Production Control Effect on Composite Material Quality and Stability

John Tomblin, Yeow Ng, Beth Clarkson, Allison Crockett

The Joint Advanced Materials and Structures Center of Excellence

Production Control Effect on Composite Material Quality and Stability

Motivation and Key Issues
Quality control tests on prepreg or lamina (i.e. receiving inspection or acceptance tests) may not always detect material defects Material suppliers (e.g. fiber, resin, prepregger, etc.) and part fabricators need to have an understanding of each others roles and responsibilities

Objectives
Develop essential information on the nature of the controls required at various producer levels to assure the continuation of stable and reliable composite raw material for aerospace usage
Develop and clarify requirements

Provide guidance to NASAs National Center for Advance Materials Performance (NCAMP)

Approach
Develop production control guidelines Use NCAMP as the proofing ground Document what works and what doesnt Define aerospace grade
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FAA Sponsored Project Information

Principal Investigators & Researchers
John Tomblin, Yeow Ng, Beth Clarkson, Allison Crockett

FAA Technical Monitor

Curtis Davies

Other FAA Personnel Involved

Larry Ilcewicz, Peter Shyprykevich (retired), Lester Cheng, Evangelina Kostopoulos, and David Ostrodka

Industry Participation
40 Aircraft Companies & Tier-1 Suppliers 16 Material Suppliers

Other Partners
CMH-17 (formerly MIL-17), SAE P-17, SAE PRI Nadcap, SAE PRI QPL, ASTM D30 University of British Columbia and Center for Nondestructive Evaluation at Iowa State University
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Material Key Characteristics (KC) and Key Process Parameters (KPP) Monitoring

Developed protocols to monitor KC and KPP variations over time

Control Chart

Everything varies at least a little bit. So how do you tell when you are just experiencing normal variation versus when something out of the ordinary is occurring? Control charts were designed to make that distinction As long as all points lie inside the upper and lower control limits, the variation is presumed to be normal or a common cause variation. When a data point falls outside those limits, its time to look for a reason for the variation Two-sided monitoring for all properties including strength
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Example Control Chart

X-bar Chart for Fill Compression ETW

78 76 UCL = 76.34 CTR = 72.53 LCL = 68.72

X-bar

74 72 70 68 0 10 20 30 40 50

Subgroup
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Advantages of Control Charts

Ideally the control limits lie inside the spec limits.

Then the manufacturer can respond to the any out-of-control condition PRIOR to any out-of-spec product being produced.

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X-Bar Chart for Fill Compression ETW with 6 sigma spec limit added
78 76 74 X-bar 72 70 68 66 64
1 11 21 31 41 51

Subgroup

X-bar

UCL

LCL

6 Sigma Limit

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Control Limits & Acceptance Criteria

Acceptance Criteria is set such that the producers risk is 0.01 (per DOT/FAA/AR-03/19) Control limits are set at 3 standard deviations, corresponding to producers risk of 0.003 Thus, the acceptance limit is set tighter than the traditional control chart limits.
The use of modified CV (larger than measured CV) to establish specification limits may minimize this problem (i.e. reduce false alarm rate) Retest may minimize the problem (but retest is not typically used in SPC) Should producers risk be reduced from 0.01 to 0.001? More industry experience is needed to devise a solution!
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X-Bar Chart for Fill Compression ETW with acceptance limit added
78 76 74 X-bar 72 70 68 66 64
1 11 21 31 41

Subgroup

X-bar

UCL

LCL

= .01

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Investigate the Applicability of Western Electric Rules

Rule 1: A single point falls on or outside the 3 sigma limit. Rule 2: Two out of three consecutive points fall in zone A or beyondall on the same side of the center line. Rule 3: Four out of five consecutive points fall in zone B or beyondall on the same side of the center line. Rule 4: Eight consecutive points fall in zone C or beyondon the same side of the center line. Rule 5: A long series of points (about 14) are high, low, high, low, without any interruption in the sequence. (Systematic variables.)
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Investigate the Applicability of Western Electric Rules

Rule 6: Seven consecutive points all increasing or all decreasing. (monotonically is a stricter requirement) Rule 7: Fifteen or more consecutive points fall in zone C either above or below the centerline. (Stratification) Rule 8: Eight consecutive points fall on both sides of the centerline, with none falling in zone C. (Mixture pattern)

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Prepreg PCD Preparation Guide

A guide for prepreg material suppliers to prepare a prepreg process control document (PCD) A prepreg PCD is a recipe for the production of prepreg
Defines qualified raw materials, equipment, production parameters, etc. HIGHLY PROPRIETARY
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Prepreg PCD Preparation Guide

PCD is used to control the prepreg material properties and to manage changes Reviewed by the FAA, CMH-17, SAE P-17, material suppliers and major aircraft companies Matured guidelines will be incorporated into the final report of this project

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Co-efficient of Variation (CV)

CV is the standard deviation divided by the mean.

