Workshop on Glass and Glass-Ceramics
OVERVIEW OF RESEARCH ACTIVITIES / GLASS AND GLASS -CERAMICS FOR ADVANCED APPLICATION
Dr. François O. MÉAR Dr. Grégory TRICOT, Dr. Laurent DELEVOYE, Dr. Julien TREBOSC, Dr. Frédérique POURPOINT, Prof. Olivier LAFON, Prof. Lionel MONTAGNE, Prof. Em. Jean-Paul AMOUREUX
Unité de Catalyse et de Chimie du Solide - UMR CNRS 8181 Université Lille Nord de France 59655 Villeneuve d’Ascq Cedex – France http://uccs.univ-lille1.fr UNIVERSITY OF SCIENCE AND TECHNOLOGY OF LILLE
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⇒ 20 000 students (First University after Paris for the number of degrees awarded)
⇒ 39 laboratories (30 supported by CNRS) → 1000 permanent researchers
Workshop on Glass and Glass-Ceramics 2 CATALYSIS AND SOLID STATE CHEMISTRY UNIT
Director: Prof. Lionel Montagne Deputy Director: Prof. Franck Dumeignil
3 Departments 13 research groups 125 permanent staff 70 PhD students
Research projects: Energy and Sustainable development
Workshop on Glass and Glass-Ceramics 3 CATALYSIS AND SOLID STATE CHEMISTRY UNIT
3 DEPARTMENTS HETEROGENEOUS SOLID-STATE MOLECULAR CHEMICAL CATALYSIS CHEMISTRY CATALYSIS
Workshop on Glass and Glass-Ceramics 4 CATALYSIS AND SOLID STATE CHEMISTRY UNIT
3 DEPARTMENTS HETEROGENEOUS SOLID-STATE MOLECULAR CHEMICAL CATALYSIS CHEMISTRY CATALYSIS
ENERGY SYNTHESIS AND STRUCTURE ENANTIOSELECTIVE OF SMART OXYDES PHASES CATALYSIS
ENVIRONNEMENT OXYGEN CONDUCTING VEGETAL CHEMISTRY AND MATERIALS CATALYSIS
BIOMASS VALORISATION SOLID-STATE CHEMISTRY OF SUPRAMOLECULAR NUCLEAR MATERIALS CATALYSIS
MODELISATION & GLASSES AND SOLID-STATE POLYMERISATION SPECTROSCOPY NMR CATALYSIS
NANOMATERIALS & PHOTONICS
Workshop on Glass and Glass-Ceramics 4 CATALYSIS AND SOLID STATE CHEMISTRY UNIT
3 DEPARTMENTS HETEROGENEOUS SOLID-STATE MOLECULAR CHEMICAL CATALYSIS CHEMISTRY CATALYSIS
ENERGY SYNTHESIS AND STRUCTURE ENANTIOSELECTIVE OF SMART OXYDES PHASES CATALYSIS
ENVIRONNEMENT OXYGEN CONDUCTING VEGETAL CHEMISTRY AND MATERIALS CATALYSIS
BIOMASS VALORISATION SOLID-STATE CHEMISTRY OF SUPRAMOLECULAR NUCLEAR MATERIALS CATALYSIS
MODELISATION & GLASSES AND SOLID-STATE POLYMERISATION SPECTROSCOPY NMR CATALYSIS
NANOMATERIALS & PHOTONICS
Workshop on Glass and Glass-Ceramics 4 PROJECTS : SUSTAINABLE DEVELOPMENT
⇒ BIOMASS ß Catalytic processes ß Bioraffinery (Eurobioref FP7 project) ⇒ ATMOSPHERIC POLLUTANTS ß Catalytic remediation ß Postcombustion, NOx traps ⇒ GREEN CHEMISTRY ß Supramolecular catalysis ß Asymmetric catalysed syntheses ß Catalytic vegetal chemistry ⇒ LIGHTER AERONAUTIC MATERIALS ß Antioxidation of carbon brakes ß Enameling of SiC exhaust parts
Workshop on Glass and Glass-Ceramics 5 PROJECTS : METHODOLOGIES
⇒ SYNTHESES ß Mesostructured catalysts ß Chiral molecules ß Smart oxides ß Ferroelectric thin layers
⇒ HP HP MODELISATIONS excitati1 convers2 on ion t2 S S observati ß Magnetic properties t P P 1 π + π on + 1 1 / 2 2 ß Reaction mechanism 0 0 - -1 ß NMR parameters - 1 1 - ⇒ CHARACTERISATIONS ß Solid-state NMR ß Crystallography ß Operando
