‐NMR spectra of the mixture of FGE and DPMBMI kept at 60 °C fo...Figure 6.21 1H‐NMR spectra of (a) the adduct of FGE and DPMBMI and (b) the r...Figure 6.22 13C‐NMR spectra of (a) the adduct of FGE and DPMBMI and (b) the ...Figure 6.23 FTIR spectrum of cured FGE/MHHPA/DPMBMI polymer.Figure 6.24 DSC heating traces of cured FGE/MHHPA/DPMBMI polymer (heating ra...Figure 6.25 FTIR spectra of cured DGFA/FGE blends. The sample IDs and compos...Figure 6.26 DSC heating traces of the cured blends of DGFA and FGE (heating ...Figure 6.27 DMA spectra of the cured blends of DGFA and FGE: (a) DF91; (b) D...Figure 6.28 Molecular weight between cross‐links of the cured epoxy, M_c, and...Figure 6.29 Characteristic surface Raman peak area ratios of the cured blend...

      7 Chapter 7Scheme 7.1 Dissociation–association of alkoxyamine derivatives.Scheme 7.2 Dynamic crossover or exchange reactions in blended PCMS polymers ...Scheme 7.3 Synthesis of PCMS‐TEMPO. 2, 1‐hydroxy‐2,2,6,6‐tetramethylpiperidi...Scheme 7.4 Synthesis of PCMS‐TEMPO‐EOPh. 6, 1‐(1‐phenyl‐ethoxy)‐2,2,6,6‐tetr...Figure 7.1 Gel formation due to crossover reaction of macromolecular radical...Figure 7.2 DSC heating traces of PCMS‐TEMPO, PCMS‐TEMPO‐EOPh and PCMS‐TEMPO/...Scheme 7.5 Dissociation–association of alkoxyamine 6 (HO‐TEMPO‐EOPh). 13, 4‐...Figure 7.3 Repeated ESR spectra of alkoxyamine 6 (HO‐TEMPO‐EOPh) recorded du...Figure 7.4 Temperature dependence of relative ESR signal intensities.Figure 7.5 Temperature dependence of relative ESR signal intensities.Scheme 7.6 Dissociation–association of a mixture of alkoxyamines 6 and 14. 1...Figure 7.6 ESR spectra of an equimolar mixture of alkoxyamines 6 (HO‐TEMPO‐E...Figure 7.7 ESR spectra of PCMS‐TEMPO/PCMS‐TEMPO‐EOPh blends recorded at diff...Figure 7.8 (a) Normalized ESR integral spectra of PCMS‐TEMPO/PCMS‐TEMPO‐EOPh...Scheme 7.7 Dynamic de‐cross‐linking, crossover cross‐linking, or exchange re...Scheme 7.8 Synthetic route of alkoxyamine‐based cross‐linked PS.Figure 7.9 Typical ESR spectra of reversibly cross‐linked PS (with molar fee...Figure 7.10 (a) Normalized absorption lines obtained from ESR data of revers...Figure 7.11 (a, b) Pyrolytic behaviors of linear PS, reversibly cross‐linked...Figure 7.12 Temperature dependences of (a) loss factor of reversibly cross‐l...Figure 7.13 DMA spectra of reversibly cross‐linked PS measured by repeated s...Figure 7.14 Typical critical stress, σ_crit versus crack length, l/R, of...Figure 7.15 Temperature dependence of dimensional change for linear PS, reve...Scheme 7.9 Synthesis of alkoxyamine‐containing epoxy (diEP).Scheme 7.10 Thermally remendable epoxy containing alkoxyamines.Figure 7.16 (a) Typical ESR spectra of N‐epoxy measured at various temperatu...Figure 7.17 Relative ESR signal intensities of (a) N‐epoxy and (b) 828/diEP ...Figure 7.18 (a, b) Pyrolytic behaviors of cured epoxies.Figure 7.19 Temperature dependence of (a) storage modulus and (b) tan δFigure 7.20 Temperature dependence of (a) storage modulus and (b) tan δFigure 7.21 Repeated impact damaging‐healing of an 828/diEP specimen.Figure 7.22 Effect of healing time on healing efficiency of 828/diEP. Healin...Scheme 7.11 (a) Dissociation–association of the designed alkoxyamine derivat...Scheme 7.12 (a, b) Synthesis of CTPO.Figure 7.23 Typical ESR spectra of (a1) CTPO and (b1) ICPEG2000 measured at ...Figure 7.24 (a) Impact strengths of virgin ICPEG2000 specimens and the repea...Figure 7.25 Repeated macro‐repairing of impacted ICPEG2000 specimen (tempera...Figure 7.26 (a) Schematic drawing of the sample for depth profile analysis o...Scheme 7.13 Synthesis of PU prepolymers.Scheme 7.14 Synthesis of PU prepolymers.Figure 7.27 Operation principle of the two‐way shape memory effect of the pr...Figure 7.28 Programming of the cross‐linked PU toward two‐way shape‐memory e...Figure 7.29 (a) Typical ESR spectra of the cross‐linked PU collected at vari...Figure 7.30 Typical stress relaxation curves of (a) cross‐linked PU and (b) ...Figure 7.31 (a) Length variation of the programmed cross‐linked PU during he...Figure 7.32 Typical time dependence of strain of the programmed cross‐linked...Figure 7.33 Typical tensile stress–strain curves of the cross‐linked PU heal...Figure 7.34 Shape memory effect assisted intrinsic self‐healing of a wider c...

