Corrosion of refractories and ceramic materials · Outline • Introduction, materials,...
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Corrosion of refractories and ceramic materials
Agersted, Karsten
Publication date:2012
Link back to DTU Orbit
Citation (APA):Agersted, K. (Author). (2012). Corrosion of refractories and ceramic materials. Sound/Visual production (digital)
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Co osionCorrosion
of refractories and ceramic materials of refractories and ceramic materials
Karsten [email protected]
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Outline
• Introduction, materials, fundamentals and share of experience
• Ever fascinating corrosion in glass furnaces
• Corrosion in gassification furnaces
• Aqueous corrosion of technical ceramics
• Degradation of zirconia electrolytes in solid oxide cells• Degradation of zirconia electrolytes in solid oxide cells
DTU Energy Conversion, Technical University of Denmark2 7 May 2012
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DTU Energy Conversion, Technical University of Denmark3 7 May 2012
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AcidityyLewis acid-base; electron pair acceptor-donor
Acid Neutral
Gas NOx SO3 SO2 CO2 BOx VOxGas x 3 2 2 x x
Solid SiO2 TiO2 ZrO2 Fe2O3 Cr2O3 Al2O3
Neutral Base
Gas VOx Na K
Solid Al2O3 FeO NiO MnO MgO CaO Na2O K2O
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Refractory groups
• Ceramic bondedSome have glassy grain boundaries, some have notSome are very porous, some are notSome are “basic” some are “acidic” some are “neutral”Some are “basic”, some are “acidic”, some are “neutral”
• Chemically bonded Often MgCl2 and MgSO4 bonded magnesite or phosphate bonded high-Often MgCl2 and MgSO4 bonded magnesite or phosphate bonded highalumina
• Carbon bondedOften Magnesite, Magnesia, Alumina or Zircon based
• FusedOft M llit Al i Ch it d Zi i b dOften Mullite, Alumina, Chrome-magnesite and Zirconia based
• Monolittic; stamping, gunning, groutingOften a combination of cement-bonding or phosphate bonding with pre-Often a combination of cement bonding or phosphate bonding with prefiring
• Fibrous
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Often resin- or phosphate-bonded high-temperature fibres, eg. alumina.
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Binder types in refractories
• Cements – High alumina cements; AH, AH3, C3AH6, C2AH8, CAH10Magnesia cements; MgCl2 and MgSO4
• Phosphates – polyphosphates, Hn+2PnO3n+1, Aluminium phosphate, MAP, Al(H2PO4)3
S di h h t “N C PO ” M (H PO ) > M P OSodium phosphate, “NaCaPO4” w. Mg(H2PO4)2 > MgP2O7Aluminium chloro phosphate, APCH, Al(HPO4)Cl:4H2O
• Polymeric silicates; Na SiO Si(OEt) • Polymeric silicates; Na2SiO3, Si(OEt)
• Carbon and tar
• Resins; Phenol- and fural-based resins
• Other; Clay, Boric acid, Boehmite (Rho-alumina)• Other; Clay, Boric acid, Boehmite (Rho alumina)
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Refractory materials
Magnesite (>60% MgO) Steel furnaces
Magnesia-carbon High wear resistance in steel industry
Chrome-magnesite Wall lining in Siemens-Martin steel furnaces
Magnesia-alumina Cement furnace linings, crucible linings for steel
D l it (C M )(CO ) Sl i t t li iDolomite (CaMg)(CO3) Slag resistant lining
Forsterite (2MgO-SiO2) Furnace lining
Chamotte Cheap lining medium temperature resistance Chamotte Cheap lining, medium temperature resistance, alkali
Graphite-chamotte Crucibles for metal processing (>2000y)
High-alumina (>45%Al) Versatile, higher slag resistance
Alumina-carbon Used in contact with liquid metals
Sili t F li i hi h h i l t th t HTSilicate Furnace linings, high mechanical strength at HT
Zirconia Glass furnaces, tubings for metal industry, saggers
Sili C bid Kil f it l i i i d t i i t
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Silicon Carbide Kiln furniture, aluminium industry, incinerators
Silicon nitride Linings in aluminium production
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Never look only at the overall chemical composition
Al f bi d hAlways focus on binder phases
Material composition: Material composition: 15% A, 80% B, 5% C
Binder phase composition: 20% A, 60% B, 20% C
Given that all C is in the binder phase, melt composition is: 40% A 20% B 40% C t 40% A, 20% B, 40% C at operating temperature of 1500oC
All C is dissolved => liq. Phase ~50% of binder and 12.5% of the entire material
Will this material then be mechanically stable at 1500oC?
