challenges facing ksc in corrosion management and the nasa
TRANSCRIPT
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Challenges Facing KSC in Corrosion Management and the NASA/KSC Corrosion Technology Testbed
Luz Marina Calle
Corrosion Technology Testbed
NASA, Kennedy Space Center, Florida, USA
2005 C3P-NASA International Pollution Prevention Workshop, Lisbon, Portugal
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OutlineEffects of corrosionCost of corrosionWhat is corrosionEvaluation of corrosionAtmospheric exposure studiesElectrochemical measurementsEnvironment at KSCChallenges:
Highly corrosive environmentAcidic exhaust from SRBsEnvironmental issues
Materials and Coatings SelectionCorrosion Protective CoatingsCorrosion Resistant Alloys
NASA Corrosion Technology Testbed
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Effects of Corrosion
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Cost of Corrosion in the US
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Cost of Corrosion in the US
$ = Billion 1998 dollarswww.corrosion-doctors.org
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What is Corrosion?
Corrosion is the deterioration of a material due to its reaction with its environment (M.G. Fontana).
Corrosion is the destructive attack of a metal by chemical or electrochemical reaction with its environment (H.H. Uhlig).
Metal atoms in nature are present in chemical compounds (i.e. minerals).
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What is Corrosion?
The same amount of energy that is needed to extract metals from their minerals is emitted during the chemical reactions that produce corrosion. Most corrosion is electrochemical.Corrosion returns the metal to the minerals or similar compounds from which the metal was extracted.Corrosion has been called extractive metallurgy in reverse
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Electrochemical Nature of Metallic Corrosion
Chemical reaction involving the transfer of electrons at the metal surface.
Metal is oxidized (anodic reaction)Fe Fe2+ + 2e-
Something else is reduced (cathodicreaction)
2H+ + 2e- H2
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Requirements for Corrosion
1. Anode sites on a metal surface2. Cathode sites on a metal surface3. Electrolyte in contact with anode and
cathode (provides path for ionic conduction)
4. An electrical connection between anode and cathode (allows electrons to flow between anode and cathode)
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Evaluation of Corrosion
Field Exposure TestsElectrochemical MethodsAccelerated Exposure
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Coupon Exposure Stands
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Atmospheric Exposure
Atmospheric exposure provides valuable data but it takes a long time and relies on human visual inspection.
NASA Technical Standard for Protective Coatings requires 18 months of good performance for preliminary approval and continued good performance for 5 years for final approval of a coating system.
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Electrochemical Techniques
Corrosion rate measurement by dc methods usually involve applying a small amplitude dc signal, of either voltage or current, to a corroding metal. The resulting current or voltage is measured and a polarization resistance can be calculated.
Corrosion rate is inversely proportional to polarization resistance.
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Electrochemical Methods
Corrosion PotentialDirect current methods
Linear polarizationTafel plotsCyclic polarizationPotentiodynamic scanning
Electrochemical ImpedanceSpectroscopy
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EIS
EIS is an electrochemical technique in which a small amplitude sinusoidal potential perturbation is applied to the working electrode at a number of discrete frequencies, ω. At each of these frequencies, the resulting current waveform will exhibit a sinusoidal response that is out of phase with the applied potential signal by a certain amount (θ) and has a current amplitude that is inversely proportional to the impedance of the interface.
Z(ω) = V(ω)/I(ω)
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EIS Experiments
AC Waveforms for an Applied Voltage and Resulting Current
Time
E
I
θ
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Environment at KSC
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Introduction
Corrosion studies began at KSC in 1966 during the Gemini/Apollo Programs.
Saturn V
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NASA/KSC Beach Corrosion Test Site
LAUNCH COMPLEXES39A 39B
KSC BEACH CORROSION LABORATORY
COUPON EXPOSURE STANDS ATLANTICOCEAN
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Introduction
The launch environment at KSC is extremely corrosive:
• Ocean salt spray• Heat• Humidity• Sunlight• Acidic exhaust from
SRBs
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Corrosion Rates of Carbon Steel
L o c a ti o nT y p e O f
E n v i r o n m e n t µ m / y rC o r r o si o n
r a te (a ) m i l s/ y r
E s q u im a lt , V a n c o u ve r Is la n d , B C , C a n a d a
R u ra l m a rin e 1 3 0 . 5
P i t t s b u rg h , P A In d u s t r ia l 3 0 1 . 2C le ve la n d , O H In d u s t r ia l 3 8 1 . 5
L im o n B a y , P a n a m a , C Z
T ro p ic a l m a rin e 6 1 2 . 4
E a s t C h ic a g o , IL In d u s t r ia l 8 4 3 . 3B ra z o s R ive r, T X In d u s t r ia l m a rin e 9 4 3 . 7
D a y t o n a B e a c h , F L M a rin e 2 9 5 1 1 . 6P o n t R e y e s , C A M a rin e 5 0 0 1 9 . 7
K u re B e a c h , N C (8 0 ft . fro m o c e a n )
M a rin e 5 3 3 2 1
G a le t a P o in t B e a c h , P a n a m a C Z
M a rin e 6 8 6 2 7
K e n n e d y S p a c e C e n t e r, F L (b e a c h )
M a rin e 1 0 7 0 4 2
(a) Two-year average
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Corrosion Rate Change
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Space Shuttle Launch
SRB Exhaust
In 1981 the Space Shuttle introduced acidic deposition products
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Solid Rocket Booster Fuel Reaction
NH4ClO4(s) + Al(s) ⎯⎯⎯⎯⎯⎯ →⎯ 32 , OFebinder Al2O3(s) +HCl(g) + H2O(g) + NOx(g)
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Materials and Coatings Selection
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HistoryA 1969 Study determined that inorganic zinc-rich primers (ZRPs) outperformed organic zinc in the KSC seacoast environment and that, in general, top-coats were detrimental to the long-term performance of the inorganic ZRPs. Some of the panels exposed at the Beach Site for this study are still in perfect condition.
