Search

Understanding how late an inhibitor can be released once corrosion initiated without compromising corrosion protection may help in developing more efficient anticorrosion coatings. We explored this idea through time-controlled Ce(NO3)3 availability to AA2024-T3 immersed in 0.05 M NaCl. Ce(NO3)3 was supplied at 0, 30, 60, and 180 s from the start of immersion to get a concentration of 0.001 M. Detailed visualization of surface changes at the intermetallic particle level was obtained using in-situ reflected microscopy. SEM-EDX and confocal laser microscopy confirmed the extent of intermetallic degradation and local inhibitor deposition corresponding to operando changes. When the inhibitor is supplied within 60 s of immersion, the surface changes slowdown earlier and are visually less extensive than in uninhibited systems. Furthermore, our results highlight the potential of reflected microscopy for local corrosion inhibition studies and underscore the importance of understanding the interaction between inhibitor release timing and corrosion protection., Group Garcia Espallargas, Team Arjan Mol

The interaction of 2,5-dimercapto-1,3,4-thiadiazole (DMTD) with the AA2024-T3 local microstructure (S-phase, secondary phases and matrix) as function of the NaCl concentration is studied. The inhibiting power and the local interaction of DMTD with the metal were studied by in–situ opto-electrochemistry, XPS and Raman spectroscopy. The stability of the inhibiting layers was evaluated by re-exposing the samples to NaCl solutions without inhibitor. The amount of DMTD and its interaction state (chemisorption/physisorption) vary with the local microstructural composition and NaCl concentration. Higher stability of the inhibiting layers is obtained when these are formed in presence of small amounts of NaCl (0.025–0.25 M)., Novel Aerospace Materials, ChemE/Product and Process Engineering

In this work a diffusion-driven inhibitor transport model is used to help in the design of inhibitor-loaded carriers for anticorrosive primers. The work focuses on inhibitor release at damaged locations of different dimensions exposed to electrolyte and is validated experimentally. The damage dimensions are first simulated to determine the minimal inhibitor release rate necessary to reach the required inhibitor concentrations for corrosion protection of the exposed metal. Kinematic and mass conservation laws are then used as first-order approximations to study the effect of different characteristics of nano- and micro-particles loaded with inhibitors embedded in an organic coating during the first 100 s of immersion. The simulated results are validated experimentally using epoxy coatings containing cerium-loaded zeolites and diatomaceous earth as nano- and micro-carriers respectively. These experiments confirmed the simulated predictions, showing that under the used exposure conditions nano-particles are only able to protect relatively small damages of micron size dimensions. Micron-sized carriers on the other hand allow sufficient release to protect larger damages, even at lower pigment volume concentrations. Additional simulations on rapid electrolyte diffusion pathways inside the coating are also in good agreement with the experiments, indicating the presence of diffusion pathways might play an important role in sustained inhibitor release and corrosion protection at local damages., Novel Aerospace Materials, Team Arjan Mol

Autonomous through-thickness scratch repair (healing) in coatings requires scratch closure and interfacial molecular sealing. Although qualitative aspects of the first stage of self-healing have been addressed, quantitative description enabling the control over the healing process need further understanding. In this work the polymer-architecture-dependent stored entropic energy during deformation is quantified using the rubber elasticity theory and correlated to the scratch closure degree experimentally observed in microscopic measurements. Using well-defined thermoplastic healing polyurethanes with variable soft phase fraction contents these studies show that pressure-free damage closure of scratches maintaining mechanical integrity during healing is governed by the capability of the polymer to store entropic energy during damage. The storage (and release) of energy is controlled by varying the damage and healing temperatures in relation to the specific viscoelastic length transition (TVLT) and the glass transition temperature (Tg). Damage closure increases linearly with the entropy release and is controlled by two parameters of the network, the junction density and damping factor. If mechanical damage does not lead to storage of mechanical energy healing does not occur., Novel Aerospace Materials

This work investigates an integrated analysis of in-situ optical data and time-frequency information from electrochemical potential noise (EPN) data to study the effectiveness and durability of an anodic and cathodic corrosion inhibitor. Two different corrosion inhibiting species, cerium(III) (Ce(III)) and phytic acid (PHA), are tested on aluminum alloy AA2024-T3. Corrosion of AA2024-T3 serves as a negative reference. Time-frequency analysis of EPN data provides a direct insight in the kinetics of the electrochemical processes related to different types of corrosion and/or inhibitor activity over time. The simultaneous, in-situ optical technique allows visualizing and quantifying the surface changes associated with the electrochemical signals. Both Ce(III) and PHA were not capable to inhibit corrosion to a large extent, as re-immersion led to electrochemical (corrosion) activity for both inhibitors. Time-variant changes between corrosion, inhibitor activity, inhibited state and re-activation can effectively be discriminated from each other., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., Team Arjan Mol, Novel Aerospace Materials

Autonomous through-thickness scratch repair (healing) in coatings requires scratch closure and interfacial molecular sealing. Although qualitative aspects of the first stage of self-healing have been addressed, quantitative description enabling the control over the healing process need further understanding. In this work the polymer-architecture-dependent stored entropic energy during deformation is quantified using the rubber elasticity theory and correlated to the scratch closure degree experimentally observed in microscopic measurements. Using well-defined thermoplastic healing polyurethanes with variable soft phase fraction contents these studies show that pressure-free damage closure of scratches maintaining mechanical integrity during healing is governed by the capability of the polymer to store entropic energy during damage. The storage (and release) of energy is controlled by varying the damage and healing temperatures in relation to the specific viscoelastic length transition (TVLT) and the glass transition temperature (Tg). Damage closure increases linearly with the entropy release and is controlled by two parameters of the network, the junction density and damping factor. If mechanical damage does not lead to storage of mechanical energy healing does not occur., Novel Aerospace Materials

