Chemistry At Kennedy Space Center or The Chemistry of ... · PDF fileChemistry At Kennedy...
Transcript of Chemistry At Kennedy Space Center or The Chemistry of ... · PDF fileChemistry At Kennedy...
KSC Engineering Directorate Materials Science Division
Chemistry At Kennedy Space Center or
The Chemistry of Getting into Space
Tim Griffin, Ph.D.
NASA, KSC
Chemical Analysis Section
September 2007
https://ntrs.nasa.gov/search.jsp?R=20120003297 2018-05-06T07:35:19+00:00Z
KSC Engineering Directorate Tim's Background Materials Science Division _________________________________________________
• Earned Bachelor of Science Degree in Chemistry - University of Kansas
• Earned Ph.D. in Analytical Chemistry - University of Florida
- Focus of Mass Spectrometry Instrument Development
• Areas of Work - Chemistry of Failures on Center
- Instrument Development
KSC Engineering Directorate KSC Role Materials Science Division
KSC Premier Spaceport - Most Unmanned Flights Launched - All Manned Flights Launched
Unmanned - Deep Space Exploration
> Galactic Pair - Two Galaxies Interacting II > Spiral Galaxy —Ultraviolet Image of M81 Spiral Galaxy II
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KSC Engineering Directorate Human Space Flight Materials Science Division
Past - Apollo E - SkyLab and ApoIIo-Soyuz
Present - Shuttle E - International Space Station (ISS) I1
Future - Aries/Orion - Moon and Beyond > / - - -
H
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KSC Engineering Directorate MSL at Kennedy Space Center
Materials Science Division
• Different Areas of Materials Science Division • Failure Analysis
- Mechanical - Electrical - Materials
MetrologyWork Together to Solve Problems - Measure Dimensions
• Physical Testing - Break Things
Rapid Prototyping - Concept to Final Product
• Chemical Analysis - Determine What is What
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KSC Engineering Directorate Inorganic Chemical Analysis Materials Science Division
• Elemental Analysis • Bulk Analysis Techniques
- Inductively Couple Argon Plasma (ICAP) > Excellent Quantitation Technique/Destructive
- Arc/Spark > Good Quantitation Technique/Damage Surface
- X-ray Fluorescence (XRF) > Screen for Alloy Type/Non-Destructive
- Ion Chromatography (IC) > Ions in Solution, Primarily water/Destructive
• Small Area Analysis - Particle/Surface
- Scanning Electron Microscopy with Energy Dispersive Waveform Spectroscopy (SEM/EDS)
> ID of Elements/Typically Non-Destructive, Must Fit in Chamber > High Magnification Pictures
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KSC Engineering Directorate Inorganic Chemical Analysis
Materials Science Division (Bulk)
-.
Inductively Couple Argon Plasma
(ICAP)
Arc/Spark
X-ray Fluorescence (XRF)
KSC Engineering Directorate Inorganic Chemical Analysis
Materials Science Division(Liquid)
'
___
- Ion Chromatography (IC)
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: - --. i k •
1
' KSC Engineering Directorate Inorganic Chemical Analysis
Materials Science Division (Spot/Surface)
l/fl
:'I
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KSC Engineering Directorate Organic Chemical Analysis Materials Science Division ______________________________________________________
• Analysis of Structure
- How elements are bonded together
- Class type of compounds (e.g., paraffin, ester)
- Chemical Formula
• Bulk Analysis Techniques
- Fourier Transform Infrared Spectroscopy (FT-lR) > ID Compounds > Non-Destructive
- Gas Chromatography/Mass Spectrometry (GC/MS) > ID Compounds > Quantitation > Low Level Analysis > Destructive
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KSC Engineering Directorate Organic Chemical Analysis Materials Science Division
Fourier Transform Infrared Spectroscopy (FT-IR)
-
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KSC Engineering Directorate Organic Chemical Analysis Materials Science Division
Gas Chromatography Mass Spectrometry (GCIMS)
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I.
I 1.1111+11-,.
U
U
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KSC Engineering Directorate Cadmium Plated Bolts Materials Science Division
The Office of the Inspector General (lG) sent samples to the Material Science Laboratory to be analyzed
and compared to specifications to ensure compliance for safety concerns.