-10-15 -20 -25 -30 -35
Workshop on Glass and Glass-Ceramics 6 INTERNATIONAL COLLABORATIONS
Workshop on Glass and Glass-Ceramics 7 SOLID STATE CHEMISTRY DEPARTMENT
Supervisor : Prof. Rose-Noelle VANNIER
5 research groups 45 permanent staff 25 PhD students
SYNTHESIS AND STRUCTURE OF SMART OXYDES PHASES Research activities → Solid-state chemistry for the synthesis and characterization of OXYGEN CONDUCTING MATERIALS materials for energy applications → Synthesis of mixed valence compounds for magnetic applications SOLID-STATE CHEMISTRY → OF NUCLEAR MATERIALS Synthesis of thin layer ferroelectric compounds - characterization with local AFM probes GLASSES AND → Strong expertise in crystallography, electronic microscopy and SOLID-STATE NMR solid-state NMR NANOMATERIALS & PHOTONICS Workshop on Glass and Glass-Ceramics 8 SOLID STATE CHEMISTRY DEPARTMENT
SYNTHESIS AND STRUCTURE OF SMART OXYDES PHASES
OXYGEN CONDUCTING MATERIALS
SOLID-STATE CHEMISTRY OF NUCLEAR MATERIALS
GLASSES AND SOLID-STATE NMR
NANOMATERIALS & PHOTONICS Workshop on Glass and Glass-Ceramics 9 GLASSES AND SOLID -STATE NMR APPLICATIONS : E NERGY
⇒ FUELS ß Removal of sulfur from gasoil (Total, IFP) ß New fuels from biomass ß Fisher-Trospch synthesis ⇒ NUCLEAR ß Solid-state Chemistry of new nuclear fuels and nuclear processes ß Vitrification of special nuclear wastes ⇒ HYDROGEN ß Synthesis of electrochemical active components ß Oxygen conductivity in ceramic electrolytes ß Self-healing Glass seals
Workshop on Glass and Glass-Ceramics 10 GLASSES AND SOLID -STATE NMR
Supervisor : Prof. Lionel MONTAGNE
8 permanent staff 1 Post-doc 10 PhD students
SYNTHESIS AND STRUCTURE OF SMART OXYDES PHASES
OXYGEN CONDUCTING MATERIALS
SOLID-STATE CHEMISTRY OF NUCLEAR MATERIALS
GLASSES AND SOLID-STATE NMR
NANOMATERIALS & PHOTONICS Workshop on Glass and Glass-Ceramics 1 1 GLASSES AND SOLID -STATE NMR 1- GLASS FORMULATION AND PREPARATION
Na 2O 1 0 0 0
7 5 5 2
5 0 0 5
F A E 2 5 5 7 B C D G
0 0 0 1
B2O3 0 25 50 75 100 SiO 2
Workshop on Glass and Glass-Ceramics 12 GLASSES AND SOLID -STATE NMR 2- ADVANCED STRUCTURAL CHARACTERIZATION WITH SS -NMR
Workshop on Glass and Glass-Ceramics 13 GLASSES AND SOLID -STATE NMR 3- MEASURING GLASS PROPERTIES
→ Glass transition temperature → Dilatometric softening temperature → Coefficient thermal expansion → Viscosity → Crystallisation/phase separation phenomena: SEM-TEM → Hot-stage microscopy: viscosity points, sintering and wettability behavior → In-situ XRD (HT and H 2-H2O atm)
Workshop on Glass and Glass-Ceramics 14 GLASSES AND SOLID -STATE NMR 4- FROM STRUCTURE TO PROPERTIES
Workshop on Glass and Glass-Ceramics 15 GLASSES AND SOLID -STATE NMR PHOSPHATES FOR WASTE IMMOBILIZATION