In this work a diffusion-driven inhibitor transport model is used to help in the design of inhibitor-loaded carriers for anticorrosive primers. The work focuses on inhibitor release at damaged locations of different dimensions exposed to electrolyte and is validated experimentally. The damage dimensions are first simulated to determine the minimal inhibitor release rate necessary to reach the required inhibitor concentrations for corrosion protection of the exposed metal. Kinematic and mass conservation laws are then used as first-order approximations to study the effect of different characteristics of nano- and micro-particles loaded with inhibitors embedded in an organic coating during the first 100 s of immersion. The simulated results are validated experimentally using epoxy coatings containing cerium-loaded zeolites and diatomaceous earth as nano- and micro-carriers respectively. These experiments confirmed the simulated predictions, showing that under the used exposure conditions nano-particles are only able to protect relatively small damages of micron size dimensions. Micron-sized carriers on the other hand allow sufficient release to protect larger damages, even at lower pigment volume concentrations. Additional simulations on rapid electrolyte diffusion pathways inside the coating are also in good agreement with the experiments, indicating the presence of diffusion pathways might play an important role in sustained inhibitor release and corrosion protection at local damages., Novel Aerospace Materials, Team Arjan Mol

The use of self-healing (SH) polymers to make 3D-printed polymeric parts offers the po-tential to increase the quality of 3D-printed parts and to increase their durability and damage toler-ance due to their (on-demand) dynamic nature. Nevertheless, 3D-printing of such dynamic poly-mers is not a straightforward process due to their polymer architecture and rheological complexity and the limited quantities produced at lab-scale. This limits the exploration of the full potential of self-healing polymers. In this paper, we present the complete process for fused deposition model-lingof a room temperature self-healing polyurethane. Starting from the synthesis and polymer slab manufacturing, we processed the polymer into a continuous filament and 3D printed parts. For the characterization ofthe 3D printed parts,we used a compression cut test, which proved useful when limited amount of material is available. The test was able to quasi-quantitatively assess both bulk and 3D printed samples and their self-healing behavior. The mechanical and healing behavior of the3D printed self-healing polyurethane was highly similar to that of the bulk SH polymer. This indicates that the self-healing property of the polymer was retained even after multiple processing steps and printing. Compared to a commercial 3D-printing thermoplastic polyurethane, the self-healing polymer displayed a smaller mechanical dependency on the printing conditions with the added value of healing cuts at room temperature., Novel Aerospace Materials

A hyphenated optical-electrochemical technique and image analysis protocol is used to quantify global and local (intermetallic) corrosion process and kinetics. Our findings reveal an early stage (< 60 s) composition-dependent hierarchical local activation of all IMs that can be attributed to IM dealloying. This is followed by local trenching initiated at matrix locations adjacent to regions of the IMs previously dealloyed, which in turn develops into concentric trenching around the IMs. These stages have quantifiable activation times and kinetics. While dealloying kinetics are found to be strongly dependent on IM composition and slightly dependent on IM size in the case of the S-phases, trenching kinetics are IM composition and size independent., Novel Aerospace Materials

The effects of the soft block fraction and H-bond state in thermoplastic polyurethanes on autonomous entropy-driven scratch closure and barrier restoration are studied. To this aim, comparable polyurethanes with different segmentation states are applied as organic coatings on plain carbon steel plates, scratched under very well-controlled conditions, and the scratch closure and sealing kinetics are studied in detail. The scratch closure is measured optically, while the barrier restoration is probed by the accelerated cyclic electrochemical technique (ACET). Scratch closure, attributed to entropic elastic recovery (EER), is followed in a marked two-step process by barrier restoration governed by local viscous flow and the state of the interfacial hydrogen bonding. Polyurethanes with a lower soft phase fraction lead to a higher urea/urethane ratio, which in turn influences the healing efficiency of each healing step. Interestingly, softer polyurethanes leading to efficient crack closure were unable to sufficiently restore barrier properties. The present work highlights the critical role of the soft/hard block and urea/urethane H-bond state content on crack closure and barrier restoration of anticorrosive organic coatings and points at design rules for the design of more efficient corrosion-protective self-healing polyurethanes., Novel Aerospace Materials

The elastic modulus of corrosion product (Ecp) has been reported with significant variations in the literature. This study aims to investigate the Ecp of naturally-generated chloride-induced corrosion products formed in different concrete mixes. Microstructural characterization was conducted through nano-indentation, electron microscopy and Raman spectroscopy. The corrosion products were mainly composed of a goethite matrix with portions of maghemite, independently of the concrete composition. Microscopic analysis suggest that layers of corrosion products grow at different times and under different physico-chemical conditions. Our measurements showed that Ecp varied between 80−100 GPa, which can be suggested for numerical models of corrosion induced cracking., Materials and Environment, Novel Aerospace Materials

The use of self-healing (SH) polymers to make 3D-printed polymeric parts offers the po-tential to increase the quality of 3D-printed parts and to increase their durability and damage toler-ance due to their (on-demand) dynamic nature. Nevertheless, 3D-printing of such dynamic poly-mers is not a straightforward process due to their polymer architecture and rheological complexity and the limited quantities produced at lab-scale. This limits the exploration of the full potential of self-healing polymers. In this paper, we present the complete process for fused deposition model-lingof a room temperature self-healing polyurethane. Starting from the synthesis and polymer slab manufacturing, we processed the polymer into a continuous filament and 3D printed parts. For the characterization ofthe 3D printed parts,we used a compression cut test, which proved useful when limited amount of material is available. The test was able to quasi-quantitatively assess both bulk and 3D printed samples and their self-healing behavior. The mechanical and healing behavior of the3D printed self-healing polyurethane was highly similar to that of the bulk SH polymer. This indicates that the self-healing property of the polymer was retained even after multiple processing steps and printing. Compared to a commercial 3D-printing thermoplastic polyurethane, the self-healing polymer displayed a smaller mechanical dependency on the printing conditions with the added value of healing cuts at room temperature., Novel Aerospace Materials