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KSC Engineering Directorate Cadmium Plated Bolts Materials Science Division -________________________________
Multi-discipline Analyses Required
• Chemical Composition • Coating Thickness Determination • Hardness • Tensile Strength
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KSC Engineering Directorate Cadmium Plated Bolts
Materials Science Division
Element New Screw 1
(Element %)
Used Screw 15
(Element %)
Std. 8740 (Element %)
______________
(AISI 8740) (Element %)
_____________ ______________ Carbon* 0.41 0.41 NA 0.38-0.43 Chromium 0.57 0.498 0.52 0.40-0.60 Manganese 0.84 0.85 0.89 0.75-1.00 Molybdenum 0.221 0.251 0.23 0.20-0.30 Nickel 0.437 0.446 0.51 0.40-0.70 Phosphorus 0.019 0.016 0.004 0.035 Max Sulfur 0.008 0.029 0.019 0.040 Max Silicon 0.313 0.233 0.252 0.15-0.35 Iron Balance Balance• Balance Balance
-
New Screw
Used Screw
- . ,... . .....
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KSC Engineering Directorate Cadmium Plated Bolts / Materials Science Division
.s;
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KSC Engineering Directorate Cadmium Plated Bolts
Materials Science Division Conclusions
• Chemical composition, hardness, and tensile strength meet design specifications.
• Cadmium coating thickness for the new lot of bolts was below specifications indicating potential corrosion problems.
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KSC Engineering Directorate Contamination Analysis Materials Science Division __________________________________________________
• Examine Utilizing Inorganic and Organic Methods - Same or similar techniques as examining materials
- Sample extraction often required for Organic contamination
• One of the Most Often Requested • Used to Determine Origin of Contamination
- Compare contamination against possible sources
- Original ID can help narrow possible sources
• Sample Can Be Obtained By Wipes or Swabs - Require a blank, unused, wipe or swab
- Ensure focus analysis on contamination
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Gas Chromatograp
• S. •.• .5 5.ffi±tti 7
( Rtx-5MS
O.5uL \(typicál)
Mass Spectrometer Electron Impact
(El)
• S••.• 55 S •S•ft.••.S.•I •.........i
i m'Ic'!
roXGci QQQ.QJ 0•
[5ssiJ
KSC Engineering Directorate Gas Chromatography/Mass Spectrometry
Materials Science Division (GC/MS)
Computer
time
AA_ Spectra
(second order) A AA m/z mlz
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4 KSC Engineering Directorate Gas Chromatography/Mass Spectrometry
Materials Science Division (GC/IVIS)
• Gas Chromatograph coupled to a Mass Spectrometer - Not separate units - Give two orders of verification
> Time > Spectrum
• Gas Chromatograph - Separate compounds in time - Gas phase
• Mass Spectrometer - Obtain Structural information - Determine mass-to-charge (m/z) of fragments - Can obtain molecular weight information
Is a method to ID compounds • Is a semi-quantitative method
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KSC Engineering Directorate Contamination Analysis
Materials Science Division Example
• Catastrophic failure of 13,800 Volt feed line to the launch pads - main power supply
• Failure occurred at splice • These analyses were to assist the investigation of the failure • Analyses aimed at four different areas of concern
- Contamination - water intrusion - curing of materials - arc path determination
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- - __.l i 'u• - •. -
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1%6
0 r?
KSC Engineering Directorate Contamination Analysis
Materials Science Division Example
Figure 1. Figure 2. Sample location of the Failed Cable Splice Sample Locations of Non-Failed Wire
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KSC Engineering Directorate Contamination Analysis
Materials Science Division Example
Thlc Cnnthmin2tion Sources
Sample
Location
Possible Contamination Sources
Semi-con EPR Yellow Red Rubber Outer Sleeve DCC Glycerin
lip x x x x x x
41P X X X X X X X
81P X X X X X
IOIP X X X X X
II X X X
X - indicates components from that source were detected
Unknown Source
Table. Water Contamination
Sample Location Water Present
BI Yes
Cl Yes
Dl Yes
12 No
Gl No
Unable to test failed splice - failed in water Water Intrusion into outer sleeve but not inner sleeve
KSC Engineering Directorate Contamination Analysis
Materials Science Division Example
Curing of Material - Most of the sampled material were properly cured. However
some of the red mastic showed indications of not being fully cured.
• Arc Path - There was an arc path along with metal deposits throughout the
insulating area - Materials do not appear related to the tin plated copper splice
• Contamination - Analysis indicated presence of a contamination - The contamination was in an unusual physical state
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KSC Engineering Directorate GC/MS
, Materials Science Division Example - ISS
• Contamination on International Space Station • Extracted Wipe • Could not see via FTIR
- Buried in background of wipe - Very low amount
• Injected directly onto GC/MS • After ID
- Obtained sample of possible contamination source - Not primary contamination source - Was able to see low amount of contamination from source
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,,4KSC Engineering Directorate
GC/MS
Materials Science Division Example — ISS
NL: 1.99E6 TIC MS cnt-02
16.84
SampleContamination
14.81
13.7515.76
14.25 16.76 I 1525
16.3117.3
1363
1692
- 14.81 -
Blank15.76
13.75
50,
16.75 40 . 17.38
14.25 16.30
30'15.37 . 1 18.72
i 17.952057
20 1580 1753 1880 1467;
1620 V 1653 185 10
2002
1362 \.. I 0 .......... -''i*rt..r''1' --'. . ., -..-..........-, -.--........---..-i-......_ --------V.--- V.'' '...............