⇒ Phosphate based process for the vitrification of fly ashes with high- heavy-metal chlorides ADEME (environment committee funding) x2 PhD thesis (2000) ⇒ Phosphate glasses for nuclear wastes with high sulfate content CEA (Atomic Energy Commission) – CNRS GNR MATINEX (2007-10) ⇒ Phosphate glasses for radioactive immobilization CEA PhD thesis T. Lemesle (2010-13)
Workshop on Glass and Glass-Ceramics 16 JAPANESE WORKS : I ODINE PHOSPHATE GLASSES
⇒ Glass matrice: 3AgI – Ag 4P2O7 ß Pourvoyeur : AgI (Tfusion =558 °C) ß Glass : TElaboration =350-450 °C ß Weight loss: 0.1 % ß Incorporation : 33 % wt (1.65 % vol) ⇒ Chemical durability evaluated by static test (test MCC1) ß Static (pure water without replacement) -1 ß S/V = 0.1 cm (S : Surface, V : leaching solution volume) pure water T=35 °C ß Layer of AgI created by precipitation on the surface Glass matrix Diffuse Bulk -2 -1 ß Leaching : 0.145 g.m .d (14 days) 3AgI-Ag 4-P2O7 layer sol. Initial state ß Ag + Glass transition temperature (Tg) : 55 °C Ag P O 4 2 7 P O 4- Incongruent 2 7 ⇒ Standard fixed dissolution 3AgI
ß Tg ≈200 °C et Incorporation> 0.6% vol Transitional AgI + ß -2 -1 Ag Vinitial < 10 g.m .d à 90-100 °C 4- state Ag 4P2O7 P2O7 3AgI Ag +, I - Cross linking agent: Al 2O3 or Fe 2O3 Steady state AgI + 4- Ag 4P2O7 Ag , P 2O7 Sakuragi T. et al. « Immobilization of radioactive iodine using AgI vitrification technique for + - the TRU wastes disposal: Evaluation of leaching and surface properties » Materials research Congruent 3AgI Ag , I society symposium proceedings 1107 (2008) 279-285 dissolution
Workshop on Glass and Glass-Ceramics AgI layer Leaching Dissolution [Sakuragi et al., MRS, 2007] GLASS SYSTEM: Ag 2O-(1-x)P 2O5-Al 2O3-xB 2O3-AgI
Ag/P=1 AgPO : AgPO + x +Al xO Al O P O 3 3 2 3 2 3 2 5 Ag P O + x Al O Ag/P=1.665 3: Ag10 5P3O210 3+ x Al 2O3 0.00 1.0 Ag P O + x Al O Ag/P=2 : 4Ag2 4P7 2O7 +2 x 3Al 2O3 Ag PO Ag/P=3 :3 Ag 43PO 4 0.8 0.25 Variation
0.6 ß Ag/P ratio
0.50 ß O/P ratio ß Al/P ratio 0.4
0.75 Substitution 0.2 ß Al 2O3 for P 2O5 and Ag 2O ß B2O3 for P 2O5 1.00 0.0 Al O Ag O 2 3 0.00 0.25 0.50 0.75 1.002
7% mol: Al 2O3 incorporation limit
Addition of 1% vol iodine (30% mol AgI, 20%wt iodine)
Workshop on Glass and Glass-Ceramics VARIATION OF TG AS A FUNCTION OF IODINE CONTENT IN
THE SYSTEM: Ag 2O-(1-x)P 2O5-Al 2O3-xB 2O3-AgI
⇒ An increase in the AgI amount 260
leads to a decrease of Tg 240
220 AgI-AgPO3-3Al ⇒ AgI-Ag5P3O10-3Al For AgI-bearing glasses, impact on AgI-Ag4P2O7-3Al 200 AgI-AgPO3-3Al-5B the Tg is more important for glasses with boron substituted for 180 Tg (Tg C) a small amount of phosphate and 160 having a low Ag/P ratio 140
⇒ 120 No more Tg variations are observed even with modified Ag/P ratios at 100 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 nearly 1% of iodine content by % vol of iodine volume
Workshop on Glass and Glass-Ceramics GLASSES AND SOLID -STATE NMR PHOSPHATES FOR AERONAUTIC APPLICATIONS
⇒ Alumino-phosphates as antioxydation coatings of C/C composites Snecma PhD thesis E. Creton (2006-09) Snecma PhD thesis A. Gatoux (2010-13) ⇒ Formulation of cosmetic enamels Snecma Post-doc S. Perez (2009-11)
