Sensor Technology for RTM Processes

A Critical Review and Technology Assessment

May 2000

Table of Contents
List of Figures ....................................................................................................................... vi
List of Tables .......................................................................................................................viii
1.0

EXECUTIVE SUMMARY ........................................................................................ 1

2.0

INTRODUCTION....................................................................................................... 2

2.1
Process Modeling versus Process Control....................................................................................... 3
2.1.1
Process Modeling.......................................................................................................................... 3
2.1.2
Process Modeling for RTM.......................................................................................................... 4
2.1.3
Process Control............................................................................................................................. 6

3.0

RESIN CURE............................................................................................................... 7

4.0

PROCESS MONITORING TECHNIQUES .......................................................... 9

4.1
Optical and Spectroscopic Sensor Techniques............................................................................... 9
4.1.1
Introduction................................................................................................................................... 9
4.1.2
Off-Line Measurements..............................................................................................................10
4.1.3
On-Line Measurements ..............................................................................................................14
4.2
Ultrasonic Testing .............................................................................................................................38
4.2.1
Introduction.................................................................................................................................38
4.2.2
Direct Measurements Using Ultrasound Technique.................................................................42
4.2.3
Interface Waves Versus Reflection Technique.........................................................................43
4.2.4
On-Line Process Monitoring......................................................................................................44
4.3
Electrical Properties .........................................................................................................................53
4.3.1
Introduction.................................................................................................................................53
4.3.2
Cure Monitoring Techniques .....................................................................................................55
4.3.3
Examples of Cure Monitoring Techniques ...............................................................................56

5.0

SOFTWARE-AIDED CURE TECHNIQUES...................................................... 76

5.1
Introduction........................................................................................................................................76
5.2
Sensors Mounted As Roving Threads (SMART) .........................................................................76
5.2.1
Comparison Between Dielectric And Ultrasonic Cure Monitoring Data................................80
5.3
Finite Element Method.....................................................................................................................82
5.4
Artificial Neural Networks...............................................................................................................83

6.0

CONCLUSIONS AND RECOMMENDATIONS................................................ 85

7.0

REFERENCES .......................................................................................................... 86

AMPTIAC

List of Figures
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11
Figure 12
Figure 13
Figure 14
Figure 15
Figure 16
Figure 17
Figure 18
Figure 19
Figure 20
Figure 21
Figure 22
Figure 23
Figure 24
Figure 25
Figure 26
Figure 27
Figure 28
Figure 29
Figure 30
Figure 31
Figure 32
Figure 33
Figure 34
Figure 35
Figure 36
Figure 37
Figure 38
Figure 39
Figure 40
Figure 41
Figure 42
Figure 43
Figure 44
Figure 45
Figure 46

The Basic RTM process.................................................................................................................. 5

