STUDENT ID: 4104669

3.0 ULTRASONIC EVALUATION AND MONITORING OF THE CURE STATE OF

EPOXY ADHESIVE

Adhesive bonding technologies have found various and wide applications in the
production and assemblage processes of many manufacturing industries.

The need for quality control during production and post-production quality assurance and
reliability of adhesive bonded joints gave rise to the need for monitoring and evaluation
of adhesive curing process. It has been noted that the curing process impacts on the
joints performance and defects such as delaminations, kissing-bonds, cracks, voids,
missing adhesion etc usually found in adhesive bonded joints can result from improper
curing process [11].

The curing or hardening of the epoxy adhesive is a chemical process during which the
polymeric epoxy mixture translates from a viscous liquid characterized by low molecular
weight into a highly cross-linked solid with the application of heat [12,13]. The curing
process involves gelation and vitrification stages. At gelation, the mixture cease to flow
and begins to form elastic cross-links. While at vitrification, a solid glass is formed and
chemical reactions cease as glass transition temperature goes above the cure
temperature of the epoxy[14,15]. The real-time tracking of the chemical reactions and
the accompanying changes in the physical state that take place during cure is referred to
as cure monitoring.

Effective curing of adhesive is a function of a number of parameters such as resin-

hardener mix ratio, cure temperature, time etc [12]. In order to achieve a properly
cured adhesive and hence a good adhesion strength, cure parameters are appropriately
set by monitoring and evaluating the progress of the hardening process in real time. In
order words, if the curing process is not monitored and it goes wrong, though the
adhesive may be bonded to its substrates, the required cohesive properties of the
adhesive joint would not be achieved i.e it is either too rubbery or too brittle. Thermoset
epoxy is usually cured for longer time than necessary in order to avoid undercure, but
this is not time efficient. In order to avoid undercure and also minimize time and cost, a
cure monitoring technique that can detect the time the cure reaction ends is very
essential.

Not only this, cure monitoring is being used in a feedback loop system to control and
efficiently optimize cure temperature and time. This is to say that if the curing process is
going too fast(which could lead to overcure), the temperature could be lowered to slow it
down and if the cure rate is too slow, the temperature could be raised to restore the
process to normalcy. Also, through cure monitoring, mix ratio variations i.e excess and

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insufficient hardener/curing agent have been noted to have significant effect on curing
as well as cure rate.

Various techniques have been employed to follow the process of epoxy curing, but the
Ultrasonic method has been favoured as it is simple, convenient, non-destructive and
allows in-process monitoring of the hardening process. The ultrasonic techniques, during
curing, employ the changes in the behaviour of sound wave as it propagates through the
epoxy mixture, to follow and characterize the state of cure. Parameters such as
ultrasonic velocity, amplitude attenuation and acoustic impedance can be used to follow
curing process. Ultrasonic velocity increases as the epoxy translates from liquid to solid.
Consequently, the arrival time of echo from the epoxy decreases as cure progress. Also,
this increase in sound velocity coupled with the assumption that the density(ρ) of the
epoxy is constant during cure, results in a higher acoustic impedance(Z=ρV) as also
noted by Challis et al [3].

The ultrasonic pulse-echo mode, shown in figure 3.0, can be simply employed for these
velocity, acoustic impedance and attenuation measurements using the ultrasonic signal
waveforms.

1 Al

2 Epoxy

3 Al

(a) (b)

Fig. 3.0: Pulse-echo mode (a) and typical ultrasonic signal waveform (b)

The sound velocity(V) in the epoxy layer can be calculated from the thickness of the
sample and a measure of the time of flight difference between the reflected pulses from
the sample boundaries as follows;

V= 2D/∆t (3.0)
where D is the thickness of the epoxy sample and ∆t is the time of flight difference
between echoes from upper and lower epoxy interfaces/boundaries.
The attenuation measurement is based on the changes in the echo amplitude from the
epoxy interface. The echo amplitude is dependent on the interface refelection
coefficient(r), which in turn relates with the acoustic impedance(Z) by equation (1.0) in

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part 1, where medium 1 is the Al substrate and medium 2 is the epoxy mixture. Hence,
as both velocity and acoustic impedance increase as cure progresses; reflection
coefficient changes, which in turn leads to changes in echo amplitude(from which
attenuation can be measured). Figure 3.1 presents typical changes in sound velocity
and attenuation during cure. It is also noteworthy that acoustic impedance only gives
information about the cure state at the epoxy interface.
Sound velocity(m/s)

Attenuation(Np/m)

(a)
Cure time(mins) (b) Cure time(mins)
0
Fig. 3.1: Typical changes in Sound velocity(a) and attenuation during adhesive cure(b)

Many researchers have investigated the use of ultrasonic techniques to monitor and
evaluate adhesive cure state. Maeva et al. [12] recently used the pulse-echo reflection
mode to analyse the acoustic parameters and how they relate with the degree of cure
and cohesive strength of the epoxy adhesive. They used the same transducer to transmit
pulse and receive echo reflections from the interfaces of an epoxy-metal substrate
layered sample as shown in figure 3.2 taken from Maeva et al. [12].

