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Temperature-Programmed Desorption Study of the Reaction of Water and Epitaxial Graphene
on Silicon Carbide KAREN PORTER-DAVIS
CHAMBLEE CHARTER HIGH SCHOOL
STEP-UP PROGRAM 2013
THE ORLANDO GROUP
GEORGIA INSTITUTE OF TECHNOLOGY
Benefits of Nuclear Power -‐Much less greenhouse gases released -‐Produce more electric power for less cost -‐Technology already understood
However….
Plant Vogtle in Waynesboro, GA. Two new reactors will start producing electricity 2016 and 2017. First new reactor built in US in 30 years. (NRC approved 4 to 1 in Feb. 2012) AP1000 reactors with ZIRLO cladding.
Safety and Fuel-Cladding Disaster at Fukushima 1 Nuclear Power Plant in March of 2011 has brought concern over the safety of nuclear power.
The tsunami waves destroyed cooling system and caused the reactors to overheat.
Zircaloy fuel-‐cladding oxidized and produced hydrogen gas. Hydrogen gas led to explosions in reactors. Need for longer-‐lasZng materials for fuel-‐cladding that are able to hold up to loss-‐of-‐cooling accidents (LOCA).
Fuel-Cladding
NUCLEAR FUEL ASSEMBLY Zirconium alloys are used as cladding materialh?p://www.miningweekly.com/arFcle/network-‐advances-‐beneficiaFon-‐and-‐rd-‐2012-‐11-‐02
h?p://crisasantos.com.br/com/nuclear-‐rods-‐melFng
cladding
Fuel-‐cladding is used to separate the radioacZve fuel from the coolant so the neutrons, gamma rays and alpha and beta parZcles that are created during the fission process are not released into the environment.
Fuel-Cladding There are several factors to consider when deciding on the type of Fuel-‐Cladding material but most notably: 1) Transparency to neutrons 2) High Thermal ConducZvity 3) Low Thermal Expansion Coefficient
4) Chemical CompaZbility 5) Mechanical Strength
Current Materials for Fuel-Cladding MeeZng the aforemenZoned requirements Zirconium (Zr) and alloys of Zr (Zircaloy and ZIRLO) are the most used fuel-‐cladding materials.
However, at high temperatures and high energy radiaZon exposure (like LOCA) exothermic reacZons of Zr with water/steam yield hydrogen in great amounts which could lead to
1) Hydrogen Embriblement
2) ProducZon of hydrogen gas
h?p://www.bing.com/images/search?q=hydrogen+gas+explosion+nuclear+reactors&FORM=HDRSC2#view=detail&id=14AB280C0A377C6DE796707775601E56B1935EC3&selectedIndex=0
Hydrogen Gas explosion at Fukushima Dai-‐ishi
h?p://www.machinerylubricaFon.com/Read/573/moisture-‐contaminaFon-‐targets
Additional Materials for Fuel-Cladding Promising research into Silicon Carbide (SiC) as a replacement for fuel-‐cladding Epitaxial Graphene (EG) on SiC meets the thermal and mechanical needs for fuel-‐cladding and since graphene has a hydrophobic nature it is thought to be less reacZve to steam and therefore less likely to produce hydrogen. Single-‐layered graphene has not been fully tested under extremely high temperatures or under condiZons that mimic LOCA.
Epitaxial Graphene Mono-‐layered graphene in a 2-‐D honeycomb arrangement of carbon atoms Studied for its electrical, chemical, thermal and mechanical properZes. Epitaxial means that the graphene is grown on a surface of a crystal material and mimics the arrangement of that substrate. Sample from Dr. de Heer’s group using a “Confinement Controlled SublimaZon” to grow high quality layers of EG on SiC.
Epitaxial Graphene on Silicon Carbide h?p://cnx.org/content/m29187/latest/
Raman Spectroscopy
J. Phys. Chem. C 2008, 112, 10637–10640. Copyright 2008 American Chemical Society; h?p://www3.ntu.edu.sg/home/yuFng/papers/nano%20research-‐review%20graphene.pdf
Used to detect low frequency modes in a sample. InelasZc scabering (KE is not conserved)
h?p://www-‐che.engr.ccny.cuny.edu/courses/che5535/lecture5/sld002.htm
Raman Data of EG on SiC The sample of EG on SiC showed the characterisZc G (1500 – 1620 cm¯ˉ¹) and 2D (2700-‐2750 cm¯ˉ¹). SiC was subtracted.