      8 Chapter 8Scheme 8.1 Structures of the disulfide compounds.Scheme 8.2 Macromolecules resembling the target polymer.Figure 8.1 (a) HLPC chromatograms of mixtures containing equivalent amounts ...Scheme 8.3 TBP‐catalyzed metathesis between low‐molecular‐weight disulfides....Scheme 8.4 TBP‐catalyzed disulfide metathesis within a polysulfide network....Figure 8.2 (a) FTIR spectra of EPS‐sh and control‐1 compared with that of EP...Figure 8.3 Storage shear modulus, G′, and loss shear modulus, G″, as functio...Figure 8.4 Typical tensile stress–strain curves of virgin and healed EPS‐sh....Figure 8.5 (a, b) Reshaping and (c, d) reprocessing of EPS‐sh through compre...Figure 8.6 Typical tensile stress–strain curves of recycled EPS‐sh subjected...Figure 8.7 Typical tensile creep strain–time curves for EPS‐sh and the contr...Scheme 8.5 Structures of PU‐HEDS‐400 and its control PU‐BDO‐400.Figure 8.8 (a) HPLC analysis of an equimolar mixture of DEDS and HEDS in ace...Figure 8.9 Absorbance and transmittance of PU‐HEDS‐400 (0.8 mm thick) as a f...Figure 8.10 Images showing repeated healing of scratched PU‐HEDS‐400 film (0...Figure 8.11 (a) Tensile stress–strain curves of virgin and healed PU‐HEDS‐40...Scheme 8.6 Hydrogen bonds formed between PU‐HEDS‐400 macromolecules.Figure 8.12 Sunlight‐aided recycling. (a) Pulverized PU‐HEDS‐400. (b) Molded...Figure 8.13 Tensile stress–strain curves of (a) virgin and solar recycled PU...Figure 8.14 Schematic illustration of fabrication of the sandwich structured...Figure 8.15 (a) UV–visible transmittance spectra of PU and AgNWs/PU composit...Figure 8.16 Relative resistance change, ΔR/R_o, as a function of tensile stra...Figure 8.17 (a) SEM photo of a cross‐section of the sandwiched PU/AgNWs/PU c...Figure 8.18 Typical relative resistance changes, ΔR/R_o, of (a, b) sandwiched...Figure 8.19 Typical relative resistance changes, ΔR/R_o, of (a) sandwiched PU...Figure 8.20 SEM images of (a) the scratched and (b) the sunlight healed surf...Figure 8.21 (a) Quantification of repeated sunlight driven self‐healing of e...Scheme 8.7 Flow chart showing preparation procedures of the cross‐linked sil...Scheme 8.8 Synthesis of the cross‐linked silicone elastomer.Figure 8.22 (a) GC chromatograms of disulfide metathesis between equimolar D...Figure 8.23 Transmittance of SR‐SH and SR‐ref (0.75 mm thick) versus wavelen...Figure 8.24 (a) GPC curves of SS‐MTQ before and after xenon light exposure i...Figure 8.25 Typical tensile stress–strain curves of virgin and healed (a–c, ...Figure 8.26 Recycling of sheeted SR‐SH