TY - JOUR
AU - Montagne,, Lionel
AB - Abstract In situ high-temperature healing of cracks in composites made of glass and vanadium boride (VB) particles was observed using an environmental scanning electron microscope equipped with a high-temperature chamber (HT-ESEM). HT-ESEM is an adequate tool for studying the self-healing property of these materials. The change in crack length as a function of redox atmospheric conditions is reported. No self-healing behaviour was observed under reducing conditions, while a complete and rapid healing of the cracks was measured under oxidizing conditions. HT-ESEM image analyses enabled the monitoring of the healing effect. The self-healing mechanism was identified as a consequence of the VB active particles oxidation and subsequent pouring of fluid oxides into the cracks. These innovative composites offer an interesting potential in the domain of solid oxide fuel cell sealants. self-healing, temperature, composite, environmental scanning electron microscopy (ESEM), solid oxide fuel cell (SOFC) Introduction Since the last two decades, efforts in research and development of smart materials have been increasing rapidly, specifically towards high-performance and small-volume applications. In recent years, it has been realized that an alternative strategy can be followed to make materials effectively stronger and more reliable by damage management, i.e. materials that have a built-in capability to repair the damage incurred during use. Self-healing materials in polymers, metals, ceramics and their composites have attracted broad attention. When damage through a thermal, mechanical or chemical process is formed, the material has the ability to heal and restore its original set of properties [1]. Much of the work in the development of self-healing in composite materials has concentrated in polymer systems [2–9]. However, particular self-healing ceramic composites have also been developed for high-temperature applications [10–16]. The concept of self-healing has been extended to glassy and glass–ceramic materials used as sealant for solid oxide fuel cells (SOFCs). These electrochemical systems enable the production of clean electrical power from the combustion of hydrogen fuel. However, their lifetime is limited by the formation of cracks in the glass seals used to separate the different gas manifolds. The healing effect is obtained by overheating of the system above the seal glass-softening temperature, and surface defects or cracks were found to disappear or self-heal [17–21]. Self-healing can thus be obtained in two ways: extrinsic or intrinsic. Intrinsic self-healing is fully autonomic but requires an external constraint such as temperature increase. On the other hand, extrinsic self-healing involves healing agents encapsulated in the material, and their reactivity is activated by a constraint (mechanical, chemical or thermal) [22]. A new generation of self-healing composites was elaborated by Coillot et al. [22,23] in order to avoid overheating that may induce deformation of the system. Composite seals were produced by adding vanadium boride (VB) particles to a standard seal glass. At high temperature, VB generates the formation of V and B oxides with a low viscosity, susceptibility to flow and ability to heal a crack. It was demonstrated that the healing effect occurs at a temperature below glass softening, thus avoiding the risk of seal deformation. An environmental scanning electron microscope (ESEM), equipped with a heating stage mounted on the specimen stage, is an excellent tool for the in situ and continuous observation of the healing effect. It enables the recording of images of the morphological changes during heat treatment with both high magnification and high focus depth. The experiments can be carried out under different conditions, e.g. different heating rates, different gases, variable pressure, final temperature and soak time, to observe their influence on the studied phenomenon. Some authors have already reported specific