S CV = x
If CV is erroneously high we will accept too many bad materials If CV is erroneously low we will reject too many good materials
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Modified C.V. Approach

The variation inherent to all processes can be partitioned into several sources. Two potential sources of variation that are NOT included in the qualification sample:
Variation due to the testing process; all samples are tested within a short period of time (unrelated to material property variation) Variation due to the prepreg production process; all 3 or 5 batches of qualification prepreg are produced within a short period of time (related to material property variation)

Modified CV is used to compensate for variation not captured in material qualification process

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Effects of Modified CV
In order to compensate for the additional variation, the CV is increased PRIOR to computing the A and B basis values. The effect of this will be:
Slight decrease in the computed A-basis and Bbasis values, thereby increasing the margin of safety when designers use those values. Slight decrease in pass/fail limits, thereby decreasing the number of failures during equivalence and material acceptance.

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CV Modification Formula
If CV < 4%:
Modified CV = 6%

If CV is between 4% and 8%, adjust upward according to the following formula:

Modified CV = CV + 4%

If CV is between 8% and 10%:

Modified CV = CV

If CV > 10%:
Modified CV = 10%
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Comparison of CVs

12%

10%

Value of C.V.

8%

6%

4%

2%

0%

Calculated CV

Modified CV

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Investigate the Effects of Modified CV Approach

Currently approved for short-term use only What are the effects of long-term use?
Desirable or undesirable? What are the implications on material property control? What are the implications on building block approach? What if material suppliers & users agree to use modified CV forever?

Need balance between tolerable level of rejection rate and acceptable level of quality
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Prepreg Aging Study

Age may affect producibility and part quality Modern parts are larger and require longer handling life and staging life A reliable and simple method of measuring prepreg age is highly desirable

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Prepreg Aging Study

Collaboration with University of British Columbia, Toray Composites America, Avpro, and Center for Nondestructive Evaluation at Iowa State University Prepreg aged (exposed to out-time) at Wichita State University and sent to collaborating partners in dry ice PLAN: Incorporate the effects of aging into process modeling
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Aged prepregs were sent to participating members in dry ice (Prepreg: Toray T700SC 2510 PW)

Freezer Storage Time <10F See Note 2

Out Time at 70 10F < 2 day 9 ??/1 3 days 9 ??/3 5 days 9 ??/5 7 days 9 ??/7 10 days 9 ??/10 12 days 9 ??/12 15 days 9 ??/15 18 days (Note 1) 9 ??/21

Property Short Beam Strength Gel Time Tack Drape HPLC DSC Photomicrography and void content (and C-scan) Photoacoustic Infrared Spectrum Tests related to process modeling APA 2000 or similar tests

Method/Condition ASTM D 2344-00, RTD ASTM D3532-99 NCAMP Test Plan NCAMP Test Plan SACMA SRM 20R-94 SACMA SRM 25R-94 MIL-HDBK-17-1F, sec 6.6.7.3 CNDE Procedures As needed As needed

# Replicates 8 3 3 3 2 2 As needed As needed As needed As needed

Members NCAMP Toray NCAMP NCAMP Toray Toray NCAMP CNDE UBC Avpro 22

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Rheometric Dynamic Analyzer (RDA-III), Frequency Sweep

8.00E+05 Storage Modulus, Pa 6.00E+05 4.00E+05 2.00E+05 0.00E+00 1 10 Time in days 100 Loss Modulus, Pa 0.2Hz 0.32Hz 0.5Hz 0.8Hz 1.26Hz 2.00E+06 1.50E+06 1.00E+06 5.00E+05 0.00E+00 1 10 Time in days 100 0.2Hz 0.32Hz 0.5Hz 0.8Hz 1.26Hz

3 2.5 Tan delta 2 1.5 1 1 10 Time in days 100 0.2Hz 0.32Hz 0.5Hz 0.8Hz 1.26Hz

Experiment performed by Avpro (Tom Rose)

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HPLC per T700SC-12K-50C/#2510, F6273C-07M Specification

HPLC_Peak Area%-Out-Tim e Test

80.00 75.00 70.00 65.00 60.00 55.00 50.00 45.00 40.00 35.00 30.00 25.00 20.00 15.00 10.00 5.00 0.00

Peak 1, % Peak 2, % Peak 3, % Peak 5, % Peak 4, %

10

12

15

18

21

24

27

30

33

36

39

42

45

48

51

54

57

60

Outt ime, Days

Experiment performed by Toray Composites America

The Joint Advanced Materials and Structures Center of Excellence

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Gel Time per T700SC-12K50C/#2510, F6273C-07M Specification