Fig 3.2: Showing origin of echoes(a) and typical A-scan(b):1-echo from buffer-rod/epoxy
interface; 2-echo from epoxy/metal interface. (copied from Maeva et al. [12]).

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Using the echo waveforms, the longitudinal sound velocity and the attenuation of sound
wave in samples of known thicknesses were measured during the cure at different and
increased cure temperatures.

Their results show that longitudinal sound velocity increases during the curing process
and the velocity curve’s (shown in Fig 3.1a) slope rises as the cure temperature
increases [12]. This means that, at temperatures higher than specified cure
temperature, gelation occurs earlier, which leads to overcuring or the degrading of the
polymer as it becomes more brittle. Also, sound attenuation peaks at the onset of the
curing process and diminishes afterwards.

In the same vein, Faiz et al. [16] employed the pulse-echo reflection method to follow
the curing process of an epoxy resin and then did a comparison with the results achieved
from using a pulse transmission mode. In their experiment, the vessel containing the
resin and hardener mix and the transducer were immersed in a water tank as shown in
figure 3.3, taken from Faiz et al. [16].

Fig. 3.3: Pulse-echo experimental set-up from Faiz et al. [16]

Phase velocity, attenuation and acoustic impedance measurements, extracted in the

time domain, were used to monitor the curing of different mix of epoxy(resin &
hardener), in order achieve the best percentage of hardener needed for proper curing.

Their results show that phase velocity increase during the curing process, while
attenuation peaks as curing progresses, but diminishes as the epoxy sets(solidifies).
Also, epoxy normal setting time reduces(i.e earlier gelation time) as the percentage of
the hardener increases, which represents overcure of the epoxy. Slow cure rate and
probably undercure result, when the hardener percentage is below the manufacturer’s
recommended value. Moreso, they showed that acoustic impedance is a measure of
epoxy cure state at the vessel-epoxy interface and that the curing process is
nonhomogenuous throughout the sample as curing actually starts from the centre
towards the vessel walls.

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Their transmission mode, which incorporates a reference epoxy sample, gave results
that are in corformity with the ones from the reflection mode.

On the other hand, the use of ultrasonic guided waves in wires to monitor cure reaction
was investigated by Vogt et al. [17]. Figure 3.4, taken from Vogt et al. [17], shows a
magnetostrictive device used to generate longitudinal and torsional waves at low
frequencies, which were then guided into the epoxy sample by a steel wire. For high
frequencies, a piezoelectric transducer was used to excite a longitudinal mode as an
alternative and the waveguide in this case is steel bar.

Fig.3.4: Cure Monitoring using a magnetostrictive device to guide waves in steel wire
(copied from Vogt et al.[17])

They presented two methods using a wire waveguide that is partially inserted in the
epoxy adhesive. Attenuation measurements, due to bulk wave leakages from the
waveguide into the surrounding epoxy, form the basis of their first method. The second
method measures the wave reflection that occurs at the entry point of the waveguide
into the epoxy as shown in figure 2.5, taken from Vogt et al. [17]. Both methods employ
the tangible changes in attenuation and reflection during cure.

Fig 3.5: Schematic representation of entry reflection (copied from Vogt et al. [17])

Using a software tool called DISPERSE, they modelled the attenuation of sound wave in
the inserted steel wire waveguide as the epoxy translate from liquid(precure state) to
solid (postcure state). The prediction shows that only bulk longitudinal waves leak away
in an ideal liquid epoxy, while both longitudinal and shear waves radiate in solid epoxy.
Also, the entry reflection was modelled, using the finite-element and modal prediction,
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based on the idea that the shear velocity increases as the epoxy cures; and as the
impedance mismatch between the free portion of the waveguide in air and the inserted
portion increases, the entry reflection becomes large. The variation in density of the
epoxy resin was assumed to be negligible during the curing process and the reflection
coefficient was treated to be independent of the longitudinal bulk wave.