13 14 15 16 17 18 19 20 21 Time (mm)
flU. IC.t50t1.U()
100
90
80
70
U cu 60
50
40
30
20
10
0 100-
90
80
70
60
32
17.8318.72
20721.14
11.95 16.53 18.79 1931 1969 ?Q
.03 - --
NL: 1.01E6
-TIC MS
t060419
083748
Possible Contamination (spectrum)
Contamination (spectrum)
KSC Engineering Directorate GC/MS
V Materials Science Division Example — ISS
110-02 #2214 RT. 1683 02: I 741' 43365 1 . 5 Fi10 nil SO 00-650,00)
1*01
55
00
IS
80,
I
35206.1
91.1
25
20
15 602 1232
10
062 1*2.1 2050 207.1
1652 777.2 238.1 - -2*7.2 2397 287.2 0137 .1152300.3 4072 456.7 561.9 5378 559.1 5935
00 700 751) 200 250 350 350 *00 450 500 550 500
011102 *21671 III: 1972 OV 1 NL: 42450 1: c Fuji us 5)05.050,50)
072
45
90'
85
00
7722
551 05
847 1312
55753.2
50
1542
- 7527
toe,
25 -2262
70822072
70 * ' - 227.3
- ' ' . 2672
5 - 3272 - 2552 2571 305.2 4372
0- 273 3502 5062 5403 6752
60 50 700 ISO 706 25* 300 350 400 450 505 550 000 650
Different Retention Times
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KSC Engineering Directorate GC/MS
Materials Science Division ._Example - ISS
N IL.) - LI LU
100.
90
80-
70:
60
50
40:
30
20-
1 0
0 - 100
90-i
80
70H
16.71
1673 Sample
16.6716.76
16.80
16.89 16.99
13.15 13.77 14.28 14.66 15.39 16.12 16.33 . ". 1727,17.63 i821 18,73 19.07 19.59
16.63
Possible Source p6.65
NL: 2.71E4 m/z= 197.5-198.5 MS cnt-03
19.80 20.64 21.19
2.08E3 rn/zr 197,5-198.5 MS cnt-02 ci)
0 C ci)
'C C
ii) > ci) ci)
60- 14.99 '9 '
'16.09 1685
50' I
40.1460 1524 -
14.28 1b31
30 14.25' ,I 1551
15.8117.41 1752
20 '1818:50 ? 876 1906 1964 2011
2060 20.96
1380 1391,
f.11
I 1012 76
1347 I -
I
1 I' . .' ' ' '
I : 0
..... :. II
100 .-- 15.3
----'
7.04E2 1577
rn/z - 197.5-
8O I r.L' . 198.5 MS
70I III I
14.80 I- crit-
01 060419 18.77 08748
14.29 17.38 50.: 14.25 1462 15.26 16.44
16.361742
18.71
20.51 2096 40:: 16.66 1678
17.641818
19.12
30,1506,
1 I.1iI16.93iH19 6 H 20.08
1
1377 I I 20 I
13.94 -I' ' ' '
12,7713_41.', H ri'.; .
H'T 'II I . .. II!:,
I i .y :._ ............................----------13 14 15 16 17 18 19
-
20 21 Time (mm) 34
KSC Engineering Directorate GC/MS
Materials Science Division Example - Halogens
• Obtained sample wanted to know if halogenated compound present - If present how much
• Direct Inject
• Very high level
• Used internal standard
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8.19 NL: 2.40E6 TIC MS ICISOII-02
8.81 8.01805
7 ° . ?1J? I \8 m 87
,. . ) 7.5 8.0 8.5 9.0
Time (mm)
95
1 d.o
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4 KSC Engineering Directorate GC/MS
Materials Science Division Example — Halogens
D:\Analysis\2006\0166\Oil-02 04112/06 04:57:04 PM 200 ppm TCLP B/N mix; 15 exposure: 1 mm desorb RT5.24 - 10.02 . --
.-.... -. .....--..---. . .---
100_ Tetrachloroethylene (unknown) 6.42 546
90
85
80
75 /
707
65-
60 a) 0 C a) 55 0 C
50
451 a) 1
401
35H1
207.
