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

5 Chapter 5Scheme 5.1 Chemical structure of GMA.Figure 5.1 Optical microscopic images of GMA‐loaded microcapsules prepared a...Figure 5.2 FTIR spectrum of PMF‐walled microcapsules containing GMA in compa...Figure 5.3 DSC heating traces of GMA/DETA and ground GMA‐loaded microcapsule...Figure 5.4 Thermogravimetric analysis (TGA) and differential thermogravimetr...Figure 5.5 Typical load–displacement curves recorded during TDCB tests. The ...Figure 5.6 FTIR spectra of epoxy resins cured at different DETA/epoxy ratios...Figure 5.7 Effect of content of GMA‐loaded microcapsules on healing efficien...Scheme 5.2 Schematic drawing of crack healing in epoxy composite containing ...Figure 5.8 Effect of healing temperature on healing efficiency at a constant...Figure 5.9 SEM micrographs of the fractured surface of (a) virgin self‐heali...Scheme 5.3 Schematic drawing of crack healing in epoxy composite containing ...Figure 5.10 Time dependences of healing efficiency in comparison with that o...Figure 5.11 Effect of DETA to epoxy ratio on molecular weight between cross‐...Scheme 5.4 Schematic drawing of crack repair by living copolymerization of G...Figure 5.12 Profile of a multilayered microcapsule.Scheme 5.5 Mechanism for ATRP.Figure 5.13 1H‐NMR spectrum of resultant PMMA‐Br initiated with 2‐EBiB/CuBr/...Figure 5.14 Characteristics of living polymerization of MMA. (a) ln([ M ] 0/[ M ]...Figure 5.15 (a) GPC curves of PMMA before and after chain extension reaction...Figure 5.16 (a) Healing efficiency of PMMA composites containing 15 wt% GMA‐...Figure 5.17 SEM micrographs of fractured surfaces of PMMA composites contain...Figure 5.18 In‐situ confocal Raman microscopy observation [25]. (a) The typi...Figure 5.19 Healing effect of PMMA composites with styrene‐ and styrene/epox...Figure 5.20 Schematic drawing of the route for preparing the multilayered mi...Figure 5.21 3D distribution of the GMA‐loaded multilayered microcapsules in ...Figure 5.22 Time dependence of healing efficiency of the thermally molded se...Figure 5.23 Healing efficiencies of the thermally molded self‐healing PS com...Figure 5.24 Healing efficiencies of the thermally molded self‐healing PS com...Figure 5.25 Effect of the content of the GMA‐loaded multilayered microcapsul...Figure 5.26 (a) Raman spectrum collected from the re‐fractured surface of a ...Figure 5.27 Thermal decomposition 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 6and 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 critversus 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 δ Figure 7.20 Temperature dependence of (a) storage modulus and (b) tan δ Figure 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...