NASA - Alternative To Nitric Acid Passivation

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R=20160001416 2020-06-22T06:00:17+00:00Z
Alternative to Nitric Acid Passivation
NASA Corrosion Technology Laboratory

&
NASA Technology Evaluation for Environmental Risk Mitigation
1
Outline
• Background
• Risk
• Specifications
• Benefits
• Objective
• Testing
• Collaboration
• Summary
2
Background
• Corrosion is an extensive problem that affects the National Aeronautics and Space Administration
(NASA) and European Space Agency (ESA).
• The deleterious effects of corrosion result in steep costs, asset downtime affecting mission readiness,
and safety risks to personnel.
• It is vital to reduce corrosion costs and risks in a sustainable manner.
3
Background
• The standard practice for protection of stainless steel is passivation.

• Passivation works by forming a shielding outer (metal oxide) layer that reduces the impact of
deleterious environmental factors such as air or water.
• Typical passivation procedures call for the use of nitric acid; however, there are a number of
environmental, worker safety, and operational issues associated with its use.
http://www.koslow.com http://www.koslow.com http://www.koslow.com http://www.koslow.com

Non-Passive Stainless Steel Passivation Process Stripped Down to the Bare Metal Return to Passive Stainless Steel
• Free iron particles (un-alloyed iron) • Stainless steel is degreased, • Raw stainless steel after damaged • The spontaneous formation
• Damage or a scratch to the passive cleaned and prepped passive film and contaminates have of a fresh passive film.
layer • Stainless steel is immersed in been dissolved • Stainless steel now ready for
• Also called active because surface an acid bath and rinsed • Allow 8 – 24 hours to allow stainless a corrosion free service
can be prone to corrosion steel to oxidize
4
Risk
• Nitric acid passivation results in fumes that contain nitrogen dioxide and nitrogen oxide (NOx)
emissions which are considered greenhouse gases; Best Available Technology (BAT) to be employed
to control nitric acid and NOx emissions
• Nitric acid passivation requires 25% or 50% concentration of the strong acid.
• Wastewater generated from the passivation process is regulated under the U.S. Environmental
Protections Agency’s (EPA) Metal Finishing Categorical Standards
• Nitric acid can remove beneficial heavy metals (nickel, chromium, etc.) that give stainless steel its
desirable properties.
HNO3
http://www.theguardian.com
http://commons.wikimedia.org http://www.offshoreenergytoday.com
5
Specification
• ASTM A 967 (Standard Specification for Chemical Passivation

Treatments for Stainless Steel Parts) and AMS 2700 (Passivation
Treatments for Corrosion-resistant Steel), both allow for the use
of citric acid in place of nitric acid.
https://www.agra-net.net
• Citric acid is similarly called out in the ASTM A 380 (Standard
Practice for Cleaning, Descaling, and Passivation of Stainless
Steel Parts, Equipment, and Systems) standard.
• Citric acid passivation is not a new technology; it was developed
(many years ago) for the beverage industry in Germany to process
containers that were free of iron which causes an unwanted taste
to the beverage.
• While citric acid use has become more prominent in industry in
the U.S., there is little evidence that citric acid is a technically
sound passivating agent, especially for the unique and critical
applications encountered by NASA and ESA.
http://www.dowlandbach.com
6
Benefits of Citric Acid Passivation
• Citric acid is a bio-based material that helps government agencies

meet the procurement requirements of the Farm Security and
Rural Investment Act of 2002
http://vegnews.com
• There are no toxic fumes created during the citric acid passivation
process making it safer for workers. C6H8O7
• Nitric acid passivation requires 25% or 50% concentrations of the
strong acid which are extremely corrosive and hazardous to
workers.
• Citric acid removes iron from the surface more efficiently than http://commons.wikimedia.org
nitric acid and therefore uses much lower concentrations reducing
material costs.
• Citric acid-based processing baths retain their potency for longer
periods requiring less frequent refilling and reduced volume and
potential toxicity of effluent and rinse water.
7
Benefits of Citric Acid Passivation
KSC Corrosion Lab recorded the following data:
• 4% Citric Acid has a pH of 2.39

