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010530ppt

ChemicalFingerprinting

Programfor RSRM Critical

MaterialsPresented by:

William H. McClennenDennis J. Fife

Michael O. KillpackRick P. Golde

September 16-18, 2002

ATK

THIOKOL PROPULSION

https://ntrs.nasa.gov/search.jsp?R=20020092098 2020-01-11T05:07:23+00:00Z

IIi I I I I I I THIOKOLPROPULSION

Presentation Outline

• Background

• Objectives andApproach

• Accomplishments

• Description of DatabaseViewer

• Success Stories

• Direct and AdditionalBenefits

• Continuing Challenges

• Acknowledgements

010971ppt

1

Propellant

,, THIOKOL PROPULSION

Reusable Solid Rocket Motor (RSRM)Components Involving Critical Materials

Forward

Center

Center

,CastingSegments

• Segmented steel case

• Movable nozzle

• Case-bonded, compositesolid propellant

• Elastomeric internal

insulation

• Nozzle ablative liner

• Nozzle insulator and

structural shell

• Clean bonding surfaces

• Effective adhesives

Nozzle Protective Plug

010971ppt

2

I II I I I I I I II THIOKOLPROPULSION

n _Background: Chemical Fingerprint Definitio ,IDiagnostic Combination of Analytical _,lleth_d,, _or

Detailed Characterization of a MateriaW

• Key importance is a chemical fingerprint that can be used ioidentify a material, to differentiate it from similar looking materials,or lead to its source

In the past, fingerprinting methods were used to characterize

materials and processes

Following a failure or noncompliance

Ad hoc, reactive, and incomplete generation and storage of data

Database scattered overdozens of file cabinets

Few techniques were ,-=O

adopted for receiving _inspection/process _---control =

___ ,'_ ............................. Proton

F

I ,

. HPLC

NMR

UlUY/lppt

3

ATI(_,_c.sY_ THIOKOL PROPULSION

Objectives of Chemical Fingerprinting(Recognize, Reduce, Resolve Problems)

• Detailed understanding of material composition

• Enhanced ability to detect changes in a material due to

vendor changes or subtler supplier changes

• Improved acceptance testing based on chemical composition

• Improved understanding of how a material works,ages, degrades, etc.

• Standardized approach to material fingerprinting

• Develop methods for monitoring all key ingredients

• Develop a comprehensive material database

• Reduced probability of unexpected and unrecognized

changes to critical materials and processes

I II I THIOKOL PROPULSION

Approach: State of Art Facilities

Chem ical Characterization• NMR (300 and 400 MHz)• Surface analysis

• ESCA/XPS

• Auger• SIMS• ISS

• RAMAN I FTIR/NIR• Metals analysis

• ICP emission• AA/GFAA• ICPMS

• X-Ray Fluorescence• Chromatography

• HPLC/HPLC-MS• GPC

• GC (variousdetectors)• GC-MS• Ion chromatography

• Flow injection auto analyzer• CHN OIS• Classical techniques• Asbestos identification

Thermal AnalysisMechanical PropertiesNon Destructive Analysis

010971ppt

5

I I I J I I III

Approach: Material Team

THIOKOL PROPULSION

Material SpecialistM&P Specialist

Design Engineer

Procurement Quality EngineerManufacturing EngineerProcess Control Lab

R&D Analytical LaboratoriesR&D Materials and Process

S&E Engineering

QualityOperationsQuality Lab (material receipt)

010971 ppt

6

, THIOKOL PROPULSION

Material Fingerprinting Approach

•.q.FECIFIC_'TION

• Select fingerprint limits

• Update specification

010971ppt

7

ATK_A_LLIANT TECHSYSTEM_S_

i ii THIOKOL PROPULSION

Data ManagementFingerprinting Data Manipulation aqd Storage

swordorilExo.iLcheo0r.wil e,cknd.xiPowerpoint Spreadsheets / ..

I I ' I, ,I I_°-"'°"'_Manual Data

Storage

I Manual I"GRAMS

ConversionData is manually

or automatically loadedinto the appropriate

storage area.

L_ib EClulpment:.: ,j v

I Automated

Data Storage

._ !FingerprintingData Loader

_TAutomated

GRAMS

Converson

* II

L

Data Storage

Quantitative Data

Nautilus Lims System

File Storage

_.,Lan Server

Raw Data, converted GRAMS, andother files are stored on theserver. Quantitative data andmaterial definition information isstored in Nautilus.

