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

3

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

4

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

5

KSC Engineering Directorate

Chemical Analysis Materials Science Division

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

7

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)

1

r

9

: - --. i k •

1

' KSC Engineering Directorate Inorganic Chemical Analysis

Materials Science Division (Spot/Surface)

l/fl

:'I

10

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

11

KSC Engineering Directorate Organic Chemical Analysis Materials Science Division

Fourier Transform Infrared Spectroscopy (FT-IR)

-

12

KSC Engineering Directorate Organic Chemical Analysis Materials Science Division

Gas Chromatography Mass Spectrometry (GCIMS)

1

E D

I.

I 1.1111+11-,.

U

U

13



14

KSC Engineering Directorate Materials Science Division (Composition of Material)

Work Flow

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.

16

KSC Engineering Directorate Cadmium Plated Bolts Materials Science Division -________________________________

Multi-discipline Analyses Required

• Chemical Composition • Coating Thickness Determination • Hardness • Tensile Strength

17

KSC Engineering Directorate Cadmium Plated Bolts


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

KSC Engineering Directorate Cadmium Plated Bolts Materials Science Division

19

-

New Screw

Used Screw

- . ,... . .....

2

KSC Engineering Directorate Cadmium Plated Bolts / Materials Science Division

.s;

20

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.

21



22

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

23

Work Flow (Contamination) KSC Engineering Directorate


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

25

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

26

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

27

/)

- - __.l i 'u• - •. -

('. p

1%6

0 r?



Figure 1. Figure 2. Sample location of the Failed Cable Splice Sample Locations of Non-Failed Wire

28



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



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

30

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

31

,,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)


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

33


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


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

35

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

36

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

37

38


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


,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

40

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

41

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

42



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------

¶

43



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


Conclusions Materials Science Division

Chemistry is an invaluable tool in ensuring safe launches.

45

KSC Engineering Directorate Links


-http://www.nasa.qov/externalflash/a pollol 1/ittidexi .html

http://www.nasa.qov/mission paqes/constellation/multimedia/index.html

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