A Chemical Fingerprinting Database for RSRM Critical Materials

1
Chemical Fingerprinting for Critical
Material Constituents
December 2003 Process Control Focus Group Toolbox
2
Chemical Fingerprinting Objectives and Overview
3
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

4
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)

5
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

6
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.

7
Material Fingerprinting Approach
Laboratory Team
Material Team
Fingerprinting Plan Phase I Development

• 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

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

Phase II Implementation
Material Team
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

• EVALUATE SIGNATURE
• Downselect applicable techniques
• Establish method/material variations
• Set preliminary fingerprinting limits

• IMPLEMENTATION
• Select fingerprint limits
• Update specification

8
Chemical Fingerprinting for the Reusable Solid
Rocket Motor (RSRM) at ATK Thiokol
9
Fingerprinting for RSRM

• ATK Thiokol uses a comprehensive system to
  fingerprint critical materials supporting the
  RSRM
• Extensive instrumentation and capabilities in RD
  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, rick.golde_at_atk.com -
  or
• Glen Curtis 435-863-6954, glen.curtis_at_atk.com

10
RSRM Components Involving Critical Materials

• 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

11
RD Analytical Laboratory Instrumentation and
Capability
12
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)

13
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

14
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

15
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

16
Fingerprinting Analysis and Database
17
RSRM Fingerprinting Data Management
18
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

19
Material Example Neoprene in EPDM Insulation
EPDM (ethylene-propylene-diene monomer) Usage in
the booster motor
20
Executive Screen for Neoprene FB
21
Method Information Screen
22
Component Info Analyze Trends
23
Method QC Duplicate Gas Permeation
Chromatography Analysis Trends
24
View Comparison Fourier Transform Infrared Data
25
Analysis Details Fourier Transform Infrared
Spectra From Aging Study
26
Fingerprinting Successes and Summary
27
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 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

28
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)

29
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

30
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

31
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