Presentation

Manager

FingerpfinlJng View er

010971ppt

8

ATKQ,_._c.__ . , , THnOKOLPRO_ULSUON

Database Components and Software(No Commercially Available Integrated System:

Integration and Data Parsing Developed Internally)

• Server-based PC Network: Novell ®

• Data loader and Viewer: developedsoftware programs internally usingPowerBuilder _

• Oracle ® database

• LIMS (Lab Information ManagementSystem) software: Nautilus ® R2B2.LabSystems

• Spectroscopic/Chromatographic Data Viewer:Grams/32 ® v. 7.0, LabSystems,Galactic Industries

Ion Chromatography Analysis

010971ppt

9

I I I I ii THIOKOL PROPULSION

Accomplishments: RSRM Fingerprinting Materials

• 55 Materials completed or in process• 11 Solvents or cleaning solutions

• Phenolic resin-and 3 phenolic composites

• 4 Compounded rubber insulations

• 2 Propellant systems

• 10 Polymeric components

• 3 Sealants and ablative compounds• 5 Rubber adhesives

• 3 Epoxy based adhesives

• 5 Paints and primers

• 7 Inorganic fillers, abrasives and reactive components

• 1 Corrosion inhibiting grease

010971ppt

10

ATK_.,_c,sY_._ ....... THIOKOLPROPULSION

Accomplishments: Database Viewer Features

• Executive view

• Material overview, reference documents, dataexamples

• Method information

• Chemical characterization methods

• Component information

• Trend analysis and visualization of keyanalytes

• Method quality control

• Trend analysis of QC parameters

• View comparison

• Direct graphical overlay of raw spectroscopicand chromatographic data

• Lab notes

01_71ppt

11

THIOKOLPROPULSION

Material Fingerprinting Success Example

Neoprene FB• Secondary polymer used as a component in case insulation EPDM

formulations

• Material no longer produced

• Fingerprinting showed that under proper storage conditions: Neoprene FBcould be stored over 10 years and still meet specification

• Storage at 40°F, low humidity, and minimal light

• Stockpiled 100,000 Ib till new EPDM formulation can be qualified

• Test methods developed to ensure material is well within specification

• Viscosity measurement.performed as a check at the vendor's storage site, whilethe GPC and. FTIR analyses confirm the molecular weight distribution and thechemical composition

• Defense program experienced solvating problem with gum stock forcarbon fiber EPDM

• Fingerprinting knowledge allowed immediate identification of the problem

• Corrective action given on controlling Neoprene FB

010971 ppt

12

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THIOKOLPROPULSION

Material Example: Neoprene FB in EPDMEPDNI Usage in Booster Motor

Systems Tunno! /

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010971ppt

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II I I II

THIOKOL PROPULSION

Component Info: Analyte Trends.., . . . .

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Executive View J Method Information Component Info J Method QC J View ComparisonsJ Lab Notes J

Project JR&D. Acceptable

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Project: R&D, Acceptable Test Method: Neoprene - Brookfield Viscosity

Analyte: Brookfield Viscosity (50C) Avg: 786000 Sigma: 77400 Max: 956000 Min:613000

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16

THIOKOL PROPULSION

Method QC: Duplicate GPC Analysis Trends

i Executiv e view ! Methoci Infoimaiion i Component ,nfo Method QC I View Comparison, I Lab Notes l

Lab IR_D Lab [_J

TestMethods IN eoprene FB-G PC Analy_i_

.: Anaiyte I RPD-MWw{RI} I;I

!'QC Parameter _=_'-_iii_iiiiiiii_iiiiiiiiiiiiiiiiiiiiiiiii_iiiiiiiiii._J

,_ Units JRPD I'1

Display Values I

Print Values & Graph Ir

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Lab: RS,D Lab Test Method: Neoprene FB - GPC Analysis Analyte: RPD - Iv_ (RI)

QC Parameter: IDUP Units: RPD Avg: 1.1 Sigma: 0.498 Max: 1.8 Min:0.6

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+2 sigma -2 sigma +3 sigma - -3 sigma average O sample data

010971 ppt

17

, THIOKOL PROPULSION

View Comparison: FTIR Data

File Edit View Insert Notebase Applications Add-0_ns Tools

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Help

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18

THIOKOL PROPULSION

Analysis Details: FTIR Spectra FromAging Study

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cm-1

t !

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1480

010gT Ippt

19

, THIOKOL PROPULSION

Material FingerprintingSuccesses/Improvements (cont'd)

HC polymer, carboxy terminated polybutadiene (CTPB)• This liquid polymer is used in the liner that bonds the propellant to the

case insulation.

• Understanding the details of the polymer and the manufacturing processenabled analysts to identify a noxious byproduct at increased levels that

was making operators sick.

• The bad lot was taken out of production and a corrective action was developed toimprove the vendor's manufacturing process.

• A detection and quantification method with new limits for the byproduct is in place foracceptance of future lots.

• In-depth fingerprinting knowledge has also been invaluable for thedevelopment of the replacement after current vendor announced theclosure of their HC polymer plant.

• Initial carboxy terminated polybutadiene (CTPB) received from a new vendor showeddistinct differences from HC polymer in small acids and molecular weights.

• Recommendations to improve reaction mixture ratios as well as process washing anddrying have enabled new vendor to produce acceptable polymer, now being tested foruse on RSRM.

• Also developing acceptance testing and spec limits for both commercial and defenseprograms with this new material.