• 50% nitric acid had a pH < 1
KSC Process Waste Questionnaire Technical Response Package =
TCLP METALS BELOW RCRA REGULATORY LEVELS
• Estimated costs for nitric or citric acid with a pH of < 2 would be
about $235/55 gal drum {€207/208L}
• Estimated costs for these wastes with pH > 2 and no other hazardous
waste concerns, such as toxic metals, would be about $80/55 gal
drum {€71/ 208L}
http://starlitewaste.com
8
Objective
• The primary objective of this effort is to qualify citric acid as an environmentally-preferable

alternative to nitric acid for passivation of stainless steel alloys.
http://www.wosupply.com
http://acidpedia.org
http://www.appliedtungstenite.com
http://advancedplatingtech.com
9
Test Specimen Preparation
The NASA Corrosion Technology Lab followed the United Space Alliance (USA) procedure for
passivation:
Degrease - Rinse #2
Grit Blast Second Degreasing Rinse #1
Initial Clean (Spray Bottle -
(Iron Media) (Bruhlin 815 GD) (DI Water)
(Acetone Wipe) DI Water)
Rinse #4
Caustic (Alkaline) (Spray Bottle - Citric Acid
Rinse #3 Rinse #5
Cleaning DI Water to Ensure Passivation
(DI Water) Appropriate Water Break (DI Water)
(Turco 4090) (Parameters Vary)
is Present)
Rinse #6
Check pH of surface Dry
(Spray Bottle -
(pH 6.0 to 8.0) (Gaseous Nitrogen)
DI Water)
10
Parameter Optimization
Test panels of each stainless steel alloy were prepared using various
process parameters
• Citric Acid Concentration: 4%

• Immersion Times: 60, 90, and 120 minutes
• Bath Temperatures: 100, 140, and 180°F
• Salt Spray Testing per ASTM B 117
• Corrosion Resistance Evaluation per ASTM D 610 every 168
hours
• Parameters resulting in the best corrosion resistance shall be used
for preparation of that substrate’s test panels for the remainder of
the testing
11
Process Parameters Used for Testing
Alloy Passivation Concentration (%) Bath Temperature (o C) Dwell Time (minutes)
AL6XN
Nitric Acid 22.5 60 20
AL6XN
Citric Acid 4 38 120
Nitric Acid 50 64 30
A286
Citric Acid 4 82 60
304
Citric Acid 4 49 120
1 Nitric Acid 50 64 30
17-4PH @ 504 Hours of ASTM B117 Exposure
Citric Acid 4 38 30
316
Citric Acid 4 60 90
321
Citric Acid 4 82 60 A286
410
Citric Acid 4 82 60
440C
Citric Acid 4 60 60
15-5PH
Citric Acid 4 82 60
Nitric Acid 50 64 30 @ 504 Hours of ASTM B117 Exposure
17-7 PH
Citric Acid 4 82 60
Note 1 = Citric acid parameters were initially determined by USA
All other citric acid parameters were determined by KSC Corrosion Lab 12
Stainless Steel Alloy Composition
Alloy C Mn Cr Mo Ni Fe Si P S Al Cu Ti
AL6XN 0.03 2 20 - 22 6 - 7 23.5 - 25.5 BAL 1 0.04 0.03 0.75
A286 0.08 2 13.5 - 16 1 - 1.5 24 - 27 BAL 1 0.025 0.025 0.35 0.5 1.9 - 2.35
304 0.08 2 18 - 20 8 - 10.5 BAL 0.75 0.04 0.03
17-4PH 0.07 1 15 - 17.5 3-5 BAL 1 0.04 0.03 3-5
316 0.08 2 16 - 18 2-3 10 - 14 BAL 0.75 0.04 0.03
321 0.08 2 17 - 19 9 - 12 BAL 0.75 0.04 0.03 0.7
410 0.15 1 11.5 - 13.5 BAL 1 0.04 0.03
440C 0.95 - 1.2 1 16 - 18 0.75 BAL 1 0.04 0.03
15-5PH 0.07 1 14 - 15.5 3.5 - 5.5 BAL 1 0.04 0.03 2.2 - 4.50
17-7PH 0.09 1 16 - 18 6.5 - 7.5 BAL 1 0.04 0.03 0.75 - 1.5
http://periodictable.com 13
Testing
Test Test Methodology References Acceptance Criteria Location

X-Cut Adhesion by Wet Tape ASTM D 3359
NASA Corrosion
Tensile (Pull-off) Adhesion ASTM D 4541
Technology Lab
Cyclic Corrosion Resistance GMW 14872
ASTM D 610 NASA Corrosion
Atmospheric Exposure Testing ASTM D 714 Technology Lab
NASA-STD-5008 Atmospheric Exposure Site
ASTM B 117 Alternative performs as well
ASTM E 4 or better than control process
ASTM E 8
Stress Corrosion Cracking
ASTM G 38 NASA Corrosion
ASTM G 39 Technology Lab
ASTM G 44 MSFC-STD-3029
Fatigue* ASTM E 466
Hydrogen Embrittlement** ASTM F 519
* = Only one alloy was tested; 17-4PH
** = Test specimens were made of AISI 4340 alloy steel, this is considered worst case
14
X-Cut Adhesion by Wet Tape Testing
24 Hour Immersion @ Ambient Temperature