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Will this material then be mechanically stable at 1500 C?
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Selected “classics”
• Clay bonded SiC looses strength in reducing atmospheres
• SiC is oxidised in oxidising atmospheres
• Bursting seen in Chrome-magnesite materials on changing pO2 (Fe3+ Fe2+)
• Reduction of free SiO2 in chamotte materials, when the atmosphere contains hydrogen
• Volume expansion on Si-Al reactions with K from the furnace atmosphere
• Sulphur decreases oxide-melt surface tension, hence facilitate penetration
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facilitate penetration
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Refractories in a glass furnace
Mayne Island Glass Foundryhtt // i l d l /170lbi t d i f hthttp://www.mayneislandglass.com/170lbinvestedsicfurnace.htm
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Refractories in a glass furnace
MgO:Al2O3
Fused ZrOFused ZrO2(Cr,Al)2O3:ZrO2
Al2O3:ZrO2:SiO2
Al2O3 (MgO)
2 3 2 2(BACOR)
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Al2O3 (MgO)
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Corrosion in a production furnace for container glass
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Insulating boards (Ca-Silicate and Vermiculite)M l i l ti b i k Diatomite or kieselgur
80 to 90% silica, traces of clay minerals ~3% alumina and ~1% iron oxide.
Moler insulating bricks
Are relatively cheap and robust insulating t i l f idi b h i
Vermiculite is a group of hydrated laminar minerals which
materials - of acidic behaviour.
hydrated laminar minerals which are aluminium-iron-magnesium silicates, resembling mica in appearance. They expand 20 30 times their They expand 20-30 times their volume, when heated.
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Two “classical” issuesQuite often seen in wood stoves
Overheating, eg. by burning coal or polymers, destroys the oven lining. Vermiculite t > 1100°CVermiculite, t > 1100 C.
Carbon deposition inside the pores of the refractory grows and causes spallation refractory grows and causes spallation. Iron Oxide even catalyses the carbon formation from CO, which is formed when oxygen to fuel ratio is low.
On longer exposure to reduced air to fuel ratio carbon has filled the pores of the ratio, carbon has filled the pores of the flexible Vermiculite, hence increased the overall heat transfer. The picture shows also that the oxygen potential has been low enough to partly reduce the vermiculite enough to partly reduce the vermiculite material on the cold side – the pale colour.