Resin Viscosity during the Cure Cycle.......................................................................................... 7
Composite Cure Monitoring using Infrared Transmitting Optical Fibers as Sensors. .............12
Reflection and transmission of ray incident from glass to vacuum...........................................15
Differential spectra of graphite fiber / composite prepreg .........................................................19
Intensity of composite prepreg amide I absorbance band in difference spectra........................20
Intensity of composite prepreg imide II absorbance band in difference spectra.......................20
Side view of prism, clamp and seal assembly. ............................................................................21
Transmission of IR spectrum of polydimethylsiloxane and methylhydrosiloxane copolymer.22
Isothermal conversion at various temperatures for 12-ppm commercial catalyst.....................22
Simulated cure for Backglass system...........................................................................................23
Simulated cure and temperature profiles with commercial and 493B catalysts........................24
Dependence of the fluorescence spectrum of excimer-forming probe 1,3-bis- (1-pyrene)
propane on the solvent viscosity. .................................................................................................26
Self-probe fluorescence of TGDDM/DDS epoxy as function of cure time and temperature. .27
FOCS fluorescence intensity signal during curing of Hercules 3501-6 laminate.....................28
FOCS fluorescence wavelength signal during curing of Hercules laminate.............................28
Fluorescence intensities of DMA-DPH at 480 nm (?) and of DPA at 415 (? ) as a function of
cure time. .......................................................................................................................................29
Ratio of the fluorescence intensity of the probe DMA-DPH (FP) and the fluorescence
intensity of the internal standard (FR) as a function of cure time..............................................30
Amine reaction plotted as function of cure time for DGEBA-DDS and DGEB-DDS.............31
Temperature dependence of the extent of amine reaction (a) as a function of cure time:
DBEB-DDS. ..................................................................................................................................31
Relative rate of change of the index of refraction of an epoxy composition during cure,
measured interferometrically at 633 nm......................................................................................33
Relative transmission through fiber optic cure sensor vs. cure time for 5-Min. Epoxy. ..........33
Conversion vs. wavelength maxima of DMANS spectra by conventional fluorimetry. ..........34
DMANS exhibited significantly larger spectral shifts than di-10-ASPPS................................35
An evanescent wave fluorescence sensor....................................................................................37
Graphical comparison of cure profiles f ......................................................................................37
Typical curve for dynamic mechanical properties as a function of polymers...........................40
Schematic Illustration of the Ultrasonic Sensor Installation. .....................................................45
Sound speed and temperature versus time during the cure of a composite specimen. .............45
Sound velocity recordings from four 16-ply panels using the standard cure cycle. .................47
Results for two 16 ply and one 64 ply panels with a hold cycle at 3500F................................47
A schematic representation of the UCMS-200 installed in a compression molding process...49
Ultrasonic sound speed vs. temperature for a CM epoxy-graphite fiber prepreg.....................50
Sound speed during compression molding of Rogers RX-640 phenolic molding compound. 50
Signal attenuation-time curves a of four commercial phenolic molding materials. .................51
Arrhenius plots of ultrasonic cure time against reciprocal absolute temperature .....................52
The dielectric loss, , measured at 1, 2, 3, 5, and 10 kHz excitation frequencies. ..................59
Dynamic viscosity vs. ionic conductivity isothermal cure of DGEBA-DDS............................62
Investigation of the frequency dependence of inverse ionic conductivity measurements........63
Change in bulk resistance during the cure of epoxy resin..........................................................64
Typical ion viscosity and temperature curve during vinyl-ester molding. ................................65
Comparison of ion viscosity curves for different mold temperatures........................................67
Comparison of ion viscosity curves for different catalyst levels ...............................................67
Log ion viscosity and temperature during curing of Hercules 3501-6......................................68
Log ion viscosity and Tg during final isothermal cure step of Hercules 3501-6......................69
Log ion viscosity versus Tg during final isothermal cure step of Hercules 3501-6.................69

vi

Sensor Technology for RTM Processes

Figure 47
Figure 48
Figure 49
Figure 50
Figure 51
Figure 52
Figure 53
Figure 54
Figure 55
Figure 56
Figure 57
Figure 58

A Critical Review and Technology Assessment

May 2000
Ionic conductivity and temperature versus cure time for two different ramp rates. .................71
Cure profile of CY225 / HY925 measured with DMA (cure temperature: 1000 C)................72
Relation between curing volume shrinkage and Tg for CY225 / HY925.................................72
Iso-Tg contours for CY225 / HY925...........................................................................................73
Log Ion Viscosity as a function of time.......................................................................................75
A SMARTweave Grid..............................................................................................................77
Experimental Set-Up.....................................................................................................................78
Results of Flow Front Reconstruction. ........................................................................................79
SMARTweave voltage versus time..........................................................................................80
Ultrasonic sound speed vs. log resistivity during fiberglass epoxy prepreg cure .....................81
Comparison of electrical resistivity and sound speed during isothermal cure..........................82
Nodes as connecting tools for elements.......................................................................................82

vii

AMPTIAC

List of Tables
Table 1
Table 2
Table 3
Table 4
Table 5

Empirical rate constants (k1, k2) and residual errors (r2) for Blackglass 493A resin and
commercial catalyst.......................................................................................................................23
List of the panels cured to date.....................................................................................................46
Cure times that include activation energies of cure reactions ....................................................52
Effects/t-Ratios of controlled variables on time to viscosity minimum and gel-inflection......66
The critical slopes, time to critical slope, and glass transition data ...........................................68

viii