studies performed using HT-ESEM. Part of these studies were devoted to the oxidation of metals [24–36], others to sintering [29,37–40], reactivity [41], microstructure modifications [30,42,43], mechanical properties [44–46], crystallization in melts [47,48] or material decomposition studies [49,50]. Furthermore, particular efforts are made to develop new instrumentation [46,51,52] and methods [53,54] in the HT-ESEM field. Several authors [55,56] have demonstrated that insitu HT-ESEM experiments can allow the simulation of pseudo SOFC operating conditions by performing high-temperature redox cycles. Furthermore, a study devoted to the effect of humidity on intrinsic crack healing in glass from in situ investigations demonstrated that ESEM is an adequate tool for the self-healing characterization of glasses [57]. In the present study, the ESEM chamber will be used as a reactor in which the samples to be characterized are introduced. In a SOFC, the cathodic side atmosphere contains mainly air and the anodic side contains both hydrogen and water. In the present study, SOFC conditions are simulated by operating at high temperature under water or air atmosphere. The atmosphere of the cathodic side of the fuel cell is thus simulated by air, whereas the anodic side of the fuel cell is simulated by the steam gas that reproduces reducing conditions. We report the first in situ observation of a high-temperature self-healing process on a glass composite, obtained below the softening temperature [23]. Image sequence recording and subsequent image treatment, associated with ex situ electron microprobe analyses, enabled us to characterize the healing behaviour of a pre-fractured glass–VB particles composite at T = 730°C. Methods The self-healing effect should be independent of the glass composition; we thus used two sealing glass compositions: SG1 and SG2. SG1 with the composition 56.4 wt.% BaO–22.1 wt.% SiO2–5.4 wt.% Al2O3–8.8 wt.% CaO–7.3 wt.% B2O3 and SG2 with the composition 65 wt.% SiO2–20 wt.% ZrO2–10 wt.% Na2O–5 wt.% K2O have been used for the in situ and ex situ observations, respectively. Both glasses were milled into fine powder. The composite obtained from SG1 mixed with 20 vol.% of VB particles (99.5% purity, particle size < 20 µm) was densified at 750°C under argon by spark plasma sintering, while the composite obtained from SG2 mixed with 10 vol.% of VB was densified at 1100°C under argon. The samples were then cut into 5 × 5 × 5 mm3 cubes and polished to 1 µm diamond grains. Vickers indentations were made by means of a microhardness testing apparatus at room temperature. All Vickers indentations were positioned in the same way so that the Vickers-induced radial cracks developed in a reproducible way from one sample to another. The cracks obtained randomly go through the glass matrix and VB grains. In situ ESEM was performed with a field emission gun electron microscope (model FEI QUANTA 200 ESEM FEG) equipped with a 1000°C hot stage. The sample was directly placed in a small ceramic crucible (5 mm inner diameter) covered with platinum paint. Once the specimen was placed in the hot stage, the chamber was evacuated and then filled with adequate gas. The observations were performed under reducing conditions by using H2O vapour or air at high temperature and operating pressure of 450 Pa. Water vapour is produced in the ESEM chamber from a water bath maintained at T = 25°C. In these conditions, the quantity of oxygen solubilized in water is approximately 8 mg.l−1 and the equivalent oxygen pressure in the water vapour is 2.025 × 10−3 Pa [58]. This value corresponds to a low oxygen fugacity and to mild reducing conditions [59]. These conditions ensure the signal amplification yielding to the secondary electron image formation using the specific gaseous secondary electron detector. Micrographs of the initial indent cracks were recorded previously to heating. The heating rate was 30°C.min−1 up to 730°C. The sample was then maintained at this final temperature during the experiment