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ZRP Panels After 8 Years of Atmospheric Exposure
Untopcoated ZRP Epoxy and urethane coated ZRP
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History
In 1981 the Space Shuttle introduced acidic deposition problems to the ZRP coatings.Studies conducted to identify coating systems to improve the chemical resistance of zinc primers10 topcoat systems were approved for use in the Space Shuttle launch environment.
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History
The coating systems selected were all solvent-basedClean Air legislation and environmental regulations began to restrict the use of solvents in paintsA 1995 Study determined that total inorganic coating systems provided excellent protection in launch environments
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Silicone Ablative CoatingsLaunch structures receive severe damage during launch due to high heatNew primerless silicone technology developed between KSC, DuPont, and Dow CorningAblative material installed in 1994 on entire 95’ level
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Protective Coating Research
EIS evaluation of inorganic ZRPs.Conductive polymer coatings.Polysiloxane coatings.Silicone coatings for blast and heat protection of launch structures.Molybdate conversion coatings as possible replacement of chromium conversion coatings.
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Development of Molybdate Conversion Coatings for Aluminum
Investigated the corrosion protection properties of six formulations of environmentally friendly molybdate conversion coatings as possible replacements for chromate conversion coatings on aluminum alloy 2024-T3.Used EIS as well as Scanning Electron Microscopy (SEM), X-Ray Photoelectron Spectroscopy (XPS), and Energy Dispersive Spectroscopy (EDS).
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The acidic chloride environment is aggressive to most metals and causes severe pitting in some of the common stainless steel alloys.
304L is susceptible to pitting corrosion that can cause cracking and rupture of both high-pressure gas and fluid systems.
The failures can be life catastrophic.
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Micrograph (100x magnification) of Pit from KSC’s Launch Pad 304L Tubing
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Tubing Split Caused by Pitting
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Electrochemical Investigation of the Corrosion Behavior of Metal Alloys in
the STS Launch EnvironmentElectrochemical characterization of the corrosion behavior of 24 alloys using DC techniques and EIS.Correlation between electrochemical data and atmospheric exposure data at the Beach Corrosion Test Site.
Cyclic Polarization for 304L - 3.55% NaCl
E(m
V)
log(I)(log(A))
-100
-200
-300
-400
-500
0
100
200
300
-3-4-5-6-7-8-9-10 -2
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Alloys
Alloy Class
304L Low carbon austenitic stainless steel
AL6XN Superaustenitic stainless steel
254SMO Austenitic stainless steel
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Alloy Composition
Alloy Fe Ni Cr Mo Mn C N Si P S Cu
304L 71.567 8.200 18.33 0.500 1.470 0.023 0.030 0.380 0.030 0.0002 0.460
AL6XN 48.11 23.88 20.470 6.260 0.300 0.020 0.330 0.40 0.021 0.0003 0.200
254SMO 55.162 17.900 20.000 6.050 0.490 0.012 0.196 0.350 0.019 0.001 0.680
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Racks at KSC’s Beach Corrosion Test Site
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Atmospheric Exposure
304L
S31603
S31703
Tubing after one year of natural seacoast atmospheric exposure (no acid rinse)
S30403 304L AL6XN
254SMO
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Electrochemistry
Corrosion potentialLinear polarizationCyclic polarizationElectrochemical Impedance Spectroscopy (EIS)Electrolyte conditions:3.55% NaCl3.55% NaCl–0.1N HCl3.55% NaCl–1.0N HCl
Electrochemical Cell
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Corrosion Potential
(a) neutral 3.55% NaCl
(b) 3.55% NaCl-0.1N HCl
(c) 3.55% NaCl-1.0N HCl
(a) (b)
(c)
-150
-100
-50
0
50
0 50 100 150 200 250 300 350 400 450
Time / hrs
OC
P / m
V
304L (0N HCl) 254SMO (0N) AL6XN (0N)
-250
-200
-150
-100
-50
0
50
100
150
0 50 100 150 200 250 300 350 400 450
Time / hrs
OC
P / m
V
304L (0.1N) 254SMO (0.1N) AL6XN (0.1N)
-400
-350
-300
-250
-200
-150
-100
-50
0
50
100
150
0 50 100 150 200 250 300 350 400 450
Time / hrs
OC
P / m
V
304L (1N) 254SMO (1N) AL6XN (1N)
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Neutral 3.55% NaCl
254SMO AL6XN
304L
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3.55% NaCl-0.1N HCl
254SMO
304L
AL6XN
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3.55% NaCl-1.0N HCl
254SMOAL6XN
304L
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Surface Morphology
(a) (b) (c)
A
B
SEM images of 304L SS in 3.55% NaCl–1.0N HCl: (a) 22X image of the sample showing the exposed area A and unexposed area B, (b) 1000X image of A, and (c) 1000X image of B.