010971 ppt

2O

ATI(_A_LLIANT TECHSYSTEM_S_

THIOKOLPROPULSION

Material FingerprintingSuccesses/Improvements (cont'd)

BRULIN 1990 GD-T

• ODC replacement for methyl chloroform vapor degreasing

• Water-based solvent used with spray-in-air technology

• Several issues developed with material during certification

• Material received with insoluble material in drums

• Material received with lower than expected pH

• Vendor asked for site visit from Thiokol's chemist

• Knowledge from fingerprinting provided information to stabilize product throughsmall changes in use of de-ionized water, mixing steps, and cycles

• Use of hydrated silicates

• Recommendation for KOH add back to spray-in-air baths

• Increased useable bath life from 8 to 90 days

• Knowledge from fingerprinting effort provided suggestion for corrosioninhibitor rinse cycle (new inhibitor currently qualified)

010971ppt

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ATK_A_LUANT TECHSYSTEM_S_

THIOKOL PROPULSION

Material FingerprintingSuccesses/Improvements (cont'd)

MAPO (Methyl Aziridinyl Phosphine Oxide)

® Used as a curative for the liner between insulation and propellant

• Recent Lot received with incomplete certification

• Acceptance testing indicated material was out of specification forreactive imine, hydrolyzable chloride and total chloride

• Additional tests were done per the fingerprinting SLP thatsupported the previous testing and included GPC data that-beganto suggest the nature of the problem

• Further testing using more detailed techniques (HPLC/MS)developed through fingerprinting in R&D Labs identified the processby-product impurities and aided vendor in finding a resolution

• Material returned to vendor for reprocessing

01 O971 ppt

22

" ATK_LLIAN T TECHS YSTE _MS_

. THIOKOL PROPULSION

Material FingerprintingSuccesses/Improvements (cont'd)

TCA - Methyl Chloroform

• Ozone Depleting Chemical (ODC) TCA has limited availability due torestrictions for defined essential use.

• A large amount of stored TCA had exceeded its shelf life anddeteriorated out of specification.

• Distillation was proposed as a recovery technique, but there was uncertaintyon its effects on the stabilization components.

• Fingerprinting analyses were able to prove the distilled material acceptableto NASA.

• Basic understanding has also identified problems with long-term

storage of the TCA from a second source due to incompatibilitybetween two components in its stabilizer package.

• Currently working with vendor, design and manufacturing engineersto assess new methods for storage to ensure this critical solvent willbe available until a replacement solvent can be qualified or, if

necessary, for the life of the RSRM program.

010971ppt

23

ATI(_UANT TECHSYSTEM_

THIOKOL PROPULSION

Material FingerprintingSuccesses/Improvements (cont'd)

• Corrosion inhibiting grease from new plant verified with FTIR• Vendor tried a new formulation but reverted to original catalyst after

fingerprinting confirmed it gave most consistent result

• D-limonene containing solvents removed from use on uncuredrubber after testing confirms degradation of cure system

• BHT identified as a minor additive to inhibit d-limonenedegradation in solvents

• Detailed fingerprinting of rubber to metal adhesives hasprovided new insight into aging processes plus new ways tomonitor aging• Aging studies indicate resin interaction as early step in degradation

• Significant reduction in shelf life with certain environments

•• New methods provide early warning of potential problems

010971ppt

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.... THIOKOL PROPULSION

Direct Benefits of Fingerprinting• Fundamental understanding of critical materials that often

equals or exceeds vendor's knowledge• Provide baseline chemical profile of materials in use

• Material changes can often be traced to their source

• Standardized approach including:.• Material team for focus and relevance

• Flexible test plan for method adaptation or development

• Laboratory team for technical expertise

• Final report and R&D procedures to document methoddevelopment

• SLP of key down-selected robust methods in standard format forroutine use in Process Control Lab

• Material team technical ownership• Analytical chemist as material specialist

• Improved communication between procurement, work centers,quality and labs

010971p_

25

THIOKOL PROPULSION

Additional Benefits of Fingerprinting

Versatile database broadly available both for new lotcomparison and problem solving

• Available plant-wide and informative on many levels of detail

• Trending of key parameters and. QC data as.well as.detailedoverlay

• Lot-to-lot consistency monitored and changes flagged

• Security functions provide protection for vendor proprietaryinformation

• Improved vendor relationships through data and methodsharing

• New methods shared with vendors to enhance their capabilities

• Vendors acknowledge our expertise and expand cooperation bytimely reporting of planned changes

• Greater efficiency and confidence in requalification/qualification of materials due to obsolescence or changesin vendor or production site

010971ppt

26

I I i

Continuing Challenges

• Down selection for Process Control Lab

• Basic chemical characterization

THIOKOL PROPULSION

• Methods robust and simple enough for routine analysis

• Key component information - what is likely to go wrong next

• History of materials and vendors

• Dependable crystal ball

• Implementation in Process Control Lab

• Training at higher level of technical expertise

• Greater demands on LIMS and data entry

• Setting limits for new acceptance criteria

• Data utilization

• Continuing education of vendors and engineers

010971ppt

27

•

Acknowledgements

THIOKOL PROPULSION

• Vision of NASA/MSFC and

Thiokol management to seethe benefits ofa formal

Fingerprinting Program

• NASA funding throughMarshall Space Flight Center

• Datasharing cooperation ofmaterial vendors

• Analytical efforts of Thiokolmaterial specialists,scientists, and engineers

010971ppt

28