duration. A series of micrographs were taken regularly during the sample heat treatment. Acceleration voltage was 24 kV during the whole experiment. An electron probe microanalyser using wavelength dispersive X-ray spectrometers was used to perform elemental analysis on SG1. The work was carried out on a Cameca SX-100 at 15 kV 15 nA for back-scattered electron images and at 15 kV 40 nA for silicon (Si), boron (B), sodium (Na), vanadium (V) and potassium (K) X-ray mappings. For mappings, a TAP crystal was used to detect the Si and Na Kα X-rays, a LiF crystal for V X-ray, a PC3 for B X-ray and a PET crystal to detect the K X-ray. Samples were embedded into epoxy resin, polished and carbon coated with a Bal-Tec SCD005 sputter coater. In the particular case of the B analyses and mapping, the presence of boron in the PC3 monochromator crystal (made of Mo-B4C layers) can potentially generate a secondary X-ray emission by fluorescence of the monochromator. No particular artefact was observed in the X-ray maps and in the quantitative analyses. This phenomenon can be neglected in the present case because the B concentrations in the samples are high enough and the characteristic B X-ray emission of the sample is higher than the secondary B X-ray emission due to the monochromator. Results and discussions The glass and VB composite used in this study can potentially offer interesting self-healing properties in the 400–750°C temperature range (lower than Tg = 750°C) [22,23]. It has been shown that the healing effect is due to the ability of VB oxidation products to fill cracks formed in the glass in this temperature domain [22]. Crack healing were thus investigated under air and steam, at T = 730°C, in order to simulate the SOFC operating conditions. The heating rates as well as the final temperatures were identical for each experiment. Steam conditions The typical crack morphologies are reported in Fig. 1a and b, corresponding to the beginning of the heat treatment at 730°C and after 110 min heat treatment, respectively. No significant change is observed for both morphologies. The VB particles are not oxidized and the crack is not healed. We thus conclude that, under wet and reducing conditions, the self-healing effect is not obtained. Fig. 1 Open in new tabDownload slide ESEM pictures of SG1-VB composite on which a crack was induced by Vickers indentation. The observation was conducted under mild reducing conditions (450 Pa water vapour atmosphere). (a) Initial morphology of the crack. (b) 110 min heat treatment at T = 730°C. Fig. 1 Open in new tabDownload slide ESEM pictures of SG1-VB composite on which a crack was induced by Vickers indentation. The observation was conducted under mild reducing conditions (450 Pa water vapour atmosphere). (a) Initial morphology of the crack. (b) 110 min heat treatment at T = 730°C. Oxidizing conditions Oxidizing conditions in the ESEM chamber are obtained by using air as the environmental gas. In these conditions, the oxygen pressure is 95 Pa. This corresponds to a relatively oxidizing atmosphere [59]. HT-ESEM pictures of the sample heated at T = 730°C, recorded at different run durations (t = 0, 8, 20, 45, 60 and 75 min), are reported in Fig. 2. From these photomicrographs, the oxidation of the VB particles and the formation of oxidized species are clearly evidenced. Post-experiment EDS analyses performed on the particles indicate that vanadium and boron oxides were formed during heat treatment, as well as an incorporation of some elements initially present in the glass (Ca and Ba). Furthermore, due to the relatively low PO2 and low level of gas renewal in the ESEM chamber, the kinetics of active particle oxidation is probably lowered in comparison with oxidation in an open medium. It was previously shown that VB is oxidized into B2O3 and V2O5, which are already molten at 700°C [23]. Their low viscosity enables the spreading of the reaction products, which begin to fill in the crack. Several vanadium oxides (V2O3, Tflow = 1970°C; VO2, Tflow = 