A hyphenated optical-electrochemical technique and image analysis protocol is used to quantify global and local (intermetallic) corrosion process and kinetics. Our findings reveal an early stage (< 60 s) composition-dependent hierarchical local activation of all IMs that can be attributed to IM dealloying. This is followed by local trenching initiated at matrix locations adjacent to regions of the IMs previously dealloyed, which in turn develops into concentric trenching around the IMs. These stages have quantifiable activation times and kinetics. While dealloying kinetics are found to be strongly dependent on IM composition and slightly dependent on IM size in the case of the S-phases, trenching kinetics are IM composition and size independent., Novel Aerospace Materials

The effects of the soft block fraction and H-bond state in thermoplastic polyurethanes on autonomous entropy-driven scratch closure and barrier restoration are studied. To this aim, comparable polyurethanes with different segmentation states are applied as organic coatings on plain carbon steel plates, scratched under very well-controlled conditions, and the scratch closure and sealing kinetics are studied in detail. The scratch closure is measured optically, while the barrier restoration is probed by the accelerated cyclic electrochemical technique (ACET). Scratch closure, attributed to entropic elastic recovery (EER), is followed in a marked two-step process by barrier restoration governed by local viscous flow and the state of the interfacial hydrogen bonding. Polyurethanes with a lower soft phase fraction lead to a higher urea/urethane ratio, which in turn influences the healing efficiency of each healing step. Interestingly, softer polyurethanes leading to efficient crack closure were unable to sufficiently restore barrier properties. The present work highlights the critical role of the soft/hard block and urea/urethane H-bond state content on crack closure and barrier restoration of anticorrosive organic coatings and points at design rules for the design of more efficient corrosion-protective self-healing polyurethanes., Novel Aerospace Materials

The elastic modulus of corrosion product (Ecp) has been reported with significant variations in the literature. This study aims to investigate the Ecp of naturally-generated chloride-induced corrosion products formed in different concrete mixes. Microstructural characterization was conducted through nano-indentation, electron microscopy and Raman spectroscopy. The corrosion products were mainly composed of a goethite matrix with portions of maghemite, independently of the concrete composition. Microscopic analysis suggest that layers of corrosion products grow at different times and under different physico-chemical conditions. Our measurements showed that Ecp varied between 80−100 GPa, which can be suggested for numerical models of corrosion induced cracking., Materials and Environment, Novel Aerospace Materials

The use of rheology and terminal flow relaxation times to predict healing behavior at long healing times is by now quite well accepted. In this work we go one step further and explore the use of macro-rheology (in particular the stored work of deformation) to predict the early stage interfacial healing properties (fracture resistance) of a set of self-healing polyurethanes. The interfacial healing is measured by single edge notch fracture experiments, using short healing times and a low healing temperature to exclude the effect of long range molecular motion on mechanical properties restoration. The systems based on aromatic diisocyanates show high fracture resistance after healing, while very limited restoration of the mechanical properties is observed for aliphatic and cycloaliphatic based polyurethanes. Linear sweep rheology and time-temperature-superposition allow obtaining the macro-rheological master curve and the mechanical relaxation spectra (H(t)). The application of a recently established deconvolution protocol to the H(t) gives the characteristic relaxation times and stored works of deformation associated to individual dynamic processes such as segmental motion, reversible bonds, and terminal flow. It is found that the calculated stored works of deformation related to the reversible bond relaxation reproduce the trend observed by fracture resistance at healed interfaces and reveal a qualitative correspondence between reversible bonds work of deformation and interfacial healing fracture resistance. Moreover, the method seems to point to the existence of a threshold interfacial work of deformation below which no efficient load transfer can be observed., Novel Aerospace Materials

Earlier studies on cerium-loaded naturally occurring silica microparticles (i.e., diatomaceous earth) demonstrated the potential to efficiently protect small scratches in epoxy-coated AA2024-T3 panels during relatively short immersion times. The current work investigates the potential of such inhibitor-loaded microparticles to protect wide and deep scribes (up to 1 mm wide) in long-time immersion testing and during cyclic (wet/dry) conditions. For this, cerium nitrate and 2,5-dimercaptothiadiazole (DMTD) were used as inorganic and organic corrosion inhibitors. The corrosion protection was evaluated using a hyphenated real-time optics/electrochemistry method and two individual local techniques measuring oxygen concentration and electrochemical impedance (LEIM) inside the scribe. SEM/EDS was used to analyze the samples after exposure. The results show significant levels of corrosion protection at damaged locations at low cerium concentrations (3.7 wt % Ce3+ relative to the total coating mass) during 30 days of immersion in salt solution. However, for a given scribe geometry, the protection was found to be dependent on the electrolyte volume with larger electrolyte/exposed metal ratios leading to short protection time. A partial replacement of the Ce3+ by DMTD in the microcarriers resulted in a higher degree of passivation than when DMTD was used alone. Wet/dry cyclic exposure tests showed that cyclic conditions can increase the buildup of stable inhibitor-containing layers in the case of cerium-loaded silica microparticles. This underlines the need for more research using wet/dry exposure conditions., Novel Aerospace Materials

The use of rheology and terminal flow relaxation times to predict healing behavior at long healing times is by now quite well accepted. In this work we go one step further and explore the use of macro-rheology (in particular the stored work of deformation) to predict the early stage interfacial healing properties (fracture resistance) of a set of self-healing polyurethanes. The interfacial healing is measured by single edge notch fracture experiments, using short healing times and a low healing temperature to exclude the effect of long range molecular motion on mechanical properties restoration. The systems based on aromatic diisocyanates show high fracture resistance after healing, while very limited restoration of the mechanical properties is observed for aliphatic and cycloaliphatic based polyurethanes. Linear sweep rheology and time-temperature-superposition allow obtaining the macro-rheological master curve and the mechanical relaxation spectra (H(t)). The application of a recently established deconvolution protocol to the H(t) gives the characteristic relaxation times and stored works of deformation associated to individual dynamic processes such as segmental motion, reversible bonds, and terminal flow. It is found that the calculated stored works of deformation related to the reversible bond relaxation reproduce the trend observed by fracture resistance at healed interfaces and reveal a qualitative correspondence between reversible bonds work of deformation and interfacial healing fracture resistance. Moreover, the method seems to point to the existence of a threshold interfacial work of deformation below which no efficient load transfer can be observed., Novel Aerospace Materials