Gel time @121C, (mins)

10.0

Gel time @121C, (mins)

0.0 0 10 20 30
Outti me, day

40

50

60

70

Experiment performed by Toray Composites America

The Joint Advanced Materials and Structures Center of Excellence

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DSC per T700SC-12K-50C/#2510, F6273C-07M Specification

DSC, Onset
145.0

Onset C

135.0

Onset, C

125.0 0 10 20 30 40 50 60 70 Outtime, Days

DSC, Peak temp

170.0 Peak temp C

Peak, C

160.0 0 10 20 30 Outtime, Days 40 50 60 70

DSC, Heat of Reaction

300.0 250.0 200.0 -J/g 150.0 100.0 50.0 0.0 0 10 20 30 Outtime, Days 40 50 60 70

-DH, J/g

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Differential Scanning Calorimetry (DSC) Analysis of Resin

300 250 Heat of Reaction (J/g) 200 150 100 50 0 0 10 20 30 Days Aged 40 50 60

Experiment performed by UBC

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Differential Scanning Calorimetry (DSC) Analysis of Resin

4 3.5 3 2.5 Tg0 (oC) 2 1.5 1 0.5 0 -0.5 -1 Days Aged 0 10 20 30 40 50 60

Experiment performed by UBC

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Differential Scanning Calorimetry (DSC) Analysis of Resin

1.60E-03 1.40E-03 1.20E-03

Example Only
unaged

150 149.5 149

T at peak rate (C)

148.5 148 147.5 147 146.5 146

Cure rate

1.00E-03 8.00E-04 6.00E-04 4.00E-04 2.00E-04 0.00E+00 100

aged 5%

120

140

160

180

200

220

240

10

20

30

40

50

60

70

Temperature (C)

Days Aged

Experiment performed by UBC

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Photoacoustic Infrared Spectroscopy Study of Out-Life Aging John McClelland and Roger Jones
Center for Nondestructive Evaluation, Iowa State University

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PAS Prediction
70 60 50 40 30 20 10 0 -10 -10 0 10 20 30 40 50 60 70

Predicted Prepreg Age (days)

Known Prepreg Age (days)

After the 33rd day, the specimens had become stiffer and lost some of its tackiness
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Infrared Photoacoustic Spectroscopy (PAS) Technology

Infrared spectroscopy is a proven technique to measure aging of epoxy prepreg, but is too tedious for routine use PAS can analyze the intact prepreg, allowing virtually all sample preparation to be skipped PAS works by sensing the infrared energy absorbed in a sample. The sample is sealed in a chamber containing a microphone. Infrared radiation shines on the sample. If the sample absorbs the radiation, its temperature and pressure oscillate, which the microphone detects as sound waves.
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Prepreg Aging Study Conclusion

PAS is the most sensitive technique for measuring prepreg out-time Other techniques are not very reliable; so aging of prepreg cannot (or need not) be incorporated into process modeling PAS is easy to perform and conducive to shop environment More research is needed to validate PAS; need to take into account the effects of humidity
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Documentation of practices and lessons learned in NCAMP

NCAMP offers a practical venue to try things out Document NCAMP experiences in the FAA report
What works and what doesnt Whats required

The roles and functions of industry organizations

CMH-17, SAE PRI, SAE Nadcap, SAE P-17, ASTM D30, NCAMP, etc.

The roles and functions of material users and various levels of material suppliers
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Understanding Each Others Roles, Requirements, and Responsibilities

CONSTITUENT MATERIAL SUPPLIERS [Fiber, Fiber precursor, Sizing, Resin, Hardener, Filler, Modifiers, Toughening Agent, etc.]

MATERIAL USERS [Aircraft Companies, Component Fabricators, etc.]

Material & Process Issues Testing Process Control Quality Improvement How to manage change (communication, impact on material properties, etc . . .) Certification Specification Limits Handling & Packaging etc . . .

INTERMEDIATE PROCESSORS [Prepregger, Weaver/Braider]

Reduce duplicate efforts while maintaining sufficient checks and balances

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How all of these fit together?

Industry Organizations
(CMH-17, SAE, Nadcap, PRI, NCAMP, ASTM D30)

Material Specifications

Audit

Process Specifications Quality Control Accreditations Processing Tolerance Limits Regulatory Agencies Qualified Products Listing
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Material Change Management Material Qualifications

Process Control Documents

Material Compatibility

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Fuji Heavy Industries

Kawasaki Heavy Industries Lewcott

A Look Forward
Benefits to Aviation
Provides solution and guidance to the industry Documents lessons learned Ensures a supply of composite materials with stable properties

Future needs
Continue to work with the industry on material & process issues
Develop other essential guidance documents such as Carbon Fiber PCD Preparation Guide

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