⇒ Low Tg durable glasses : investigation of phosphate glass network through advanced NMR methods BDI PhD thesis P. Rajbandhari (2010-13)
Workshop on Glass and Glass-Ceramics 17 GLASSES AND SOLID -STATE NMR DESIGN OF ADVANCED NMR ANALYSES
⇒ NMR methods for quadrupolar nuclei Bruker PhD thesis B. Hu PhD (2006-09) & Q. Wang (2007-10) ⇒ Ab initio calc of 17 O NMR parameters MRT PhD thesis P. Vasconcelos (2007-10) ⇒ 17 O NMR of Hydration of phosphate glasses PhD thesis N. Forler (2008-11) ⇒ High-field NMR of low gamma nuclei ⇒ DNP-NMR applied to inorganic materials ANR PhD thesis (2013-16)
Workshop on Glass and Glass-Ceramics 18 GLASSES AND SOLID -STATE NMR SEALING GLASSES FOR SOFC
⇒ Sealing of BiMeVOx to Stainless steel -6 -1 ß CTE#16-17.10 K
ß Bi 2O3 highly reactive ß Formulation of Bi 2O3-V2O5-P2O5 glass ⇒ P2O5-doped LZS, BAS, BCAS glass-ceramics ß G.P. Kothyial (BARC, Mumbai) CEFIPRA (2009-2012) ß NMR study of glass-ceramics ⇒ Self healing glasses ß Soft seals : intrinsic healed glasses (CEA collaboration) ß Rigid seals: extrinsic healed glasses & glass ceramics LZS Glass ceramics SS 321-LZSGC MRT PhD thesis D. Coillot (2007-10) DGA PhD thesis S. Castanié (2010-13)
Cu-LZSGC
Workshop on Glass and Glass-Ceramics 19 SEALING REMAINS A KEY POINT FOR LONG -TERM USE OF SOFC : CLASSIFICATION OF DEGRADATION MECHANISMS Degradation of components Design/System specific degradation
‹ Degradation of single cell ‹ Formation of hot-spots ‹ Degradation of sealing ‹ Inhomogeneous fuel gas distribution / ‹ Oxidation of interconnects utilization ‹ Degradation of contact resistances ‹ Soot formation ‹ Interaction between ‹Degradation due to unfavorable stack - Glass / interconnect integration into system - Interconnect / cell ‹Degradation due to unfavorable stack- - Contact layer / interconnect preload (especially for IC-cassettes from - Contact layer / cell pressed ferritic steel) Key points: - long term chemical stability - stability against crystallization, control of phase formation - mechanical stability (prevent crack formation) Self-healing is proposed as a solution to decrease gas leaks due to cracks Workshop on Glass and Glass-Ceramics RELATION SELF -HEALING ⇔ GLASS SEALANT
Workshop on Glass and Glass-Ceramics NON -AUTONOMIC SELF -HEALING EXAMPLE -GLASS SEALANT
Increasing temperature in air
From R.N. Singh, Appl. Ceram. Techno. 2007
disappearance of damage due to the flow of the glass phase after heating at high operating temperature
Workshop on Glass and Glass-Ceramics AUTONOMIC SELF -HEALING
EXAMPLE -CERAMIC COMPOSITE : HEALING AGENT ADDITION (SIC, B 4C …)
Oxidizing Glassy oxide layer caused by atmosphere oxidation of the surface particles
Glass flowed Particle during into the crack oxidation
Inert active particle enclosed in the ceramic Ceramic matrix matrix
A B C Ceramic Ceramic Ceramic operation during healed break
From S.K. Ghosh, Self Healing Materials: Fundamentals, Design Strategies and Applications, Willey-VCH 2009