Earlier studies on cerium-loaded naturally occurring silica microparticles (i.e., diatomaceous earth) demonstrated the potential to efficiently protect small scratches in epoxy-coated AA2024-T3 panels during relatively short immersion times. The current work investigates the potential of such inhibitor-loaded microparticles to protect wide and deep scribes (up to 1 mm wide) in long-time immersion testing and during cyclic (wet/dry) conditions. For this, cerium nitrate and 2,5-dimercaptothiadiazole (DMTD) were used as inorganic and organic corrosion inhibitors. The corrosion protection was evaluated using a hyphenated real-time optics/electrochemistry method and two individual local techniques measuring oxygen concentration and electrochemical impedance (LEIM) inside the scribe. SEM/EDS was used to analyze the samples after exposure. The results show significant levels of corrosion protection at damaged locations at low cerium concentrations (3.7 wt % Ce3+ relative to the total coating mass) during 30 days of immersion in salt solution. However, for a given scribe geometry, the protection was found to be dependent on the electrolyte volume with larger electrolyte/exposed metal ratios leading to short protection time. A partial replacement of the Ce3+ by DMTD in the microcarriers resulted in a higher degree of passivation than when DMTD was used alone. Wet/dry cyclic exposure tests showed that cyclic conditions can increase the buildup of stable inhibitor-containing layers in the case of cerium-loaded silica microparticles. This underlines the need for more research using wet/dry exposure conditions., Novel Aerospace Materials

Real-time optical analysis is used to improve the interpretation of electrochemical noise signals (EN). The concept is presented for the case of AA2024-T3 under immersion in various NaCl concentrations. An in-house developed optical-electrochemical technique allowed for high spatiotemporal resolution and was used to visualize and quantify surface changes in parallel with monitoring EN signals. EN analysis was performed in the time-frequency domain using continuous wavelet transform (CWT). Correlations between the two procedures enabled the identification of corrosion processes in time, such as de-alloying, etching, pitting and subsurface corrosion. Besides this, optical measurements at higher magnification were used to analyse a smaller section of the exposed metal with a spatial resolution below 1 μm. This enabled the quantification on the size, number and nearest neighbor distance of local corrosion events, such as pits and corrosion rings. The set-up and optical protocol allowed for the first time (i) to establish a direct relationship between EN signals and the occurrence of specific localized corrosion phenomena and (ii) an in-situ highly-resolved monitoring of local corrosion processes. As a final result of the optical analysis we introduce a straightforward illustration that allows the direct identification of EN features to macroscopic local corrosion phenomena., Novel Aerospace Materials

An in-situ hyphenated optical and electrochemical method for the real-time study of corrosion and corrosion inhibition processes is presented and validated for the case of AA2024-T3 exposed to two NaCl concentrations and six inhibitors. During testing, 5 μm resolution optical images of the exposed surface are obtained in parallel to electrochemical impedance measurements using a home-made 3D printed electrochemical cell. This method allowed obtaining both optical and electrochemical information of the studied surface with high time correlation. A data treatment analysis of the optical images was established thereby allowing the identification and quantification of corrosion-features related to intermetallic corrosion (e.g. trenching and meta-stable pitting) and co-operative corrosion (e.g. corrosion-rings, domes and surface-oxides) on a spatiotemporal scale, generally only observed through the use of ex-situ methods such as SEM. In addition, the study of the long-term corrosion inhibition of six inhibitors at concentrations ranging from 10−3 M to 10−6 M allowed quantifying inhibition kinetics as well as identifying different inhibitor and concentration dependent mechanisms (e.g. Cerium and DEDTC vs. Lithium) and decreasing incongruences between impedance and inhibition behaviour (e.g. DMTD). As a result, the use of quantifiable in-situ optical analysis is confirmed as a powerful tool to better interpret electrochemical signals or monitor electrochemical-dependent surface phenomena., Novel Aerospace Materials

Starting from experimental macro-rheological data, we develop a fitting protocol that succeeded in the separation of the overlapping relaxation phenomena in the dissipative regime for a set of intrinsic healing polymers healing most effectively near their glass transition temperature T g . To allow for a proper deconvolution, the rheological master curves are converted to a relaxation spectrum (H(τ)) and this is fitted using an optimized mechanical model, e.g. the Maxwell-Weichert model. The deconvolution of overlapping segmental mobility and reversible interactions is successfully demonstrated for a set of polyimide and polyamide polymers containing none, one and two reversible dynamic features near-T g . Through the fitting parameters, the relaxation timescale of each feature and their apparent process enthalpies are obtained. The quantitative data obtained using the fitting protocol are then compared to macroscopic healing results. As a result, a clear correspondence between the energy stored by the system to accomplish reversible (e.g. H-bonds, π-π) and chain interdiffusion relaxation transitions and the healing efficiency of such polymers are obtained. The implementation of this protocol allows for a clearer identification of the relevant mechanisms in self-healing polymers and paves the way for the development of more efficiently healable polymeric systems., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., Novel Aerospace Materials, ChemE/Advanced Soft Matter

In this work, we propose the use of regular branching of polyurethanes as a way to regulate chain dynamics and govern crystallization in highly dense hydrogen-bonded systems. As a result, robust and healable polyurethanes can be obtained. To this end, we synthesized a range of aliphatic propane diol derivatives with alkyl branches ranging from butyl (C4) to octadecanyl (C18). The series of brush polyurethanes was synthesized by polyaddition of the diols and hexamethylene diisocyanate. Polyurethanes with very short (C 4) and very long (C = 18) brush lengths did not lead to any significant healing due to crystallization. An intermediate amorphous regime appears for polymers with middle branch lengths (C = 4 to 8) showing a fine control of material toughness. For these systems, the side chain length regulates tube dilation, and significant macroscopic healing of cut samples was observed and studied in detail using melt rheology and tensile testing. Despite the high healing degrees observed immediately after repair, it was found that samples with medium to long length brushes lost their interfacial strength at the healed site after being heated to the healing temperature for some time after the optimal time to reach full healing. Dedicated testing suggests that annealed samples, while keeping initial tackiness, are not able to completely heal the cut interface. We attribute such behavior to annealing-induced interfacial crystallization promoted by the aliphatic branches. Interestingly, no such loss of healing due to annealing was observed for samples synthesized with C4 and C7 diols, which is identified as the optimal healing regime. These results point at the positive effect of branching on healing, provided that a critical chain length is not surpassed, as well as the need to study healing behavior long after the optimal healing times., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., Novel Aerospace Materials

