Chemical Fingerprinting for Critical Material Constituents

December 2003 Process Control Focus Group Toolbox

Chemical Fingerprinting Objectives and Over view

Challenge: Detecting subtle (but important) changes in supplier material constituents

Basic Problem: Raw materials (polymers, adhesives, cleaners) meet specifications, but are different enough to cause manufacturing or flight performance issues, for example:

Multiple cases of silicone contamination on various process materials from vendor changes in end item materials Differences from unplanned or unknown vendor process changes, contamination, or changes at sub-tier suppliers

Lesson Learned: Supplier process changes or contamination can produce in-spec materials that are subtly (but critically) different and can cause significant problems with hardware far downstream Solution: Fingerprint material to screen important end items and process materials; provide ongoing assurance that nothing creeps into processes to surprise at a later date
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Material Component Team

Multi-function teams define materials to fingerprint and methods to accomplish Material team representation may include:

Material Specialist / Material and Process Specialist Design Engineer Procurement Quality Engineer Manufacturing Engineer Process Control Lab Research and Development Analytical Laboratories Quality Operations Quality Lab (Material Receipt)

Fingerprint Definition
Diagnostic combination of analytical methods for detailed characterization of a material

Key is a chemical fingerprint that can be used to identify a material, to differentiate it from similar looking materials, or lead to its source Fingerprinting methods used to characterize materials and processes
Following a failure or noncompliance Ad hoc, reactive, and incomplete generation and storage of data Database scattered over dozens of file cabinets Few techniques were adopted for receiving inspection/process control

Objectives of Chemical Fingerprinting

Enhanced understanding of material composition Standardized approach to material evaluation Develop a comprehensive material characterization database Reduced probability of unexpected and unrecognized changes to critical materials and processes Enhanced ability to detect subtle changes in a material and its chemical makeup due to factors such as:

Material obsolescence Ozone depleting compound (ODC) and other environmental issues Sub-tier supplier changes

Better understand how a material works, ages, degrades, etc.

Material Fingerprinting Approach

Material Team
REVIEW RAW MATERIAL Development Review existing data Contact supplier(s) Select analytical instruments Prepare test plans Compile database reference data

Fingerprinting Plan Phase I

Laboratory Team
GENERATE TOTAL SIGNATURE Develop analytical methods Sampling Sample preparation/separation Instrument operation Determine precision and accuracy Establish quality controls Document analytical test methods Provide training/transfer to the QA lab

Phase II
Material Team
EVALUATE SIGNATURE Downselect applicable techniques Establish method/material variations Set preliminary fingerprinting limits

Implementation

Material Team
TRANSITION PERIOD Perform current and fingerprintingacceptance testing Accept material using current testing and specification Evaluate new results periodically Transition when, ready to accept fingerprinting tests

IMPLEMENTATION Select fingerprint limits Update specification 7

Chemical Fingerprinting for the Reusable Solid Rocket Motor (RSRM) at ATK Thiokol

Fingerprinting for RSRM

ATK Thiokol uses a comprehensive system to fingerprint critical materials supporting the RSRM Extensive instrumentation and capabilities in R&D analytical laboratories defined optimal fingerprinting methods RSRM Fingerprinting Data Management System manipulates and stores computerized profiles of materials Following slides outline techniques and systems used

For additional information, contact

Rick Glen

Golde: 435-863-3423, rick.golde@atk.com - or Curtis: 435-863-6954, glen.curtis@atk.com

RSRM Components Involving Critical Materials

Forward

Propellant Center Casting Segments

Center Aft

Segmented steel case Movable nozzle Case-bonded, composite solid propellant Elastomeric internal insulation Nozzle ablative liner Nozzle insulator and structural shell Clean bonding surfaces Effective adhesives

Nozzle Protective Plug

ALL RSRM materials and constituents are critical and need to be monitored
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R&D Analytical Laborator y Instrumentation and Capability

Chemical Analysis

Nuclear magnetic resonance (NMR) (300 and 400 MHz) Surface analysis

Electron spectroscopy for chemical analysis X-ray photoelectron spectroscopy (ESCA/XPS) Auger Secondary ion mass spectrometry (SIMS) Ion scattering spectrometer (ISS)

RAMAN / Fourier transform infrared (FTIR) / Near infrared (NIR) Metals analysis
Inductively coupled plasma (ICP) emission ICP-Mass spectrometer (MS) Atomic absorption/Graphite furnace atomic absorption (AA/GFAA)

X-Ray Flow injection auto analyzer Element analysis (carbon, hydrogen, nitrogen, oxygen, sulfur) Chromatography

High-performance liquid chromatography (HPLC) /HPLC-MS Gas permeation chromatography (GPC) Gas chromatography (GC) (various detectors) Gas chromatography - Mass spectrometer (GC/MS) Ion chromatography (IC)
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Classical techniques Asbestos identification

Thermal Analysis

Differential scanning calorimetry (DSC) Microcalorimeter Accelerating rate calorimeter (ARC) Adiabatic calorimeter Thermal mechanical analysis (TMA) Thermogravimetric analysis (TGA) TGA/Mass spectrometer (MS) Pyrolysis gas chromatograph / Mass spectrometer (GC/MS) Thermal conductivity Strand burner Window bomb Quench bomb Material compatibility Specialized instrumentation
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Mechanical Properties Characterization