1967°C; and V2O5, Tflow = 690°C [60]) are probably formed successively. Among them, only V2O5 is sufficiently fluid to pour into the cracks with B2O3. Fig. 2 Open in new tabDownload slide Surface morphology modifications and crack healing versus exposure duration under oxidizing conditions (450 Pa air atmosphere). (a) Initial morphology of the Vickers indentation—the magnified view in the inset corresponds to the zone that was observed at 730°C after (b) 8, (c) 20, (d) 45 and (e) 60 min. (f) Total healing of the crack is observed after 58 min heat treatment at T = 730°C. Fig. 2 Open in new tabDownload slide Surface morphology modifications and crack healing versus exposure duration under oxidizing conditions (450 Pa air atmosphere). (a) Initial morphology of the Vickers indentation—the magnified view in the inset corresponds to the zone that was observed at 730°C after (b) 8, (c) 20, (d) 45 and (e) 60 min. (f) Total healing of the crack is observed after 58 min heat treatment at T = 730°C. The series of photomicrographs indicates that the first places where the healing process occurs are in the zones where the active VB particles are oxidized. After the healing process has begun, the cracks can be completely filled relatively rapidly. One way to characterize the healing behaviour of the composite is to determine a so-called ‘healing ratio’ defined as the ratio between the length of the crack that is filled with oxidation products to the initial length of the crack. The filling of the cracks by the VB oxidation products is illustrated by Fig. 3 where the ‘healing ratio’ is reported as a function of heat treatment duration. Three distinct steps can clearly be evidenced. The first one, from 0 to 10 min, corresponds to an incubation period (I) illustrated in Fig. 2a and b. During this period, the oxidation products slowly form, pour onto the crack and begin to fill it from the bottom. After a given run duration (II), the filling of the crack is considered to begin when the oxidation products level have reached the upper part of the crack (Fig. 2c, d and e). The filling process begins simultaneously at several points of the crack and develops up to the collapsing of neighbouring zones. The healing ratio slowly and regularly increases, according to a sigmoid-like curve, to reach the value of 1. When this value is reached, the crack is completely filled (III). When looking at the zone that corresponds to the initial Vickers indent (Fig. 2f), the volume of the indent mark is totally healed. The VB particles that arise at the composite/atmosphere interface are oxidized and the oxidation products have partially reacted with the glass components. Fig. 3 Open in new tabDownload slide ‘Healing ratio’ plotted as a function of heat treatment duration. The healing ratio is defined as the length of healed crack divided by the full length of the crack. Three domains can be distinguished: from 0 to 10 min corresponding to an incubation period (I), from 10 to 58 min where the crack healing occurs up to a ratio of 1 (II), the crack is fully repaired (III). Fig. 3 Open in new tabDownload slide ‘Healing ratio’ plotted as a function of heat treatment duration. The healing ratio is defined as the length of healed crack divided by the full length of the crack. Three domains can be distinguished: from 0 to 10 min corresponding to an incubation period (I), from 10 to 58 min where the crack healing occurs up to a ratio of 1 (II), the crack is fully repaired (III). Complementary ex situ analysis were carried out on the SG2-VB composite at the interface of a crack generated in the sample. X-ray maps of V, B, Ca, Ba and Si were recorded on virgin sample (Fig. 4a) and after 1 h heat treatment at T = 700°C (Fig. 4b). The element maps indicate that the molten products that have filled the crack are rich in V and B (Fig. 4b), yielding a confirmation of the expected healing process. Only the active particles in contact with the oxygen-containing atmosphere along the crack are oxidized and lead to V2O5 and B2O3, while VB particles that remain in the bulk of the samples are unaltered. Moreover, the reaction of VB with the glass element produces a new glass with the composition 35.89 wt.