The impressive mechanical properties of natural composites, such as nacre, arise from their multiscale hierarchical structures, which span from nano- to macroscale and lead to effective energy dissipation. While some synthetic bioinspired materials have achieved the toughness of natural nacre, current production methods are complex and typically involve toxic chemicals, extreme temperatures, and/or high pressures. Here, the exclusive use of bacteria to produce nacre-inspired layered calcium carbonate-polyglutamate composite materials that reach and exceed the toughness of natural nacre, while additionally exhibiting high extensibility and maintaining high stiffness, is introduced. The extensive diversity of bacterial metabolic abilities and the possibility of genetic engineering allows for the creation of a library of bacterially produced, cost-effective, and eco-friendly composite materials., BN/Marie-Eve Aubin-Tam Lab, Novel Aerospace Materials

In this work, we propose the use of regular branching of polyurethanes as a way to regulate chain dynamics and govern crystallization in highly dense hydrogen-bonded systems. As a result, robust and healable polyurethanes can be obtained. To this end, we synthesized a range of aliphatic propane diol derivatives with alkyl branches ranging from butyl (C4) to octadecanyl (C18). The series of brush polyurethanes was synthesized by polyaddition of the diols and hexamethylene diisocyanate. Polyurethanes with very short (C 4) and very long (C = 18) brush lengths did not lead to any significant healing due to crystallization. An intermediate amorphous regime appears for polymers with middle branch lengths (C = 4 to 8) showing a fine control of material toughness. For these systems, the side chain length regulates tube dilation, and significant macroscopic healing of cut samples was observed and studied in detail using melt rheology and tensile testing. Despite the high healing degrees observed immediately after repair, it was found that samples with medium to long length brushes lost their interfacial strength at the healed site after being heated to the healing temperature for some time after the optimal time to reach full healing. Dedicated testing suggests that annealed samples, while keeping initial tackiness, are not able to completely heal the cut interface. We attribute such behavior to annealing-induced interfacial crystallization promoted by the aliphatic branches. Interestingly, no such loss of healing due to annealing was observed for samples synthesized with C4 and C7 diols, which is identified as the optimal healing regime. These results point at the positive effect of branching on healing, provided that a critical chain length is not surpassed, as well as the need to study healing behavior long after the optimal healing times., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., Novel Aerospace Materials

The impressive mechanical properties of natural composites, such as nacre, arise from their multiscale hierarchical structures, which span from nano- to macroscale and lead to effective energy dissipation. While some synthetic bioinspired materials have achieved the toughness of natural nacre, current production methods are complex and typically involve toxic chemicals, extreme temperatures, and/or high pressures. Here, the exclusive use of bacteria to produce nacre-inspired layered calcium carbonate-polyglutamate composite materials that reach and exceed the toughness of natural nacre, while additionally exhibiting high extensibility and maintaining high stiffness, is introduced. The extensive diversity of bacterial metabolic abilities and the possibility of genetic engineering allows for the creation of a library of bacterially produced, cost-effective, and eco-friendly composite materials., BN/Marie-Eve Aubin-Tam Lab, Novel Aerospace Materials

In the current paper the corrosion inhibition synergy between Ce3+ loaded NaY-zeolite (NaY-Ce) and 2-Mercaptobenzothiazole (MBT) loaded Zn-Al layered double hydroxide (LDH-MBT) containers is presented. Solutions and water-borne epoxy coatings containing different ratios of the two loaded carriers were prepared and their protection of AA2024-T3 and damaged coatings characterized using global and local electrochemical techniques and other complementary tools. The coatings containing container-combinations showed exceptional corrosion protection over a broad range of NaY-Ce:LDH-MBT weight ratios, with 90:10 being the optimal. The current work landmarks the need for synergetic inhibiting studies devoted to carrier-inhibitor systems in coatings., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., Novel Aerospace Materials

This review outlines latest developments in the field of self-healing rubbers and elastomers, analyzing their potential application to natural rubber (NR). Different validated healing concepts are presented and the possibilities of applying them to NR are discussed. Research in this field should aim at modifying the chemical structure of NR as to enhance physical or chemical reversible interactions either intermolecular or intramolecular. The realization of better mechanical properties at relevant working conditions and with milder healing conditions remains a challenge for all self-healing rubbers. This overview should be seen as setting the conceptual framework for new developments with a more clearly defined industrial focus., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., Novel Aerospace Materials

Mussel byssal threads are well-known due to their self-healing ability after the mechanical stress caused by waves. The proposed mechanism demonstrates the importance of reversible histidine-metal interactions as well as the block copolymer-like hierarchical architecture of the underlying protein structure. Taking these two aspects as inspiration for the design of synthetic analogs, different histidine-rich block copolymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The hard domain was mimicked using polystyrene and the soft domain consists of n-butyl acrylate (BA) as well as histidine moieties as ligands. The block copolymers were crosslinked using different zinc(ii) salts and the resulting metallopolymers were investigated with respect to their self-healing abilities. The observed two-step mechanism of the self-healing process was studied in detail. Furthermore, the mechanical properties were determined by nanoindentation and were correlated with other results., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., Novel Aerospace Materials