Masking Tape is Affixed to the Surface Using
a Roller; Within 90 Seconds, the Tape is
removed, Pulling (180-degree angle) Rapidly
X-cut Scribed into the Surface back upon Itself
15
X-Cut Adhesion by Wet Tape Testing
Performs as well or better than control process
Coating Systems
Primer / Topcoat
Alloy Passivation
Sherwin Williams E90H226 & V93V227 / Sherwin Williams E90H226 & V93V227 / Sherwin Williams E90W501 & V93V505 / Carboline Carboguard 893 / Sherwin Williams
Sherwin Williams F93G504 & V93V502 Sherwin Williams F93G116 Sherwin Williams F93G106 Carboline Carbothane 134 MC Polysiloxane XLE2
1 1 1 1 1
Citric 5A 5A 5A 5A 5A
AL6XN 1 1 1 1 1
Nitric 5A 5A 5A 5A 5A
1 1 1 1 1
17-4PH 1 1 1 1 1
1 1 1 1 1
286 1 1 1 1 1
1 1 1 1 1
304 1 1 1 1 1
1 1 1 1 1
17-7PH 1 1 1 1 1
1 1 1 1 1
410 1 1 1 1 1
1 1 1 1 1
155 1 1 1 1 1
1 1 1 1 1
321 1 1 1 1 1
1 1 1 1 1
316 1 1 1 1 1
1
Note = 5A is the highest rating available; no peeling or removal of the coating at the scribe 16
Tensile (Pull-Off) Adhesion
The pull-off test is performed by securing a loading fixture (dolly) to the surface of the coating with an
adhesive. After the adhesive is cured, a testing apparatus is attached to the loading fixture and aligned to apply
tension normal to the test surface. The fixture is pulled from the surface of the panel and the burst pressure is
recorded, that value is converted to produce a value for pull-off tensile adhesion (POTS).
17
Tensile (Pull-Off) Adhesion – Phase I
2
Result PSI (ave)
Alloy Primer Only Passivation
Nitric Citric
1
A-286 Carboline Carboguard 893 1504 1064
1
304 Carboline Carboguard 893 847 1383
1
AL6XN Carboline Carboguard 893 1297 1292
1
17-4PH Carboline Carboguard 893 1131 1292
1
Note = NASA-STD-5008 Approved Products List
2
Note = Pull-off values over 500 psi are considered passing
All pull-off values were over 500 psi, and the mode of failure
was predominantly related to the adhesive used to glue the dolly
to the surface of the panel.
18
Tensile (Pull-Off) Adhesion – Full Alloy Set
2 2 2
Result PSI (ave) Result PSI (ave) Result PSI (ave)
Alloy Primer Only Passivation Alloy Primer Only Passivation Alloy Primer Only Passivation
Nitric Citric Nitric Citric Nitric Citric
AL6XN 987 985 AL6XN 1016 1005 AL6XN 504 517
17-4PH 704 753 17-4PH 2159 2390 17-4PH 1052 1252
704 841 775 748 286 1045 1212
286 286
304 459* 512
304 699 757 304 631 678 1
17-7PH Carboline Carboguard 893 536 534
17-7PH Sherwin Williams E90H226 & V93V2271 739 816 17-7PH Sherwin Williams E90W501 & V93V505
1 531 707
410 481* 528
410 858 946 410 756 819
155 496* 523
155 979 1127 155 683 784 321 523 523
321 995 945 321 757 726 316 489* 572
316 753 978 316 713 735 1
Note = Coatings on the NASA-STD-5008 Approved Products List
1 1
Note = Chemical Agent Resistant Coatings Note = Chemical Agent Resistant Coatings 2
Note = Pull-off values over 500 psi are considered passing
2 2
Note = Pull-off values over 500 psi are considered passing Note = Pull-off values over 500 psi are considered passing Note* = 100% glue failure
2 2 2
Result PSI (ave) Result PSI (ave) Result PSI (ave)
Alloy Coating Passivation Alloy Plating Alloy Plating Passivation
Passivation
Nitric Citric Nitric Citric
Nitric Citric
AL6XN 1201 1221
AL6XN 1259 1266 AL6XN 957 958 17-4PH 1629 1718
17-4PH 1164 1040 17-4PH 1871 1989 286 1857 2069
286 1025 1105 286 2359 2113 304 1368 1553
304 771 918 304 1542 2287 17-7PH Cadmium Plating
1
516 680
1
17-7PH Sherwin Williams Polysiloxane XLE 402* 438* 17-7PH Hard Chrome Plating
1
1255 1049 410 770 894
410 432* 479* 410 1086 1189 155 803 830
155 472* 434* 321 620 716
155 942 1284
321 364* 417* 316 709 745
321 958 981 1
316 434* 452* Note = Coatings on the NASA-STD-5008 Approved Products List
1
316 880 830 2
Note = 1 Note = Pull-off values over 500 psi are considered passing
2
Note =
Note = Pull-off values over 500 psi are considered passing 2
Note* = 100% glue failure
Note = Pull-off values over 500 psi are considered passing 19
GMW 14872 Cyclic Corrosion Resistance - 80 Cycles
Each cycle consists of an 8 hour exposure under ambient conditions (25ºC, 45% RH), an 8 hour exposure
under high humidity conditions (49ºC, 100% RH), and 8 hours under drying conditions (60ºC, 30%
RH. During the initial ambient stage, the specimens are sprayed with a solution comprised of sodium
chloride (0.90%), calcium chloride (0.10%), sodium bicarbonate (0.075%) and water (98.925%).
20
ASTM D 610:
Standard Test Method for Evaluating Degree of Rusting on Painted Steel Surfaces
21
GMW 14872 Cyclic Corrosion 17-7PH – Citric
Alloy Passivation
Average Ratings After 80 Cycles
Cyclic Corrosion Resistance Citric 9
AL6XN
Nitric 9
Performs as well or better than Citric 3
control process 17-4PH
Nitric 3
Citric 5
AL6XN – Citric 286
Nitric 5 316 – Citric
Citric 5
304
Nitric 3
Citric 5
17-7PH
Nitric 5
Citric 0
410
Nitric 0
304 – Citric 410 – Citric
Citric 4
155
Nitric 3
Citric 6
321
Nitric 4
Citric 5
316
Nitric 4
22
Atmospheric Exposure Test
Phase I Phase II
23
ASTM D 610:
Standard Test Method for Evaluating Degree of Rusting on Painted Steel Surfaces
24
Atmospheric Exposure Test – Passivated Only – (Phase I Samples and Exposure)

