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Chemical
Fingerprinting
Objectives and
Overview
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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 fardownstream
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
Challenge: Detecting subtle (but important)
changes in supplier material constituents
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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
Key is a chemical fingerprint that can be used to identify a material, todifferentiate 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
Diagnostic combination of analytical methods for
detailed characterization of a material
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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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TRANSITION PERIOD
Perform current and fingerprintingacceptance testingAccept material using current testing and specification
Evaluate new results periodically Transition when, ready to accept fingerprinting tests
IMPLEMENTATION
Select fingerprint limits Update specification
EVALUATE SIGNATURE
Downselect applicable techniques
Establish method/material variations Set preliminary fingerprinting limits
REVIEW RAW MATERIAL
Review existing data Contact supplier(s) Select analytical instruments Prepare test plans Compile database reference data
Phase IIImplementation
Laboratory Team
Material Team
Material 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
FingerprintingPlan Phase I
Development
Material Team
Material Fingerprinting Approach
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Chemical Fingerprinting
for the Reusable Solid
Rocket Motor (RSRM)at ATK Thiokol
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ATKThiokol 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 Systemmanipulates 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]
Fingerprinting for RSRM
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RSRM Components Involving Critical Materials
Forward
Center
Center
Aft
CastingSegments
Nozzle Protective Plug
Propellant
Segmented steel case
Movable nozzle
Case-bonded,composite solidpropellant
Elastomeric internalinsulation
Nozzle ablative liner
Nozzle insulator andstructural shell
Clean bonding surfaces
Effective adhesives
ALL RSRM materials and constituents
are critical and need to be monitored
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R&D Analytical
Laboratory
Instrumentationand Capability
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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 linearexpansion (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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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
Nondestructive Evaluation
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Fingerprinting
Analysis andDatabase
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RSRM Fingerprinting Data Management
Manual Data
Storage
Automated
Data Storage
Data Storage
Raw Da ta , conve rted GRAM S, and
other f i les are stored on the
se rve r. Quan t i ta t i ve da ta and
m a t e r i a l d e f i n i t i o n i n f o rm a t i o n i s
stored in Naut i lus.
Quantitative Data
Nautilus Lims Sy stem
MS Word or
Powerpo in tMerck IndexChemDraw
Excel
Spreadsheets
S c a n n e d I m a g e s
Fingerprinting Data Manipulation & Storage
PresentationManager
Fingerprinting V iew erFile Stora ge
Lan Se rve r
Au tomated
GRAMS
Converson
Fingerprint ing
Data LoaderLab Equipme nt
Manual
GRAMS
ConversionData i s manua l l y
o r a u t o m a t i c a l l y l o a d e d
in to the app rop ri a te
storage area.
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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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EPDM (ethylene-propylene-diene monomer) Usage in the booster motor
Material Example: Neoprene in EPDM Insulation
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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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0
r
595
r
714
r
764
r
835
r
19
r
185
r
168
r
331
r
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
0.065
0.070
0.075
0.080
0.085
r
1480149015001510152015301540
-1
Analysis Details: Fourier Transform
Infrared Spectra From Aging Study
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Fingerprinting
Successes andSummary
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Neoprene FB Secondary polymer used as a component in EPDM formulations
(material no longer produced)
Fingerprinting showed that under proper storage conditions - NeopreneFB could be stored over10 years and still meet specification
Storage at40rF, 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 distributionand the chemical composition
Similar 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
Material Fingerprinting Successes
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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 primes 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 curesystem
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 thanone 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