% V2O5–13.56 wt.% B2O3–28.69 wt.% SiO2–7.22 wt.% ZrO2–10.94 wt.% Na2O–3.70 wt.% K2O. This new glass contributes to the crack healing and shows excellent compatibility with the glass matrix. Fig. 4 Open in new tabDownload slide Exsitu electron microprobe (Castaing microprobe) analysis of a fracture sample healed under air at 700°C for 1 h. SEM picture and X-ray element maps (a) before and (b) after heat treatment. Fig. 4 Open in new tabDownload slide Exsitu electron microprobe (Castaing microprobe) analysis of a fracture sample healed under air at 700°C for 1 h. SEM picture and X-ray element maps (a) before and (b) after heat treatment. Concluding remarks The high-temperature crack-healing behaviour of newly designed composites has been clearly demonstrated in this study. The role of the VB active particles in the healing mechanism, through the formation of fluid oxides, is now clearly established. HT-ESEM is an adequate tool for studying such a property. It transforms the SEM into a powerful tool that allows the in situ observation of chemical reactions. In particular, the locations where the first healing features become visible are easily correlated with the beginning of the active particle oxidation. The growth and change in the structure of the active particles, as well as the crack recovery, can also be followed. The versatility of the ESEM allows carrying out in situ reactivity experiments using different gases in the microscope chamber. In the particular case of this study, the behaviour of SG1-VB and SG2-VB composites under reducing or oxidizing environments are completely different. ESEM is thus demonstrated to be an efficient tool for the characterization of sealing material for the SOFC system. The electron probe microanalyser facility in Lille (France) was funded by the European Regional Development Fund. References 1 Li V C , Lim Y M , Chan Y W . Feasibility study of a passive smart self-healing cementitious composite , Compos. B Eng. , 1998 , vol. 29 (pg. 819 - 827 ) Google Scholar Crossref Search ADS WorldCat 2 Dry C . Passive tuneable fibers and matrices , Int. J. Mod. Phys. B , 1992 , vol. 6 (pg. 2763 - 2771 ) Google Scholar Crossref Search ADS WorldCat 3 Bleay S M , Loader C B , Hawyes V J , Humberstone L , Curtis P T . A smart repair system for polymer matrix composites , Compos. Appl. Sci. Manuf. , 2001 , vol. 32 (pg. 1767 - 1776 ) Google Scholar Crossref Search ADS WorldCat 4 Dry C . , Self-repairing reinforced matrix materials , 1997 US005660624 Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 5 Pang J W C , Bond I P . A hollow fibre reinforced polymer composite encompassing self-healing and enhanced damage visibility , Compos. Sci. Technol. , 2005 , vol. 65 (pg. 1791 - 1799 ) Google Scholar Crossref Search ADS WorldCat 6 Brown E N , White S R , Sottos N R . Microcapsule induced toughening in a self-healing polymer composite , J. Mater. Sci. , 2004 , vol. 39 (pg. 1703 - 1710 ) Google Scholar Crossref Search ADS WorldCat 7 Cho S H , White S R , Braun P V . Self-healing polymer coatings , Adv. Mater. , 2009 , vol. 21 (pg. 645 - 649 ) Google Scholar Crossref Search ADS WorldCat 8 White S R , Sottos N R , Geubelle P H , Moore J S , Kessler M R , Sriram S R , Brown E N , Viswanathan S . Autonomic healing of polymer composites , Nature , 2001 , vol. 409 (pg. 794 - 797 ) Google Scholar Crossref Search ADS PubMed WorldCat 9 Chen X , Wudl X , Mal A K , Shen H , Nutt S R . New thermally remendable highly cross-linked polymeric materials , Macromolecules , 2003 , vol. 36 (pg. 1802 - 1807 ) Google Scholar Crossref Search ADS WorldCat 10 Naslain R , Guette A , Rebillat F , Pailler R , Langlais F , Bourrat X . Boron-bearing species in ceramic matrix composites for long-term aerospace applications , J. Solid State Chem. , 2004 , vol. 177 (pg. 449 - 456 ) Google Scholar Crossref Search ADS