Wavenumber (cm¯ˉ¹)
Intensity
(arbitrary un
its) 2 D peak
G peak
Monitoring Desorbed molecules of EG on SiC
To test the thermal stability of the sample the desorpZon defects were measured with a special interest in hydrogen gas.
Temperature Programmed DesorpZon (TPD): the technique of observing desorbed molecules from a surface as the surface temperature is increased via a mass analyzer.
Quadrupole analyzer commonly used.
As desorpZon occurs ions are released into the chamber and guided to the quadrupole.
The ions move through the electric field formed by the rods. The strength and frequency of the field dictates if an ion of a parZcular mass will pass through the rods and therefore counted by the detector or collides into a nearby surface.
TPD Designed and created by Orlando Group Ultra High Vacuum chamber (1.4 E-‐8 Torr)
Sample stage with thermocouple abached to a thin tantalum wire acZng as a spring clip, allowing direct contact with the sample.
Nitrogen chamber to keep out pump oil and other impuriZes.
Temperature range 500°C to 1000°C (5 minute intervals)
Temperature controlled by adjusZng current 7 A – 19/20 A
Empty chamber, SiC , EG on SiC (with and without water – dose set for 2.5 E -‐10 A.
Quadrupole analyzer Quadera sooware
Thermal Programmed Desorption Sample stage
Vacuum Chamber
Quadrupole
Water Source
Orla
ndo Grou
p Ge
orgia InsFtute of T
echn
ology
TPD Data of H2
0
0.2
0.4
0.6
0.8
1
1.2
0 0.2 0.4 0.6 0.8 1 1.2
Time (s)
Ion Cu
rren
t Inten
sity (A
)
0.00E+00
2.00E-‐11
4.00E-‐11
6.00E-‐11
8.00E-‐11
1.00E-‐10
1.20E-‐10
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Run 1 Empty Chamber_H2O
Run 1 SiC_H2O
Run 1 EG on SiC_H2O
Run 1 EG on SiC_No H2O
TPD Data of CO2
0.00E+00
1.00E-‐11
2.00E-‐11
3.00E-‐11
4.00E-‐11
5.00E-‐11
6.00E-‐11
7.00E-‐11
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Run 1 Empty Chamber_H2O
Run 1 SiC_H2O
Run 1 EG on SiC_No H2O
Run 1 EG on SiC_H2O
Time (s)
Ion Cu
rren
t Inten
sity (A
)
TPD Data of CO
0.00E+00
1.00E-‐11
2.00E-‐11
3.00E-‐11
4.00E-‐11
5.00E-‐11
6.00E-‐11
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Run 1 Empty Chamber_H2O
Run 1 SiC_H2O
Run 1 EG on SiC_No H2O
Run 1 EG on SiC_H2O
Time (s)
Ion Cu
rren
t Inten
sity (A
)
TPD overlay of CO and CO2
0.00E+00
2.00E-‐11
4.00E-‐11
6.00E-‐11
8.00E-‐11
1.00E-‐10
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Run 1 EG on SiC_H2O
Run 1 EG on SiC_H2O
Time (s)
Ion Cu
rren
t Inten
sity (A
)
CO
CO2
FINAL THOUGHTS Graphene appears to not react with water at high temperatures to produce hydrogen gas
More research on EG on SiC in LOCA condiZons
Further quanZfy and characterize the TPD tested sample
1) High ResoluZon Transmission Electron Microscopy
2) Raman spectroscopy
Future DirecZon 1) Wrapped EG around Zircaloy
2) Grow Chemical Vapor Deposited (CVD) on Zircaloy
TesZng both in TPD chamber to analyze H2 desorpZon
ACKNOWLEDGEMENTS I would like to thank the following people and groups for this rewarding opportunity: NaZonal Science FoundaZon (NSF) Dr. Leyla Conrad and the STEP-‐UP Program Giovanni DeLuca Dr. Thomas Orlando The Orlando Group
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