Workshop on Glass and Glass-Ceramics OUTLINE
Glass Sealant for SOEC/SOFC
Viscous Seal Rigid Seal
Non-Autonomous Non-Autonomous Autonomous Self-Healing Self-Healing Self-Healing
Workshop on Glass and Glass-Ceramics OUTLINE
Glass Sealant for SOEC/SOFC
Viscous Seal Rigid Seal
Non-Autonomous Non-Autonomous Autonomous Self-Healing Self-Healing Self-Healing
Workshop on Glass and Glass-Ceramics VISCOUS SEALANT FOR SOEC GLASS SELECTION FROM SPECIFICATIONS Requirements → 7.6 TLittleton (η = 10 Poise) = 800˚C 12 → Low viscosity at 900˚C 10 → No crystallization at 800˚C → Limited interactions with other 8 TL (log η = 7,6) components of electrochemical 6
systems ηlog poise / Selection criteria 4 → Tg > 600˚C 2 → 750˚C < TLittleton < 900˚C → TEC > 5 ×10 -6 K-1 0 → 600 800 1000 1200 Limited amount of P 2O5 Temperature/ °C
Workshop on Glass and Glass-Ceramics VISCOUS SEALANT FOR SOEC VSC 3 DEVELOPMENT Requirements → 7.6 TLittleton (η = 10 Poise) = 800˚C → Low viscosity at 900˚C → No crystallization at 800˚C
Objective decrease of thermal characteristics → ZrO 2 substituted by SiO 2 and/or B 2O3
Workshop on Glass and Glass-Ceramics VISCOUS SEALANT FOR SOEC STUDY OF SEAL FORMING AT 900 °C: HSM → Is the viscosity low enough to allow the seal forming at 900˚C ? → Heat treatment : 10h at 900˚C
100 Temperature / °C 1400 Vsc31 Vsc32 90 1200 Vsc33 Vsc34
80 1000 °C/ Temperature
70 800 / % 0
S/S 60 600
50 400
40 200
30 0 0 10000 20000 30000 40000 Time / s ⇒ Seal elaboration: easy at lower viscosity ⇒ Good wettability for Vsc31 and Vsc32 (θ < 90˚) Workshop on Glass and Glass-Ceramics VISCOUS SEALANT FOR SOEC SEAL STABILITY : C ROFER 22APU SUBSTRATE (78.50%Fe-20.00%Cr-0.03%C-0.80%Mn-0.50%Si-0.12%Al-0.50%Cu, wt.%)
Vsc31 ⇒ chromium oxide formation at the interface (1.4 µm)
Vsc32 ⇒ chromium oxide formation at the interface (1.8 µm)
Workshop on Glass and Glass-Ceramics VISCOUS SEALANT FOR SOEC SEAL STABILITY : MACOR SUBSTRATE
(46%SiO 2-17%MgO-16%Al 2O3-10%K 2O-7%B 2O3-4%Fe, wt.%)
Vsc31 ⇒ important diffusion of Mg in glass ( ~20µm), important crystallization
Vsc32 ⇒ diffusion of Mg in glass ( ~10µm), low crystallization
Workshop on Glass and Glass-Ceramics VISCOUS SEALANTS FOR SOEC SELF -HEALING TEST : IN -SITU OBSERVATION BY HT-ESEM
Vsc32 / Air
Workshop on Glass and Glass-Ceramics VISCOUS SEALANTS FOR SOEC SELF -HEALING TEST : IN -SITU OBSERVATION BY HT-ESEM
Vsc32 / H 2O
Workshop on Glass and Glass-Ceramics OUTLINE
Glass Sealant for SOEC/SOFC
Viscous Seal Rigid Seal
Non-Autonomous Non-Autonomous Autonomous Self-Healing Self-Healing Self-Healing
Workshop on Glass and Glass-Ceramics RIGID SEALANT FOR SOFC COMPOSITIONS INVESTIGATED
Effect of P 2O5 in BCABS glass system ⇒ Improve adhesion and reduce BaCrO 4 formation by addition of P 2O5 ⇒ Study the modification on the thermo-physical properties ⇒ Correlate these to structural insights from NMR and XRD