We present a systematic study of the role of the aromatic dianhydride structure on the self-healing behavior of dimer diamine-based polyimides. By means of solid-state NMR and rheology, we studied the molecular and microscale dynamics of four polyimides comprising the same aliphatic branched diamine yet with variable dianhydride rigidities and correlated these to their macroscopic healing kinetics measured by tensile testing. Following the two-step kinetics of the healing process, we were able to differentiate and quantify the extent of mechanical strength recovery in each of the healing stages separately. Moreover, the detailed rheology and solid-state NMR allowed us to shed light on the role of the aromatic interactions and branches on the mechanical properties and mechanical integrity during macroscopic healing. The study reveals the relevance and interplay of primary and secondary interactions in the development of non-cross-linked strong and healing polymers able to maintain mechanical integrity during healing., Novel Aerospace Materials

Superabsorbent polymers (SAPs) are well known for their ability to absorb and hold high water amounts accompanied by a high volume expansion. In this work we show the benefits of this underlying property of SAPs to induce underwater crack closure with subsequent barrier restoration in damaged protective coatings. For the proof of concept, three layer epoxy-polyester (EP) powder coating systems were developed and applied on carbon steel. In these systems the middle EP layer (also called functional layer) contained crosslinked acrylamide/acrylic acid copolymer SAPs in different amounts ranging from 0 to 40 wt%. The capability of the SAPs to close damages and extend barrier and corrosion protection was evaluated by electrochemical impedance spectroscopy (EIS), NaCl aqueous solution immersion test and optical microscopy. It was found that coatings loaded with a 20 wt% SAP led to the best overall corrosion protection for the studied systems. In order to proof the potential use of this extrinsic healing concept for multiple healing events wet-dry cycles on scratched systems were performed and the corrosion performance was followed by EIS. Although not yet optimal, the results show the potential of the concept for multiple healing events under wet-dry conditions., Novel Aerospace Materials

In this work, a new concept is introduced for active corrosion protection at damaged sites aiming at overcoming existing limitations of currently proposed strategies based on dispersed inhibitor-loaded nanocontainers in coatings. The underlying principle is based on the formation of low-density and/or humidity responsive interconnected paths of inhibitor in the coating, what is called inhibiting nanonetworks. Such an approach allows for (on-demand) long-term local supply of corrosion inhibitor at the damage site. For the proof-of-concept, water responsive inhibiting nanonetworks based on polyvinyl alcohol and two known efficient corrosion inhibitors for AA2024-T3 (cerium chloride and lithium carbonate) using electrospinning are developed. The inhibiting nanonetworks are obtained by subsequently embedding the electrospun fiber mats in thermoset epoxy coatings applied on AA2024-T3. The coated panels are scratched and exposed to NaCl solutions for a month while continuously monitoring the protective properties electrochemically and optically in a hyphenated setup. The effect of the corrosion inhibitor type and the partial crosslinking of the mat on release and protection are analyzed. Protection levels at relatively big damaged sites are obtained for at least a month immersion thereby proving the benefits of high inhibitor quantities continuously released in time., Novel Aerospace Materials

Mussel byssal threads are well-known due to their self-healing ability after the mechanical stress caused by waves. The proposed mechanism demonstrates the importance of reversible histidine-metal interactions as well as the block copolymer-like hierarchical architecture of the underlying protein structure. Taking these two aspects as inspiration for the design of synthetic analogs, different histidine-rich block copolymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The hard domain was mimicked using polystyrene and the soft domain consists of n-butyl acrylate (BA) as well as histidine moieties as ligands. The block copolymers were crosslinked using different zinc(ii) salts and the resulting metallopolymers were investigated with respect to their self-healing abilities. The observed two-step mechanism of the self-healing process was studied in detail. Furthermore, the mechanical properties were determined by nanoindentation and were correlated with other results., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., Novel Aerospace Materials

In the current paper the corrosion inhibition synergy between Ce3+ loaded NaY-zeolite (NaY-Ce) and 2-Mercaptobenzothiazole (MBT) loaded Zn-Al layered double hydroxide (LDH-MBT) containers is presented. Solutions and water-borne epoxy coatings containing different ratios of the two loaded carriers were prepared and their protection of AA2024-T3 and damaged coatings characterized using global and local electrochemical techniques and other complementary tools. The coatings containing container-combinations showed exceptional corrosion protection over a broad range of NaY-Ce:LDH-MBT weight ratios, with 90:10 being the optimal. The current work landmarks the need for synergetic inhibiting studies devoted to carrier-inhibitor systems in coatings., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., Novel Aerospace Materials

This review outlines latest developments in the field of self-healing rubbers and elastomers, analyzing their potential application to natural rubber (NR). Different validated healing concepts are presented and the possibilities of applying them to NR are discussed. Research in this field should aim at modifying the chemical structure of NR as to enhance physical or chemical reversible interactions either intermolecular or intramolecular. The realization of better mechanical properties at relevant working conditions and with milder healing conditions remains a challenge for all self-healing rubbers. This overview should be seen as setting the conceptual framework for new developments with a more clearly defined industrial focus., Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., Novel Aerospace Materials

We present a systematic study of the role of the aromatic dianhydride structure on the self-healing behavior of dimer diamine-based polyimides. By means of solid-state NMR and rheology, we studied the molecular and microscale dynamics of four polyimides comprising the same aliphatic branched diamine yet with variable dianhydride rigidities and correlated these to their macroscopic healing kinetics measured by tensile testing. Following the two-step kinetics of the healing process, we were able to differentiate and quantify the extent of mechanical strength recovery in each of the healing stages separately. Moreover, the detailed rheology and solid-state NMR allowed us to shed light on the role of the aromatic interactions and branches on the mechanical properties and mechanical integrity during macroscopic healing. The study reveals the relevance and interplay of primary and secondary interactions in the development of non-cross-linked strong and healing polymers able to maintain mechanical integrity during healing., Novel Aerospace Materials

