Chemical

Fingerprinting for
Critical Material
Constituents
December 2003
Process Control Focus Group Toolbox
 Chemical
Fingerprinting
Objectives and
Overview
 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)

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 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

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 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.

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 Material Fingerprinting Approach
Laboratory Team
Material Team Fingerprinting
REVIEW RAW MATERIAL Plan Phase I GENERATE TOTAL SIGNATURE
• Review existing data Development • Develop analytical methods
• Contact supplier(s) • Sampling
• Select analytical instruments • Sample preparation/separation
• Prepare test plans • Instrument operation
• Compile database reference data • Determine precision and accuracy
• Establish quality controls
• Document analytical test methods
• Provide training/transfer to the QA lab

Phase II
Implementation Material Team
Material Team
TRANSITION PERIOD
EVALUATE SIGNATURE • Perform current and “fingerprinting”acceptance testing
• Downselect applicable techniques • Accept material using current testing and specification
• Establish method/material variations • Evaluate new results periodically
• Set preliminary fingerprinting limits • Transition when, “ready to accept fingerprinting tests”

IMPLEMENTATION
• Select fingerprint limits
• Update specification

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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 Golde: 435-863-3423, [email protected] - or
 Glen Curtis: 435-863-6954, [email protected]

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 RSRM Components Involving Critical Materials
 Segmented steel case
 Movable nozzle
 Case-bonded,
composite solid
Forward propellant
 Elastomeric internal
Propellant
insulation
Center
Casting
Segments
 Nozzle ablative liner
 Nozzle insulator and
Center structural shell
Aft
 Clean bonding surfaces
 Effective adhesives

ALL RSRM materials and constituents

Nozzle Protective Plug
are critical and need to be monitored
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 R&D Analytical
Laboratory
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)
• Classical techniques
• Asbestos identification
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 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
•Fourier transform infrared
•SurfMap-II
•Thermal Imaging
•Sensors
•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

MS Word or Excel
ChemDraw Merck Index
Powerpoint Spreadsheets
Scanned Images

Manual Data Data Storage

Storage
Quantitative Data Presentation
Manual Manager
GRAMS
Conversion
Data is manual ly
or automaticall y loaded
into the appropriate
storage area.
Nautilus Lims System

File Storage Fingerprinting Viewer

Automated
Data Storage

Fingerprinting
Lab Equipment Data Loader
Lan Server

Automated Raw Data, converted GRAMS, and

GRAMS other files are stored on the
server. Quantitative data and
Conv erson material definition information is
stored in Nautilus.

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 Database Viewer Features
 Executive View
 Material overview, reference documents,
data examples
 Method Information
 Chemical characterization methods
 Component Information
 Trend analysis and visualization of key analytes
 Method Quality Control
 Trend analysis of QC parameters
 View Comparison
 Direct graphical overlay of raw spectroscopic
and chromatographic data
 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

0.050
835 hr
764 hr
714 hr

0.045
595 hr

0.040
331 hr

0.035

0.030

0.025
185hr

0.020

0.015
168 hr

0 hr
19 hr

0.010

1540 1530 1520 1510 1500 1490 1480

cm-1

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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 40F, 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 vendor’s 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
 Vendor requested site visit by prime’s chemist
 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
 Recommendation for additive to spray in air baths
 Increased useable bath life from 8 to 90 days
 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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