Mechanical testing equipment

Five servo-hydraulic machines Nine electro-mechanical machines Two DMA spectrometers Impact testers

Tensile properties Dynamic properties Fracture energy Hardness Thermal coefficient of linear expansion (TCLE) Volume dilatation Environmental control Test rates to 10,000 ipm Simulation to full-scale article testing Machining and sample preparation Aging
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Nondestructive Evaluation
Surface Characterization Systems Eddy Current Ultrasonics Thermal Imaging Sensors
Fourier transform infrared SurfMap-II

Fiber Optic Strain Systems Mid IR Fiber Optic Chemical Sensing Piezoelectric Sensors Acoustic Waveguides

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Fingerprinting Analysis and Database

RSRM Fingerprinting Data Management

Fingerprinting Data Manipulation & Storage
M Wr o S od r P wr o t o ep in Ecl xe S r a s et pe d h es C e Da hm r w Mr kIn e ec d x
Scanned Images

Manual Data Storage Mn a aul GA S RM C n es n o v r io

Data Storage
Quantitative Data

Pe e t t n r s naio Mn g r aae

Data is manually or automatically loaded into the appropriate storage area.

Nautilus Lim System s

Automated Data Storage F gr r t g in epinin Dt L a e aa o d r

File Storage

Fin epinin Vie e gr r t g w r

Lab Equipment

Lan Server

A t mt d uo ae GA S RM C n es n ovro

Raw Data, converted GRAMS, and other files are stored on the server. Quantitative data and material definition information is stored in Nautilus.

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Database Viewer Features

Executive View

Material overview, reference documents, data examples Chemical characterization methods Trend analysis and visualization of key analytes Trend analysis of QC parameters Direct graphical overlay of raw spectroscopic and chromatographic data

Method Information

Component Information

Method Quality Control

View Comparison

Lab Notes

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Material Example: Neoprene in EPDM Insulation

EPDM (ethylene-propylene-diene monomer) Usage in the booster motor

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Executive Screen for Neoprene FB

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Method Information Screen

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Component Info: Analyze Trends

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Method QC: Duplicate Gas Permeation Chromatography Analysis Trends

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View Comparison: Fourier Transform Infrared Data

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Analysis Details: Fourier Transform Infrared Spectra From Aging Study

0.085 0.080 0.075 0.070 0.065 0.060 0.055 Absorbance

0.035 0.030 0.025 0.020

331 hr

0.040

595 hr

0.045

168 hr

0.010

1540

19 hr

1530

1520

1510 cm-1

0 hr
1500

0.015

185hr

714 hr

764 hr

835 hr

0.050

1490

1480

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Fingerprinting Successes and Summary

Material Fingerprinting Successes

Neoprene FB
Secondary polymer used as a component in EPDM formulations (material no longer produced) Fingerprinting showed that under proper storage conditions - Neoprene FB could be stored over 10 years and still meet specification

Storage at 40F, low humidity, and minimal light Stockpiled 100,000 lbs 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 vendors storage site, while the GPC and FTIR analyses confirm the molecular weight distribution and the chemical composition

Similar program experienced solvating problem with gum stock for carbon fiber EPDM
Fingerprinting knowledge allowed immediate identification of the problem Corrective action given on controlling Neoprene FB

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Material Fingerprinting Successes

Brulin 1990 GD

Environment-friendly 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 Knowledge from fingerprinting provided information to stabilize product through small changes in use of de-ionized water, mixing steps and cycles Use of hydrated silicates Increased useable bath life from 8 to 90 days

Vendor requested site visit by primes chemist

Recommendation for additive to spray in air baths

Knowledge from fingerprinting effort provided suggestion for corrosion inhibitor rinse cycle (new inhibitor currently qualified)
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Material Fingerprinting Successes

Carbon Cloth Phenolic (CCP)

Carbon cloth prepreg phenolic resin used to fabric nozzle components Test methods developed to enhance characterization of phenolic resin
Detailed

analysis of CCP prepreg enables monitoring of compositional factors that can affect material behavior

ITGA (Isothermal Gravimetric Analysis) - new method to quickly determine adequate carbonization of cloth
Test

discriminates material propensity for pocketing

Eddy current method developed to measure cloth carbonization in cloth and prepreg materials

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Material Fingerprinting Successes

HD2 grease from new plant verified

Conoco tried new formulation, but reverted to original catalyst after fingerprinting confirmed it gave most consistent result

D-limonene containing solvents removed from use on uncured rubber after testing confirmed degradation of cure system BHT identified as a minor additive to inhibit d-limonene polymerization in PF degreaser Chemlok aging studies based on FTIR suggests that one resin component shows significant degradation in less than one year after exposure to ambient air

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General Benefits of Fingerprinting

More fundamental understanding of critical materials Provide baseline chemical profile of materials in use Lot-to-lot consistency can be monitored and changes flagged Material changes can be traced to their source Acceptance testing for small supplier who cannot afford lab support Instills technical ownership for critical materials Enhances re-qualification of changes at vendor or production Improved vendor relationship through data sharing Database available for failure analyses

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