Cure Monitoring: Microdielectric Techniques: 13.1 The Dielectric Response

13
Cure Monitoring:
Microdielectric
Techniques
13.1 The Dielectric Response ...................................................13-1
13.2 Changes In Resistivity During Cure ................................13-2
Process Control through Dielectric Feedback Process
Control through DielectricThermal Feedback
David R. Day
Micromet Instruments, Inc.
13.3 Summary............................................................................13-5
References .....................................................................................13-5
Developments in the area of microelectronics now enable the fabrication of microdielectric sensors that
can analyze drying, curing, and diffusion phenomena in coatings.1 Several types of microdielectric sensors
have evolved in the past few years, the most sensitive being based on interdigitated electrodes and field
effect transistors fabricated on a 3 5 mm silicon chip.2 The chip sensor is housed in a polyamide package
and configured for ease of placement in various processing environments (Figure 13.1).
13.1 The Dielectric Response

The dielectric response arises from mobile dipoles and ions within the material under test. As a coating
cures, the mobilities of dipoles and ions are drastically reduced, sometimes by as much as seven orders
of magnitude. Microdielectric sensors are sensitive enough to follow those changes and are therefore
useful for cure monitoring, cure analysis, and process control.3
The dielectric response is typically expressed by the quantities of permittivity or dielectric constant
(E) and loss factor (E):
E = Eu +
E =
Er Eu
1 + 2
s
E Eu
+ r
e 0 1 + 2
(13.1)
(13.2)
where (E4 Eu)/(1 + wt2) is the dipole term, se0 is the conductivity term, and
E = dielectric constant
E = loss factors
s = bulk ionic conductivity
e0 = permittivity of free space (a constant)
13-1
2007 by Taylor & Francis Group, LLC
13-2
Coatings Technology: Fundamentals, Testing, and Processing Techniques
Connector
.375"
Sensing Area
15"
.018"
FIGURE 13.1 Schematic diagram of microdielectric sensor.
= frequency 2
= dipole relaxation time
Er = relaxed permittivity (low frequency E)
Eu = unrelaxed permittivity (high frequency E)
In addition to ions and dipoles, other factors, such as electrode polarization4 or inhomogeneities, may
influence the dielectric response; however, these generally play a minor role and are usually ignored.
The dielectric loss factor is the most useful quantity for monitoring cure reactions. Dipole relaxation
times or ionic conductivity levels may be monitored during cure. However, dipole relaxation times are
usually difficult to determine, because the conductivity response often dominates the dipole term in
Equation 13.2. On the other hand, conductivity usually can be determined throughout the entire cure
process, especially if low frequencies (<10 Hz) are monitored during the end of cure. The inverse of the
measured conductivity, resistivity, is often proportional to viscosity of the material under test before
gelation and is related to rigidity after gelation.5 Figure 13.2 shows loss factor data during an isothermal
cure of an epoxy resin. Figure 13.3 compares the log (resistivity) calculated from the data in Figure 13.2
to degree of conversion as determined by the fractional generated heat method using differential scanning
calorimetry (DSC). Figure 13.3 shows that the dielectric response can monitor the entire cure and is far
more sensitive to the last few percent of cure than DSC.
13.2 Changes In Resistivity During Cure

Figure 13.4 plots changes in resistivity during isothermal cure versus changes in the glass transition
temperature. These data demonstrate the utility of microdielectric sensors for monitoring and process
control in coatings.
Using the previously described techniques, ionic conductivity (or its reciprocal, resistivity) can be
obtained in real time by continuously monitoring a range of frequencies. It can then be used to control
the reaction through variation in either temperature or pressure. Several ways exist in which dielectric
feedback may be used. Some of these are as follows:
Temperature may be held constant or controlled until a desired viscosity (measured dielectrically)
is attained.
Viscosity may be held constant or varied at will through controlled variation in temperature.
13-3
Cure Monitoring: Microdielectric Techniques
3
.1 Hz
2
Log E
100
10 KHz
Log Cond
10
10
1K
11
2
0
20
40
60
Time (min)
12
100
80
FIGURE 13.2 Dielectric loss factor data of isothermal (392C) epoxyamine cure. Frequencies range from 101 to
104 Hz.
11.2
100
Log Resistivity
DSC % Cure (alpha)
80
60
40
20
6.4
0
0
20
40
60
Time (min)
80
100
FIGURE 13.3 Ionic resistivity data from Figure 13.1 and degree of conversion as determined by DSC versus time.
Pressure, vacuum, or mold opening may be activated upon attainment of a critical viscosity of
dielectric reaction rate.
Reaction may be terminated when the dielectric reaction rate decreases below some critical value.
13.2.1 Process Control through Dielectric Feedback