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NASA Corrosion Technology Testbed
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http://corrosion.ksc.nasa.gov
The Corrosion Technology Testbed is a capability outfitted with state-of-the-art equipment and facilities to develop new corrosion control technologies and to
investigate, evaluate, and determine material behavior in many different corrosive
environments.
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StaffStaff present at the KSC facilities include scientists, engineers, and technicians with degrees and expertise in the following areas:
Discipline PhD MS BSPhysical Chemists 2 0 0Chemical Engineers 1 0 0Corrosion Engineers 0 1 2Analytical Chemists 2 0 0Material Scientists 1 0 1
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Corrosion Technology Testbed
Electrochemistry laboratoryAccelerated corrosion equipmentCoatings application laboratoryAtmospheric exposure siteSeawater immersion systemSurface analysis
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Seawater Immersion System
Two immersion tanks with a continuous once-through, filtered supply of seawater is used to evaluate test coupons, component hardware, or full scale test articles. Temperature, salinity, dissolved oxygen, conductivity and pH are closely monitored.Can be utilized for the evaluation of protective coatings, metal alloys, reinforced concrete, composites and other materials in a seawater environment. Specialized tests can be designed to study impingement-corrosion, erosion-corrosion, cavitation and other velocityeffects.
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Accelerated Corrosion Laboratory
Salt fog testing to study the ability of a material to resist corrosion.
Capabilities include traditional salt spray techniques, as well as advanced cyclic and acidic methods.
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Surface AnalysisSurface Analysis
State of the art electron microscopes and experienced staff study corrosion mechanisms through surface chemistry, depth profiling, and composition mapping. Techniques available for surface analysis include:
TEM (Transmission Electron Microscopy)
SEM (Scanning Electron Microscopy)
XPS (X-Ray Photoelectron Spectroscopy)
AES (Auger Electron Spectroscopy)
Rutherford Backscattering Spectroscopy
SIMS (Secondary Ion Mass Spectrometry)
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Representative ProjectsNon-chrome Conversion Coating Evaluation (Navy)Airplane Wing Study (Air Force)Seawater Immersion Studies of Welds for Military Applications (Navy)Launch Site Coating Development and Evaluation (Air Force)Single Coat/Rapid Cure Marine Tank Lining Evaluation (Navy)Antifouling Coating Test and Evaluation (Navy) Chloride Rinse Agent Investigation (Army)Smart Coating Development (NASA)Corrosion Resistant Tubing for Shuttle Launch Sites (NASA)Support Equipment Paint Replacement Project (NASA)Electrochemical Evaluation of Coatings for Solid Rocket Motors (Thiokol)VAB/LCC Roof (Reinforced Concrete) Corrosion Study (NASA)Refractory Concrete Study (NASA)Urethane Replacement Study (NASA)Depainting/Surface Preparation Study (NASA)Polysiloxane Coating Development (NASA)Cryogenic Storage Corrosion Study (NASA)Galvanic Coatings for Protection of Steel in Concrete (NASA)Outdoor Video Camera Corrosion Study (NASA)Corrosion of Food Processing Equipment (Industry)
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Project HighlightsPerformance of Chemical Rinse Agents on Aircraft Alloys Exposed to a Seacoast Environment
Four chloride rinse agents (CRAs) were evaluated for use on military aircraft, missiles, and various components.
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Chromate Coating Replacements for Military Aircraft
The effectiveness of replacements to currently used chromate conversion coatings is being investigated.
The coating system matrix utilizes:Four aluminum substratesNine pretreatmentsFive primersTwo topcoats
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Contact InformationLuz Marina Calle, Ph.D.
E-mail: [email protected]: 1-321-867-3278
Joseph CurranE-mail: [email protected]
Phone: 1-321-867-7558
http://corrosion.ksc.nasa.gov