# Presentation: 036331

## Chemical Fingerprinting for Critical Material

**Constituents**

**December 2003**
**Process Control Focus Group Toolbox**

## Chemical Fingerprinting Objectives and Overview 

## 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

- 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

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

## 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

- 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

- Diagnostic combination of analytical methods for
- detailed characterization of a material

## 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

**TRANSITION PERIOD**
-  Perform current and “fingerprinting”acceptance 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

**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 II**
- Implementation

**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

**Fingerprinting Plan Phase I**
- Development

**Material Team**

**Material  Fingerprinting  Approach**

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

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

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

**Fingerprinting for RSRM**

## 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

## 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**

## Thermal Analysis

**D****ifferential scanning calorimetry**** (DSC)**
**Microcalorimeter**
**Accelerating rate calorimeter**** (ARC)**
**Adiabatic calorimeter**
**Thermal mechanical analysis**** (TMA)**
**Thermogravimetric analysis (****TGA)**
**TGA/M****ass spectrometer**** (MS)**
**Pyrolysis ****gas chromatograph / Mass spectrometer**** (GC/MS)**
**Thermal conductivity**
**Strand burner**
**Window bomb**
**Quench bomb**
**Material compatibility**
**Specialized instrumentation**

## 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 **

##   Nondestructive Evaluation 

**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**** **

## Fingerprinting Analysis and Database 

## RSRM Fingerprinting Data Management

## 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**

## Material Example: Neoprene in EPDM Insulation

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

**Material Example: Neoprene in EPDM Insulation**

## Executive Screen for Neoprene FB

**Executive Screen for Neoprene FB**

## Method Information Screen

**Method Information Screen**

## Component Info: Analyze Trends

**Component Info: Analyze Trends**

## Method QC: Duplicate Gas Permeation Chromatography  Analysis Trends

**Method QC: Duplicate G****as Permeation ****Chromatography****  Analysis Trends**

## View Comparison: Fourier Transform Infrared Data

**View Comparison: ****Fourier Transform Infrared ****Data**

## Analysis Details: Fourier Transform Infrared Spectra From Aging Study

**Analysis Details: ****Fourier Transform ****Infrared**** Spectra From Aging Study**

## Fingerprinting Successes and Summary 

## 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

- 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

**Material Fingerprinting Successes**

## 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)

## 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

## 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

## 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