WorldCat 11 Osada T , Nakao W , Takahashi K , Ando K . Kinetics of self-crack-healing of alumina/silicon carbide composite including oxygen partial pressure effect , J. Am. Ceram. Soc. , 2009 , vol. 92 (pg. 864 - 869 ) Google Scholar Crossref Search ADS WorldCat 12 Quemard L , Rebillat F , Guette A , Tawil H , Louchet-Pouillerie C . Self-healing mechanisms of a SiC fiber reinforced multi-layered ceramic matrix composite in high pressure steam environments , J. Eur. Ceram. Soc. , 2007 , vol. 27 (pg. 2085 - 2094 ) Google Scholar Crossref Search ADS WorldCat 13 Viricelle J P , Goursat P , Bahloul-Hourlier D . Oxidation behaviour of multi-layered ceramic-matrix (SiC)f/C/(SiBC)m , Compos. Sci. Technol. , 2001 , vol. 61 (pg. 607 - 614 ) Google Scholar Crossref Search ADS WorldCat 14 Yang Z H , Jia D C , Zhou Z , Shi P Y , Song C B , Lin L . Oxidation resistance of hot-pressed SiC-BN composites , Ceram. Int. , 2008 , vol. 34 (pg. 317 - 321 ) Google Scholar Crossref Search ADS WorldCat 15 Zhang X , Xu L , Du S , Han W , Han J . Preoxidation and crack-healing behavior of ZrB2-SiC ceramic composite , J. Am. Ceram. Soc. , 2008 , vol. 91 (pg. 4068 - 4073 ) Google Scholar Crossref Search ADS WorldCat 16 Kessler M R , Sottos N R , White S R . Self-healing structural composite materials , Compos. Appl. Sci. Manuf. , 2003 , vol. 34 (pg. 743 - 753 ) Google Scholar Crossref Search ADS WorldCat 17 Govindaraju N , Liu W N , Sun X , Singh P , Singh R N . A modeling study on the thermomechanical behavior of glass-ceramic and self-healing glass seals at elevated temperatures , J. Power Sources , 2009 , vol. 190 (pg. 476 - 484 ) Google Scholar Crossref Search ADS WorldCat 18 Liu W , Sun X , Khaleel M A . Predicting Young's modulus of glass/ceramic sealant for solid oxide fuel cell considering the combined effects of aging, micro-voids and self-healing , J. Power Sources , 2008 , vol. 185 (pg. 1193 - 1200 ) Google Scholar Crossref Search ADS WorldCat 19 Singh N R . Sealing technology for solid oxide fuel cells (SOFC) , Int. J. Appl. Ceram. Tech. , 2007 , vol. 4 (pg. 134 - 144 ) Google Scholar Crossref Search ADS WorldCat 20 Moreira Jorge Jr A , Inoue A , Yavari A R . Surface self-healing of metallic glasses in the super-cooled liquid region △T = Tx − Tg , Rev. Adv. Mater. Sci. , 2008 , vol. 18 (pg. 193 - 196 ) OpenURL Placeholder Text WorldCat 21 Deng X , Duquette J , Petric A . Silver–glass composite for high temperature sealing , Int. J. Appl. Ceram. Tech. , 2007 , vol. 4 (pg. 145 - 151 ) Google Scholar Crossref Search ADS WorldCat 22 Coillot D, Méar F O and Montagne L (2009) Composition vitreuse autocicatrisante, procédé de préparation et utilisations. Patent submitted 23 Coillot D , Méar F O , Podor R , Montagne L . Autonomic self-repairing glassy materials , Adv. Funct. Mater. , 2010 Submitted Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 24 Knowles R W and Hardt T A (1997) High temperature specimen stage and detector for an environmental scanning electron microscope. Patent no. WO 97/07526 25 Schmid B , Aas N , Grong Ø , ØDegard R . High-temperature oxidation of nickel and chromium studied with an in-situ environmental scanning electron microscope , Scanning , 2001 , vol. 23 (pg. 255 - 266 ) Google Scholar Crossref Search ADS WorldCat 26 Schmid B , Aas N , Grong Ø , ØDegard R . In situ environmental scanning electron microscope observations of catalytic processes encountered in metal dusting corrosion on iron and nickel , Appl. Catal. A Gen. , 2001 , vol. 215 (pg. 257 - 270 ) Google Scholar Crossref Search ADS WorldCat 27 Schmid B , Aas N , Grong Ø , ØDegard R . High-temperature oxidation of iron and the decay of Wüstite studied with in situ ESEM , Oxid. Met. , 2002 , vol. 57 (pg. 115 - 130 ) Google Scholar Crossref Search ADS WorldCat 28 Oquab D , Monceau D . In-situ SEM study of cavity growth during high temperature oxidation of β-(Ni, Pd)Al , Scr. Mater. , 2001 , vol. 44 (pg. 2741 - 2746 ) Google Scholar Crossref Search ADS WorldCat 29 Srinivasan N S . Dynamic study of changes in