In this work, a new concept is introduced for active corrosion protection at damaged sites aiming at overcoming existing limitations of currently proposed strategies based on dispersed inhibitor-loaded nanocontainers in coatings. The underlying principle is based on the formation of low-density and/or humidity responsive interconnected paths of inhibitor in the coating, what is called inhibiting nanonetworks. Such an approach allows for (on-demand) long-term local supply of corrosion inhibitor at the damage site. For the proof-of-concept, water responsive inhibiting nanonetworks based on polyvinyl alcohol and two known efficient corrosion inhibitors for AA2024-T3 (cerium chloride and lithium carbonate) using electrospinning are developed. The inhibiting nanonetworks are obtained by subsequently embedding the electrospun fiber mats in thermoset epoxy coatings applied on AA2024-T3. The coated panels are scratched and exposed to NaCl solutions for a month while continuously monitoring the protective properties electrochemically and optically in a hyphenated setup. The effect of the corrosion inhibitor type and the partial crosslinking of the mat on release and protection are analyzed. Protection levels at relatively big damaged sites are obtained for at least a month immersion thereby proving the benefits of high inhibitor quantities continuously released in time., Novel Aerospace Materials

Superabsorbent polymers (SAPs) are well known for their ability to absorb and hold high water amounts accompanied by a high volume expansion. In this work we show the benefits of this underlying property of SAPs to induce underwater crack closure with subsequent barrier restoration in damaged protective coatings. For the proof of concept, three layer epoxy-polyester (EP) powder coating systems were developed and applied on carbon steel. In these systems the middle EP layer (also called functional layer) contained crosslinked acrylamide/acrylic acid copolymer SAPs in different amounts ranging from 0 to 40 wt%. The capability of the SAPs to close damages and extend barrier and corrosion protection was evaluated by electrochemical impedance spectroscopy (EIS), NaCl aqueous solution immersion test and optical microscopy. It was found that coatings loaded with a 20 wt% SAP led to the best overall corrosion protection for the studied systems. In order to proof the potential use of this extrinsic healing concept for multiple healing events wet-dry cycles on scratched systems were performed and the corrosion performance was followed by EIS. Although not yet optimal, the results show the potential of the concept for multiple healing events under wet-dry conditions., Novel Aerospace Materials

In this work we report the effect of the hard block dianhydride structure on the overall properties of partially bio-based semi-aromatic polyimides. For the study, four polyimides were synthesized using aliphatic fatty dimer diamine (DD1) as the soft block and four different commercially available aromatic dianhydrides as the hard block: 4,4'-(4,4'-isopropylidenediphenoxy) bis-(phthalic anhydride) (BPADA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4′-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA). The polymers synthesized were fully organo-soluble thermoplastic branched polyimides with glass transition temperatures close to room temperature. The detailed analysis took into account several aspects of the dianhydrides structure (planarity, rigidity, bridging group between the phtalimides, electronic properties) and related them to the results obtained by differential scanning calorimetry, rheology, fluorescence and broadband dielectric spectroscopy. Moreover, the effect of physical parameters (crystallization and electronic interactions) on the relaxation behavior are discussed. Despite the presence of the bulky branched soft block given by the dimer diamine, all polyimides showed intermolecular charge transfer complexes, whose impact depends on the electronic properties of the dianhydride hard block. Furthermore, the results showed that polyimides containing flexible and bulky hard blocks turned out fully amorphous while the more rigid dianhydride (BPDA) led to a nanophase separated morphology with low degree of crystallinity resulting in constrained segmental relaxation with high effect on its mechanical response with the annealing time. This work represents the first detailed report on the development and characterization of polyimides based on a bio-based fatty dimer diamine. The results highlight the potential of polymer property design by controlled engineering of the aromatic dianhydride blocks., Novel Aerospace Materials

Novel Aerospace Materials

This article presents development of a novel self-healing technology for asphalt pavements, where asphalt binder rejuvenator is encapsulated within the compartmented alginate fibres. The key objective of the study was to optimise the compartmented alginate fibre design, i.e., maximising amount of rejuvenator encapsulated within the fibre. The results demonstrate that optimum rejuvenator content in the alginate fibre is of 70:30 rejuvenator/alginate ratio. The fibres are of sufficient thermal and mechanical strength to survive harsh asphalt mixing and compaction processes. Furthermore, results illustrate that zeer open asfalt beton (ZOAB) asphalt mix containing 5% of 70:30 rejuvenator/alginate ratio compartmented alginate fibres has higher strength, stiffness and better healing properties in comparison to the control asphalt mix, i.e., mix without fibres, and mix containing fibres with lower rejuvenator content. These results show that compartmented alginate fibres encapsulating bitumen rejuvenator present a promising new approach for the development of self-healing asphalt pavement systems., Materials and Environment, Novel Aerospace Materials

The main aim of this work is to study the respective contribution of the hard and soft blocks of a metal-ligand containing block copolymer to the self-healing behavior. To this aim, different block copolymers containing terpyridine were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization. These block copolymers consisted of polystyrene as the hard block, n-butyl acrylate (BA) as soft block and terpyridine units as the ligand moiety placed at different locations in the soft block. These block copolymers were complexed with manganese(II) chloride to introduce transient crosslinks and, thus, self-healing behavior. Homopolymers with the hard and soft block only were also synthesized and tested. A quasi-irreversible crosslinking, i.e. by using nickel(II) nitrate, was performed in order to study the dynamics of the permanently (strongly) crosslinked network. Rheological master curves were generated enabling the determination of the terminal flow in these networks and the reversibility of the supramolecular interactions. Additionally, the macroscopic scratch healing behavior and the molecular mobility of the polymer chains in these supramolecular networks were investigated. A kinetic study of the scratch healing was performed to determine the similarities in temperature dependence for rheological relaxations and macroscopic scratch healing. In our previous work, we have explored the effect of strength of the reversible metal-ligand interaction and the effect of changing the ratio of hard to soft block. This work goes further in separating the individual contributions of the hard and soft blocks as well as the reversible interactions and to reveal their relative importance in the complex phenomenon of scratch healing., Novel Aerospace Materials