Figure 13.5 shows an example of a process-controlled cure of a graphite epoxy using microdielectric
feedback. Control was achieved using an IBM PC with modified Micromet Instruments dielectric software
and hardware. The cure was carried out in a hot press with temperature controlled from the computer.
The process control software sequence was as follows:
13-4
Coatings Technology: Fundamentals, Testing, and Processing Techniques
1. Heat and hold at 250F until a log resistivity of 7.0 is reached (allows for degassing while preventing
premature cure).
2. Hold log resistivity (viscosity) at 7.0 until 350F is reached (allows for controlled curing and
prevents second viscosity minimum).
3. Hold at 350F until the dielectric reaction rate is near zero (allows reaction to go to completion).
4. Cool and notify operator that cycle has been completed.
200
11.3
120
80
Glass Transition (C)
Log Resistivity
160
40
6.2
50
100
150
200
Time (min)
250
0
300
FIGURE 13.4 Ionic resistivity data and Tg during isothermal epoxyamine cure.
13
450
Hold Ionvisc.
at 7.0 until
Hold at 350F until
Temp. = 350F
Slope = 0
Hold at 250F
until
Ionvisc. = 7.0
12
Cool Down
350
11
10
1 & 10 Hz
300
Temperature (F)
9
250
Pressure
Signal
Issued
200
100 Hz
7
150
100
Fiberite F-934
1 K & 10 K Hz
5
50
100
Time (min)
150
FIGURE 13.5 Process control of epoxy graphite cure utilizing microdielectric feedback.
50
200
Temperature (F)
Log Ion Viscosity
400
Cure Monitoring: Microdielectric Techniques
13-5
13.2.2 Process Control through DielectricThermal Feedback

The cure in Figure 13.5 was completely controlled through both dielectric and thermal feedback from
the microdielectric sensor in contact with the graphite epoxy material. Note that the second viscosity
(resistivity) minimum typical of these materials was completely eliminated through the use of viscosity
control. This technique is useful for limiting excessive bleed in composites that are prone to such
problems. Finally, the endpoint was detected and the reaction stopped, eliminating unnecessary overcuring time.
13.3 Summary
Microdielectric sensors are useful for monitoring cures of coatings under actual processing conditions.
The ionic resistivity portions of the loss factor data correlate to viscosity during the early stages of reaction
(before gelation or solidification). As the reaction progresses, the slope of the ionic resistivity can be used
to monitor reaction rate and to detect when cure is complete. The microdielectric sensors provide a
unique capability to correlate measurements made in the laboratory to those in the factory and to provide
the necessary feedback information for adaptive process control.
References
1. D. R. Day and D. D. Shepard, J. Coat. Technol., 60(760), 57 (1988).
2. (a) S. D. Senturia, N. S. Sheppard, Jr., H. L. Lee, and D. R. Day, J. Adhes., 15, 69 (1982). (b) N. F.
Sheppard, Jr., D. R. Day, H. L. Lee, and S. D. Senturia, Sensors Actuators, 2, 263 (1982).
3. (a) W. E. Baumgartner and R. Ricker, SAMPE J., 19(4), 6 (1983). (b) D. R. Day, Proceedings of the
SAMPE Symposium, Las Vegas, 1986, p. 1095. (c) D. E. Kranbuehl, Proceedings of the SAMPE
Symposium, Anaheim, CA, 1988. (d) D. R. Day, Proceedings of the SAMPE Symposium, Anaheim,
CA, 1988, p. 594.
4. D. R. Day, T. J. Lewis, H. L. Lee, and S. D. Senturia, J. Adhes., 18, 73 (1985).
5. J. Gotro and M. Yandrasits, Proceedings of the 45th SPE ANTEC, Anaheim, CA, 1987, p. 1039.

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13

13.1 The Dielectric Response

2007 by Taylor & Francis Group, LLC

Coatings Technology: Fundamentals, Testing, and Processing Techniques

FIGURE 13.1 Schematic diagram of microdielectric sensor.

13.2 Changes In Resistivity During Cure

2007 by Taylor & Francis Group, LLC