structure and morphology during the heating and sintering of iron powder , Powder Technol. , 2002 , vol. 124 (pg. 40 - 44 ) Google Scholar Crossref Search ADS WorldCat 30 Maroni V A , Teplitsky M , Rupich M W . An environmental scanning electron microscope study of the Ag/Bi-2223 composite conductor from 25 to 840°C , Phys. C Supercond. , 1999 , vol. 313 (pg. 169 - 174 ) Google Scholar Crossref Search ADS WorldCat 31 Fischer S , Lemster K , Kaegi R , Kuebler J , Grobéty B . In situ ESEM observation of melting silver and Inconel on an Al2O3 powder bed , J. Electron Microsc. , 2004 , vol. 53 (pg. 393 - 396 ) Google Scholar Crossref Search ADS WorldCat 32 Pirttiaho L , Blakely J . Environmental scanning electron microscope observations of H2S attack on the protective oxide on an Ni–Fe alloy , Scanning , 1996 , vol. 18 (pg. 497 - 499 ) Google Scholar Crossref Search ADS WorldCat 33 Gregori G , Kleebe H J , Siegelin F , Ziegler G . In situ SEM imaging at temperatures as high as 1450°C , J. Electron Microsc. , 2002 , vol. 51 (pg. 347 - 352 ) Google Scholar Crossref Search ADS WorldCat 34 Abolhassani S , Dadras M , Leboeuf M , Gavillet D . In situ study of the oxidation of Zircaloy-4 by ESEM , J. Nucl. Mater. , 2003 , vol. 321 (pg. 70 - 77 ) Google Scholar Crossref Search ADS WorldCat 35 Reichmann A , Poelt P , Brandl C , Chernev B , Wilhelm P . High-temperature corrosion of steel in an ESEM with subsequent scale characterisation by Raman microscopy , Oxid. Met. , 2008 , vol. 70 (pg. 257 - 266 ) Google Scholar Crossref Search ADS WorldCat 36 Jonsson T , Pujilaksono B , Hallström S , Ågren J , Svensson J E , Johansson L G , Halvarsson M . An ESEM in situ investigation of the influence of H2O on iron oxidation at 500°C , Corros. Sci. , 2009 , vol. 51 (pg. 1914 - 1924 ) Google Scholar Crossref Search ADS WorldCat 37 Marzagui H , Cutard T . Characterisation of microstructural evolutions in refractory castables by in situ high temperature ESEM , J. Mater. Process. Tech. , 2004 , vol. 155–156 (pg. 1474 - 1481 ) Google Scholar Crossref Search ADS WorldCat 38 Smith A J , Atkinson H V , Hainsworth S V , Cocks A C F . Use of a micromanipulator at high temperature in an environmental scanning electron microscope to apply force during the sintering of copper particles , Scr. Mater. , 2006 , vol. 55 (pg. 707 - 710 ) Google Scholar Crossref Search ADS WorldCat 39 Sample D R , Brown P W , Dougherty J P . Microstructural evolution of copper thick films observed by environmental scanning electron microscopy , J. Am. Ceram Soc. , 1996 , vol. 79 (pg. 1303 - 1306 ) Google Scholar Crossref Search ADS WorldCat 40 Subramaniam S (2006) In Situ High Temperature Environmental Scanning Electron Microscopic Investigations of Sintering Behavior in Barium Titanate. PhD thesis, University of Cincinnati, Engineering: Materials Science, 194 p 41 Bondioli F , Bonamartini Corradi A , Ferrari A M , Manfredini T . Environmental scanning electron microscopy (ESEM) investigation of the reaction mechanism in praseodymium-doped zircon , J. Am. Ceram. Soc. , 2000 , vol. 83 (pg. 1518 - 1520 ) Google Scholar Crossref Search ADS WorldCat 42 Blanford C F , Carter C B , Stein A . In situ high-temperature electron microscopy of 3DOM cobalt, iron oxide, and nickel , J. Mater. Sci. , 2008 , vol. 43 (pg. 3539 - 3552 ) Google Scholar Crossref Search ADS WorldCat 43 Imaizumi K , Matsuda N , Otsuka M . Coagulation/phase separation process in the silica/inorganic salt systems (1) observation of state transformation , J. Mater. Sci. , 2003 , vol. 38 (pg. 2979 - 2986 ) Google Scholar Crossref Search ADS WorldCat 44 Jacobsson L , Persson C , Melin S . In-situ ESEM study of thermo-mechanical fatigue crack propagation , Mater. Sci. Eng. A , 2008 , vol. 496 (pg. 200 - 208 ) Google Scholar Crossref Search ADS WorldCat 45 Celik E , Hascicek Y S . In situ hot-stage ESEM evaluation of CeO2 buffer layers on Ni tapes for YBCO coated conductors , Mater. Sci. Eng. A , 2002 , vol. 94 (pg. 176 - 180 ) Google Scholar Crossref Search ADS WorldCat 46 Biallas