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New Challenges for Refractories with Alternate Fuels
60
Sewage WasteSewage Waste
40
50
mpt
ion
[%] Municipal WasteMunicipal Waste
AnimalAnimalMeat / Bone / FatMeat / Bone / Fat
ZincZinc
Sewage WasteSewage Waste
30
40
c Fu
el C
onsu
m
Pulp / Paper / CardboardPulp / Paper / Cardboard
PlasticPlastic
PhosphatePhosphate
20
lativ
e Sp
ecifi
c
Other Industrial Other Industrial WasteWaste
Chlorine / SulphateChlorine / SulphateChlorineChlorine
10
Re
TyresTyres
Waste OilWaste OilSolventsSolvents
Sulphur / ZincSulphur / Zinc
Chlorine / FluorineChlorine / Fluorine
01996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
Year
pp
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Distribution of thermal energy consumption from alternate fuels in GermanyAdam A. Wajdowicz, Magnesita Refratarios
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Corrosion issues in a gasifier furnace lining
C + H2O (gas) + O2 → CO + H2 + CO2 + by-products (g, s, l)(H2S, CH4, NH3, HCN, K, Na, Ca, Si, . . . )
Oxygen800-1275⁰C, 1-60 bar, slag & H2S
Products (syngas)COH2
GasClean-Up
Before
C-source
By-productsH2S CO2Sl (M id )
BeforeProduct
UseWater
Slag (Me-oxides)
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Ref: Ronald W. Breault, National Energy Technology Laboratory, DOE
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Type and abundance of “by products” strongly depends on the carbon source, eg. wood straw industrial waste etc as well
Conventional refractory after
rotary slag testing
wood, straw, industrial waste etc., as well as the gasification temperature
Alkali-attacks (Na, K) are most abundant and severe
All silicate-based materials and binder phases are severely attacked in such applications.
Alkali attacks runs through a combination of chemical reaction and pore penetration leading to spallation.
High Chrome-alumina bricks (neutral acidity) have shown acceptable service life for coal and wood gasification at high temperature (1250-1575⁰C) good sulphur resistance.
Phosphate modified high-chrome
oxide refractory material
Fused and fused cast magnesia and magnesia-spinel bricks have shown good slag resistance in gasification at moderate and moderately high temperatures (600-1000⁰C) of black liqueur.
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material
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Corrosion of SiC bearings in aqueous environment
Run at 200ºC for 20 hr –UPPER: Conventional SiC-materialLOWER: SiC sintered at optimised conditionsconditions
SiC plain bearing after 500 hr in demineralised water at 60ºC. Service life time: 1400-6500 hr
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Degradation of stabilised zirconia electrolytes, when used in electrolysis cells under high current load (> ca. 1.3 A/cm2@ 850°C)y g ( )
• Oxygen electrodes degenerate
on SOE-cells during electrolysis
at high current densities due to
a high oxygen potential that
builds up below the YSZ-builds up below the YSZ
surface, and at grain
boundaries.
• Higher cation or hole diffusion
may alleviate this
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Driving force for cation and hole migration
π
(π‐φπOCV SOFC SOEC
(π‐φ)O
CV
φ
(π‐φ)O
CV
π
φ)O
CV+iR
φφ V‐iRφiR ‐iR
∏ = electromotive potential = (μe-/F) - provides the driving force for electron(hole) migration(hole) migrationΦ = Galvani potential = (i/σ) – provides driving force for migration of oxide ions and the counter migration of cations.
T Jacobsen & M Mogensen (2008):
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T. Jacobsen & M. Mogensen (2008):
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SOEC at high current density
2ho +Oox ―› ½O2 + Vo
’’
h°O2-
Mn2,3+(π‐φ) V πSOEC
pO2 Bar
YSZOCV
SOFC
0
1e‐5
1
LS
M-Y
Cath
o
LSMSOFC 1e
1e‐10
YS
Z
od
e
PO2
Oxygen gas PO2
higher
1e‐15‐1
Oxygen gas higher
Grain boundaries:high cation (Mn) diffusivity
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• high cation (Mn) diffusivity• high hole conductivity Dr. C. Chatzichristodoulou
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A potential solution
YSZ CGO LSCNi-YSZ
Layer with higherelectron conductivity
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electron conductivity
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CONCLUSIONS / Recommendations
• Seek information on the system, characterise if necessary
• Get information on the microstructure of the refractories
• Seek information with producers and similar applications
• Slag penetration through open porosity and pore sizes • Slag penetration, through open porosity and pore sizes, are important issues
• Warm water may be an aggressive medium
• Corrosion is often based on redox-, acid-base and solubility reactionssolubility reactions
• Ceramics with mixed conductivity adds electrochemistry
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y yhereto
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Thank you for your attention
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