10
6.14
557 565 586599-
666 678 Or-
5.5 6.0 6.5 7.1
./ KSC Engineering DirectorateGC/MS
Materials Science Division Example - Shuttle
• Contamination on Shuttle Orbiter
• Connector failing conductivity
• Possible source of contamination identified
• Cotton swab used to obtain sample
• Extract swabs - including control
• Could not see by FTIR
• Injected standard
• Was able to ID contamination on the swabs
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KSC Engineering Directorate GC/MS
Materials Science Division Example - Shuttle
RT:169822O2 - -
100 2040 NL: 4.77E4
80: Sample 1 TIFCMS
05 060208
60 21.04 12137
19.36 19.60 2022 1 ° ?5i
::
17:32 17.48 17.90 i8.51852-
2070 /'-
39 -
- - -- 100-. 0.39 NL:
1.18E5 TIC MS
80 1 1,1-06
Sample 2 g60-
21.02 W4O
19.36 19.59 20.22 j \ 1 20- 19.01 19.21 . 1 19.75 1993 20.52
1888 206921.17
1712 1747 1788 - 1841 1851 34 2165
KSC Engineering Directorate GC/MS
,i Materials Science Division Conclusions
• Excellent method for low concentration organ ics in complex matrix - Can see low ppm or less - Separate out mixtures
• Must be able to be brought into gas phase - Evaporation - Degradation - Carried in gas stream
• Can/must pull sample out of sampling device (wipe, swab) - Extraction - Direct insertion probe - Pyrolysis (on order) - Headspace (on order)
• Cautions when using - Correct column selection (typically Rtx-5MS) - Temperature ramp on oven - Injector temperature - Mass range
• Complex spectra - Structural information (electron ionization - El)
> Library Matching > Compound determination
- Molecular weight information (chemical ionization - Cl) 39
KSC Engineering Directorate Chemical Analysis Materials Science Division
• Inorganic Organic
- Metals - Lubricants, Oils
- Elemental Analysis - Structural Analysis
- Chemical Bonds
• Identify Makeup of Materials - Help Determine Why Materials Act as They Do
• Determine Contamination - Originating From a Material
- Found onaSurface
• Gas Composition
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p"KSC Engineering Directorate
Gas Analysis Materials Science Division Example - Aft Gas
Orhit iii ('vlaiieuveiiny SystiruiReaction Control System Pod
LI] tJrnhilical\
Main Engines
--
L (c
'leat Shetd , Is
Ii-
Body tap
Structure
:1/! l'tiS(:i(lge Structure
Shell and Main Canted Frauie
3 BottIe side)
A ft 1•
Fuselage Access U oor
ThruSt ---Structure
--
Umbilical / Doors
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KSC Engineering Directorate Gas Analysis
Materials Science Division Example - Aft Gas
• Six Evacuated Bottles in Aft of Orbiter During Ascent
• Opened at Specific Times During Ascent
• Bottles Removed After Mission
• All Pressures Sub Ambient —2—l75torr
• Analyzed for Commodities of Interest for Main Engine - H2, He, 02, Ar, CH4, 00, 002 - Detection Limits of 0.01 %
• Used to Help Evaluate Main Engine Performance
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KSC Engineering Directorate Gas Analysis
Materials Science Division Example - Aft Gas
Utilizes GC/MS along with Custom Sample Inlet - Detect Parts-Per-Million of Commodities
- Monitor any Gas with Molecular Weight below 50 Daltons
- Can Be Sub Ambient
- Small Sample Volumes
- Performs Shuttle Aft Gas Analysis
T. I —i !
•
ft * '. •
F------
¶
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KSC Engineering Directorate Gas Analysis
Materials Science Division Example - Aft Gas
Sample Bottle Measured Oxygen Concentrations
With Redesigned Sample Bottle System (STS-71 thru STS-116)
20
19
18
17
16
15
14
11 G) C.) C 0
C
C)
5
4
3
2
0
Lower Oxygen Flammability Limit
No. 3 Right 112 ____
.V t34 • / /
/11/
.
No. 1 Right I 11.99
• ,/' -4-: •:.
•••• ••
r / : tW• •• •• /• *r9d. 6
.•• &v W. • •: • .• ••
______ No Left I INo. 2 Right° 215 fli.34 • I. _____
I ,,,l,,,I,,,
. No. I Left I 1.69 _____
I ,,,I, ,I.,,
•
I I
0 20 40 60 80 100 120 140 160 180 200 220 240
Pressure (Torr) 44
KSC Engineering Directorate
Conclusions Materials Science Division
Chemistry is an invaluable tool in ensuring safe launches.
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