Alloy Passivation 1 Month 3 Month 6 Month 18 Month
Average Ranking Average Ranking Average Ranking Average Ranking
Citric 6 5 5 4
A286
Nitric 5 4 3 3
Citric 5 5 3 3
304
Nitric 4 4 2 2
Citric 9 8 8 7
AL6XN
Nitric 7 7 7 5
Citric 4 3 3 2
17-4PH
Nitric 4 3 3 2
25
Atmospheric Exposure Test – Passivated Only - (Phase II and III Samples)
Alloy Passivation 1 Month 3 Month 6 Month 12 Month
Citric 10 8 6 5
Performs as well or better than AL6XN
Nitric 10 5 4 4
control process Citric 3 2 2 2
17-4PH
Nitric 4 3 3 3
Performs worse than control Citric 5 4 4 3

286
Nitric 5 4 3 3
process
Citric 4 3 3 3
304
Nitric 2 2 2 2
Citric 4 4 3 3
17-7PH
Nitric 4 4 3 2
Citric 4 2 2 0
410
Nitric 3 1 1 0
Citric 4 3 3 3
155
Nitric 4 3 3 3
Citric 4 3 2 2
321
Nitric 2 2 2 2
Citric 5 3 3 3
316
Nitric 2 2 2 2
26
Atmospheric Exposure Test – Passivated & Coated – (Phase I Samples Only)