Workshop on Glass and Glass-Ceramics RIGID SEALANT FOR SOFC SINTERING PROPERTIES : HSM
⇒ 4P and 5P show plateau before melting: crystallization ⇒ The first shrinkage temperature does
not change with P 2O5 ⇒ Sealing temperature too high beyond
2 mol.% P 2O5 ⇒ Flow temperature increases with P 2O5
Workshop on Glass and Glass-Ceramics RIGID SEALANT FOR SOFC
EFFECT OF P2O5 ON PHASE EMERGENCE OF BCABS GLASS Sample heat treatment: RT →→→ @100 oC/h →→→ 830 oC (40 min) →→→ @60 oC/h →→→ 800 oC (2h) @60 oC/h →→→ RT
⇒ Increasing P 2O5: BaSiO 3 phases replaced by Ba(Al 2Si 2O8) and Ba 3(PO 4)2 ⇒ This is evident on 31 P NMR
Workshop on Glass and Glass-Ceramics OUTLINE
Glass Sealant for SOEC/SOFC
Viscous Seal Rigid Seal
Non-Autonomous Non-Autonomous Autonomous Self-Healing Self-Healing Self-Healing
Workshop on Glass and Glass-Ceramics SELF -HEALING OF CRACKS IN GLASSY MATERIALS SELF -HEALING PROCESS
Active particle (Vanadium Boride, VB)
Glass matrix
Workshop on Glass and Glass-Ceramics SELF -HEALING OF CRACKS IN GLASSY MATERIALS SELF -HEALING PROCESS
Cracks form in the glassy matrix Active particle (Vanadium Boride, VB)
Glass matrix VB oxidation permitted in the open crack
Workshop on Glass and Glass-Ceramics SELF -HEALING OF CRACKS IN GLASSY MATERIALS OXIDATION CHARACTERIZATION OF ACTIVE PARTICLE : NMR
NMR 51 V NMR 11 B 400MHz 800MHz (15kHz) (30kHz)
Workshop on Glass and Glass-Ceramics SELF -HEALING OF CRACKS IN GLASSY MATERIALS OXIDATION CHARACTERIZATION OF ACTIVE PARTICLE : DTA-TG
→ 2VB + 4O 2 V2O5 + B 2O3 Tsoftening
Workshop on Glass and Glass-Ceramics SELF -HEALING OF CRACKS IN GLASSY MATERIALS SELF -HEALING PROCESS
Cracks form in the glassy matrix Active particle (Vanadium Boride, VB)
Glass matrix VB oxidation permitted in the open crack
Workshop on Glass and Glass-Ceramics SELF -HEALING OF CRACKS IN GLASSY MATERIALS SELF -HEALING PROCESS
Self-healing of the cracks with formation of V 2O5 and Active particle B2O3 from VB oxidation (Vanadium Boride, VB)
Glass matrix
Workshop on Glass and Glass-Ceramics SELF -HEALING OF CRACKS IN GLASSY MATERIALS OXIDATION CHARACTERIZATION OF ACTIVE PARTICLE : KINETIC ANALYSIS
Workshop on Glass and Glass-Ceramics SELF -HEALING OF CRACKS IN GLASSY MATERIALS SELF -HEALING TEST : IN -SITU OBSERVATION BY HT-ESEM AT 700 °C
Workshop on Glass and Glass-Ceramics SELF -HEALING OF CRACKS IN GLASSY MATERIALS SELF -HEALING TEST : IN -SITU OBSERVATION BY HT-ESEM AT 700 °C
Workshop on Glass and Glass-Ceramics EQUIPMENT OVERVIEW AVAILABLE AT UCCS
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Workshop on Glass and Glass-Ceramics 21 EQUIPMENT OVERVIEW AVAILABLE AT UCCS
Workshop on Glass and Glass-Ceramics 22 EQUIPMENT OVERVIEW AVAILABLE AT UCCS
Workshop on Glass and Glass-Ceramics 23 EQUIPMENT OVERVIEW AVAILABLE AT UCCS
Workshop on Glass and Glass-Ceramics 24 EQUIPMENT OVERVIEW AVAILABLE AT UCCS
Workshop on Glass and Glass-Ceramics 25 EQUIPMENT OVERVIEW AVAILABLE AT UCCS
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