G , Maier H J . In-situ fatigue in an environmental scanning electron microscope—potential and current limitations , Int. J. Fatigue , 2007 , vol. 29 (pg. 1413 - 1425 ) Google Scholar Crossref Search ADS WorldCat 47 Hillers M , Matzen G , Veron E , Dutreilh-Colas M , Douy A . Application of in situ high-temperature techniques to investigate the effect of B2O3 on the crystallization behavior of aluminosilicate E-glass , J. Am. Ceram. Soc. , 2007 , vol. 90 (pg. 720 - 726 ) Google Scholar Crossref Search ADS WorldCat 48 Gualtieri A F , Lassinantti Gualtieri M , Tonelli M . In situ ESEM study of the thermal decomposition of chrysotile asbestos in view of safe recycling of the transformation product , J. Hazard. Mater. , 2008 , vol. 156 (pg. 260 - 266 ) Google Scholar Crossref Search ADS PubMed WorldCat 49 Beattie S D , Sean McGrady G . Hydrogen desorption studies of NaAlH4 and LiAlH4 by in situ heating in an ESEM , Int. J. Hydrogen Energy , 2009 , vol. 34 (pg. 9151 - 9156 ) Google Scholar Crossref Search ADS WorldCat 50 Beattie S D , Langmi H W , Sean McGrady G . In situ thermal desorption of H2 from LiNH2–2LiH monitored by environmental scanning microscopy , Int. J. Hydrogen Energy , 2009 , vol. 34 (pg. 376 - 379 ) Google Scholar Crossref Search ADS WorldCat 51 Atkinson H V, Hainsworth S V, Stevenson T, Samara-Ratna P, Sykes J, Smith A J. GR/S97910/01 Final Report Feasibility Study: High Temperature Micro-Manipulation System for ESEM 52 Samara-Ratna P , Atkinson H V , Stevenson T , Hainsworth S V , Sykes J . Design of a micromanipulation system for high temperature operation in an environmental scanning electron microscope (ESEM) , J. Micromechanics Microengineering , 2007 , vol. 17 (pg. 104 - 114 ) Google Scholar Crossref Search ADS WorldCat 53 Subramaniam S , Roseman R D . Control and optimization of parameters in the ESEM at high temperatures , Microsc. Microanal. , 2005 , vol. 11 (pg. 1514 - 1515 ) Google Scholar Crossref Search ADS WorldCat 54 Wang L , Ji Y , Wei B , Zhang Y , FuJ Xu X , Han X . Charge compensation by in-situ heating for insulating ceramics in scanning electron microscope , Ultramicroscopy , 2009 , vol. 109 (pg. 1326 - 1332 ) Google Scholar Crossref Search ADS PubMed WorldCat 55 Klemenso T , Appel C C , Mogensen M . In situ observations of microstructural changes in SOFC anodes during redox cycling , Electrochem. Solid-State Lett. , 2006 , vol. 9 (pg. 403 - 407 ) Google Scholar Crossref Search ADS WorldCat 56 Nakagawa Y , Yashiro K , Sato K , Kawada T , Mizusaki J . Microstructural changes of Ni/YSZ cermet under repeated redox reaction in environmental scanning electron microscope (ESEM). Solid oxide fuel cells 10 (SOFC-X), parts 1 & 2 book series , ECS Transactions , 2007 , vol. 7 (pg. 1373 - 1380 ) OpenURL Placeholder Text WorldCat 57 Wilson B A , Case E D . Effect of humidity on crack healing in glass from in-situ investigations using an ESEM , J. Mater. Sci. , 1999 , vol. 34 (pg. 247 - 250 ) Google Scholar Crossref Search ADS WorldCat 58 Air solubility in water. http://www.engineeringtoolbox.com/air-solubility-water-d_639.html 59 Khedim H , Podor R , Rapin C , Vilasi M . Redox-control solubility of chromium in soda-silicate melts , J. Am. Ceram. Soc. , 2008 , vol. 91 (pg. 3571 - 3579 ) Google Scholar Crossref Search ADS WorldCat 60 Weast R C , Astle M J . , CRC Handbook of Chemistry and Physics , 1981 Boca Raton, FL CRC Press, Inc. Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC © The Author 2010. Published by Oxford University Press on behalf of Japanese Society of Microscopy. All rights reserved. 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TI - Characterization of self-healing glassy composites by high-temperature environmental scanning electron microscopy (HT-ESEM)
JF - Journal of Electron Microscopy
DO - 10.1093/jmicro/dfq018
DA - 2010-10-01
UR - https://www.deepdyve.com/lp/oxford-university-press/characterization-of-self-healing-glassy-composites-by-high-temperature-cKTWoMk9Fp
SP - 359
EP - 366
VL - 59
IS - 5
DP - DeepDyve
ER -