Alloy Passivation Primer Topcoat 1 Month 3 Month 6 Month 18 Month
Citric Carboline Carboguard Carboline Carbothane 10 10 10 10
A286 1 1
Nitric 893 134 MC 10 10 10 10
304 1 1
Nitric 893 134 MC 10 10 10 10
AL6XN 1 1
Nitric 893 134 MC 10 10 10 10
17-4PH 1 1
Nitric 893 134 MC 10 10 10 10
1
Note = NASA-STD-5008 Approved Products List
27
Atmospheric Exposure Test – Passivated & Coated – Phase II and Phase III
Testing On-going
28
Samples are then Placed in ASTM B
All alloys were loaded into test 117 Salt Spray Testing – 1,000 Hours
fixtures and were stressed according
to the requirements of ASTM G39.
29
After 1000 hours of the salt spray exposure, the Alloy Passivation Stress Corrosion Cracking
samples were removed, photographed, and AL6XN
Citric Microscopic evaluations showed that none of the samples
microscopically inspected for signs of stress Nitric showed any signs of stress corrosion cracking
corrosion cracking. Citric Microscopic evaluations showed that none of the samples
17-4PH
Nitric showed any signs of stress corrosion cracking
286
304
17-7PH
410
155
321
316
Nitric showed any signs of stress corrosion cracking 30
Fatigue
• 17-4PH alloy only

• Specimen with Continuous Radial Bends Between Ends; Subjected to a Constant Amplitude, Periodic
Forcing Function in Air at Room Temperature
• Stress loads and cycles selected for each substrate were based on historical S-N Curve data in air at
ambient temperature.
31
Fatigue
Testing On-going
32
Hydrogen Embrittlement
4% citric acid solution at 82ºC for 2

Cleaned ASTM F519-13 {Type 1D C-ring - AISI 4340 alloy steel} hours
Test Specimens Prior to Passivation
Upon removal from the citric acid bath, it was noticed that the
C-Rings were covered with a glossy black film (magnetite).
This film remained after the C-Rings were rinsed with
deionized water
33
Hydrogen Embrittlement
• 2.45 turns of the bolt were required to produce a 75% (to failure) loading. All C-Rings were
compressed by 2.45 turns of the nut on the ¼” – 28 steel bolt to produce the C-Rings for
evaluation for potential cracking. All four samples were exposed under ambient condition in
the laboratory.
• After 200 hours of exposure to ambient laboratory conditions, no fractures due to hydrogen
embrittlement were visible on any sample {Type 1D C-ring - AISI 4340 alloy steel}
34
Kourou Exposure Test Campaign
35
Test Panels @ ESA
Alloy Passivation Number of Panels

Nitric 3
304
Citric 3
Nitric 3
316
Citric 3
36
37
ESA Update
38
Next Steps
• Additional process optimization = only evaluated citric acid @ 4% concentration

• It is suggested that the NASA Corrosion Technology Laboratory optimize the passivation process
for the 17-4 samples
• Long term analysis of pitting of the samples at the NASA Beach Site
• Determine ESA needs and requirements for future testing
39
Summary
• Corrosion is an extensive problem that affects the National Aeronautics and Space Administration
(NASA) and European Space Agency (ESA).
• The deleterious effects of corrosion result in steep costs, asset downtime affecting mission readiness,
and safety risks to personnel.
• The standard practice for protection of stainless steel is passivation.
• Typical passivation procedures call for the use of nitric acid; however, there are a number of
environmental, worker safety, and operational issues associated with its use.
• Citric acid removes iron from the surface more efficiently than nitric acid and therefore uses much
lower concentrations reducing material costs.
• There are no toxic fumes created during the citric acid passivation process making it safer for workers.
• For a citric acid passivation concentration of 4%, the stainless steel alloys tested performed as well,
and in some cases better than nitric acid passivated panels.
• NASA and ESA will collaborate on a joint project to evaluate citric acid passivation of stainless steel
alloys.
40

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Alternative to Nitric Acid Passivation

NASA Corrosion Technology Laboratory

• The standard practice for protection of stainless steel is passivation.

http://www.koslow.com http://www.koslow.com http://www.koslow.com http://www.koslow.com

• ASTM A 967 (Standard Specification for Chemical Passivation

• Citric acid is a bio-based material that helps government agencies

KSC Corrosion Lab recorded the following data:

• 4% Citric Acid has a pH of 2.39

• The primary objective of this effort is to qualify citric acid as an environmentally-preferable

• Citric Acid Concentration: 4%

Test Test Methodology References Acceptance Criteria Location

24 Hour Immersion @ Ambient Temperature

Performs as well or better than control process

Performs worse than control Citric 5 4 4 3

Performs as well or better than control process

• 17-4PH alloy only

4% citric acid solution at 82ºC for 2

Kourou Exposure Test Campaign

Alloy Passivation Number of Panels

• Additional process optimization = only evaluated citric acid @ 4% concentration

• Determine ESA needs and requirements for future testing

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