A comparative study is performed on the monitoring of delamination healing in CFRP-ionomer sandwich composites by non-destructive techniques and destructive compression testing. Artificial delaminations of various areal dimensions and nature were introduced during production of the composites. The extent of the delamination and the healing thereof was monitored in both air and water-coupled ultrasonic C-scan experiments as well as by the frequency shift of the local defect resonance (LDR). It is shown that the LDR approach can be used to detect the early stage healing of the delaminations while ultrasonic C-scanning techniques are very effective to determine the extent of healing in the final stages of the repair process. A quasi-linear relation was observed between the delaminated area measured with ultrasonic C-scan and the compressive failure strength in destructive testing. This correlation shows the beneficial effect on the compression strength of the delaminated area reduction by on-demand healing., Novel Aerospace Materials

We report the development of an intrinsic healing glass fibre reinforced polymer (GFRP) composite based on a disulphide-containing organic-inorganic thermoset matrix. Thermomechanical experiments showed that the newly developed matrix has a combination of a Young's modulus value in the range of (800–1200 MPa), the ability to multiple thermally induced healing delamination (70–85 °C), and processability by conventional vacuum infusion process that is not yet reported in literature. The composite mechanical properties and the extent of healing were determined by flexural, fracture and low-velocity impact testing. Small sized (cm2) damage, by increasing the healing pressure provided the location of the primary damage is concentrated within the matrix phase. The polymer matrix composite introduced here represents a significant step forward from the often mechanically inferior intrinsically self-healing composites towards structural self-healing composites., Novel Aerospace Materials

Novel Aerospace Materials

We report the development of an intrinsic healing glass fibre reinforced polymer (GFRP) composite based on a disulphide-containing organic-inorganic thermoset matrix. Thermomechanical experiments showed that the newly developed matrix has a combination of a Young's modulus value in the range of (800–1200 MPa), the ability to multiple thermally induced healing delamination (70–85 °C), and processability by conventional vacuum infusion process that is not yet reported in literature. The composite mechanical properties and the extent of healing were determined by flexural, fracture and low-velocity impact testing. Small sized (cm2) damage, by increasing the healing pressure provided the location of the primary damage is concentrated within the matrix phase. The polymer matrix composite introduced here represents a significant step forward from the often mechanically inferior intrinsically self-healing composites towards structural self-healing composites., Novel Aerospace Materials

This article presents development of a novel self-healing technology for asphalt pavements, where asphalt binder rejuvenator is encapsulated within the compartmented alginate fibres. The key objective of the study was to optimise the compartmented alginate fibre design, i.e., maximising amount of rejuvenator encapsulated within the fibre. The results demonstrate that optimum rejuvenator content in the alginate fibre is of 70:30 rejuvenator/alginate ratio. The fibres are of sufficient thermal and mechanical strength to survive harsh asphalt mixing and compaction processes. Furthermore, results illustrate that zeer open asfalt beton (ZOAB) asphalt mix containing 5% of 70:30 rejuvenator/alginate ratio compartmented alginate fibres has higher strength, stiffness and better healing properties in comparison to the control asphalt mix, i.e., mix without fibres, and mix containing fibres with lower rejuvenator content. These results show that compartmented alginate fibres encapsulating bitumen rejuvenator present a promising new approach for the development of self-healing asphalt pavement systems., Materials and Environment, Novel Aerospace Materials

The macroscopic interfacial healing behaviour in a series of urea-urethane networks as function of the hydrogen bonds and disulphides content is presented. The polymers were prepared with different crosslinking densities but with the same amount of dynamic covalent bonds (disulphide linkages). Tensile and fracture measurements were adopted to evaluate the degree of recovery of the mechanical properties after damage. Healing kinetics and healing efficiencies were quantitatively determined as a function of network composition, healing temperature and contact time. Finally, the recovery of mechanical properties was correlated with the viscoelastic response of the networks through rheological measurements and time-temperature superposition principle (TTS). The application of the TTS approach on both fracture healing and DMTA and subsequent mathematical descriptive model led to a better understanding of the influence of polymer architecture and that of the amount of reversible groups on the healing process., Novel Aerospace Materials, Structural Integrity & Composites

A comparative study is performed on the monitoring of delamination healing in CFRP-ionomer sandwich composites by non-destructive techniques and destructive compression testing. Artificial delaminations of various areal dimensions and nature were introduced during production of the composites. The extent of the delamination and the healing thereof was monitored in both air and water-coupled ultrasonic C-scan experiments as well as by the frequency shift of the local defect resonance (LDR). It is shown that the LDR approach can be used to detect the early stage healing of the delaminations while ultrasonic C-scanning techniques are very effective to determine the extent of healing in the final stages of the repair process. A quasi-linear relation was observed between the delaminated area measured with ultrasonic C-scan and the compressive failure strength in destructive testing. This correlation shows the beneficial effect on the compression strength of the delaminated area reduction by on-demand healing., Novel Aerospace Materials

The main aim of this work is to study the respective contribution of the hard and soft blocks of a metal-ligand containing block copolymer to the self-healing behavior. To this aim, different block copolymers containing terpyridine were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization. These block copolymers consisted of polystyrene as the hard block, n-butyl acrylate (BA) as soft block and terpyridine units as the ligand moiety placed at different locations in the soft block. These block copolymers were complexed with manganese(II) chloride to introduce transient crosslinks and, thus, self-healing behavior. Homopolymers with the hard and soft block only were also synthesized and tested. A quasi-irreversible crosslinking, i.e. by using nickel(II) nitrate, was performed in order to study the dynamics of the permanently (strongly) crosslinked network. Rheological master curves were generated enabling the determination of the terminal flow in these networks and the reversibility of the supramolecular interactions. Additionally, the macroscopic scratch healing behavior and the molecular mobility of the polymer chains in these supramolecular networks were investigated. A kinetic study of the scratch healing was performed to determine the similarities in temperature dependence for rheological relaxations and macroscopic scratch healing. In our previous work, we have explored the effect of strength of the reversible metal-ligand interaction and the effect of changing the ratio of hard to soft block. This work goes further in separating the individual contributions of the hard and soft blocks as well as the reversible interactions and to reveal their relative importance in the complex phenomenon of scratch healing., Novel Aerospace Materials