Their experimental results, using measurement of attenuation and reflection, when

waveguide is in free air as a reference, show wave’s amplitude reduction(attenuation) on
insertion(due to leaking bulk waves) and as the epoxy solidifies, the shear wave velocity
rises and hence, attenuation rises monotonically till curing ends. Also, the entry
reflection rises as cure progresses as a consequence of the rising shear velocity in the
epoxy.

Furthermore, Lionetto et al. [18] investigated the practicality of using a customised, air-
coupled ultrasonic device to monitor the cure process of epoxy samples at room
temperature. Their experimental set-up involves the appropriate positioning (in terms of
incident angle and stand-off distance from the sample) of the two non-contact
transducers in a pitch-catch mode in order to transmit and receives compression waves
from the sample throughout the curing process as shown in figure 3.6, taken from
Lionetto et al. [18].

Fig.3.6: Wave propagation paths in the sample using air-coupled transducers to monitor
cure ( copied from Lionetto et al. [18])

The hardening process was followed by measuring the changes in the transit time of the
propagating waves from the transducer, through air and the sample, then back to the
receiver. The compression wave velocity is then calculated using the transit time (ttotal ),
the sample thickness(s), the refraction angle(β) and the wave path number(N) in the
sample as follows;

V=(N x d)/ttotal (3.1)

d=s/cos β and ttotal=ta1+ts+ta2.

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where ts is the transit time of sound wave travel through the sample and ta1 & ta2 are the
transit times of sound wave travel in air from the transmitter to the sample and from the
sample to the receiver respectively.

Their results show that the transit time and the velocity are constant at the onset of the
cure reaction, but as it progresses, transit time reduces while the velocity increases. The
increase in sound velocity results in an increase in the refraction angle(β), according to
Snell’s law, and thus an increase in the ultrasound path-length in the sample.
Consequently, during cure, the exit point of the ultrasound from the sample moves
further to the right as shown in figure 3.7 taken from Lionetto et al. [18]. Tangible
changes also were noted in the intensity and shape of the echo waveforms.

Fig.3.7: Change of exit point of ultrasound from the sample during cure (copied from
Lionetto et al. [18])

3.1 PRACTICALITIES

The Lionetto et al. [18] technique proposes the elimination of contact and coupling
effects etc, but the complexity that is inherent in analysing ultrasound propagation in air
and in optimizing the transducers to excite and receive compression waves throughout
the curing process requires skill and great effort and hence poses a limitation on the
application of this method.

The ultrasonic guided waves technique is fascinating, in that it allows the curing process
to be followed all through, even from the onset, by measuring the shear properties of
the waves [17]. However, its application requires good system design that suits the test
sample at hand. Also, the problem of multimode wave propagation in the waveguide can
complicate the measurements. Apart from this, the waveguide is stuck permanently
inside the adhesive. This is unsuitable for some applications as there is the possibility of
formation of voids around the waveguide, thereby weakening the joint strength. This
could also lead to an increase in the overall weight of the structure.

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The pulse-echo reflection technique is a simple and effective method for monitoring and
evaluating the cure state of epoxy adhesive. Although this techique could be affected by
errors arisng from couplants, surface coatings, coupling pressure and surface roughness
[3], with appropriate signal processing, the errors can be minimized. It is also good to
note that the water tank immersion, used by Faiz et al. [16], can cause water ingress
into sample, which is a problem in practical applications.

The pulse-echo reflection method will be suitable for the test component in that it is
versatile enough to monitor all cure states. Moreso, an automated device for testing
adhesive joints is available commercially.

3.2 BONDMASTER 1000E+

The Bondmaster 1000e+ shown in figure 3.8 is a robust, multipurpose instrument

produced by Olympus NDT [19]. This device incorporates three test modes: Resonance,
Mechanical Impedance analysis and Pitch-catch mode.

Fig. 3.8: BondMaster 1000e+ (Copied from www.olympusNDT.com[19])

The pitch-catch mode shown in figure 3.9 is relevant to this application. It has three
inspection methods namely pitch-catch swept, pitch-catch impulse and pitch-catch RF
methods. This mode uses ultrasonic technique (propagation of high frequency sound
wave) to excite surface waves into the test sample. Another probe, set at a distance
from the transmitting probe, receives the energy propagated into the material. Changes
in phase and amplitude of the transmitted and received signal are detected and a phase-
amplitude display is used to inspect adhesive bond and locate defects.

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Fig. 3.9: Pitch-catch Test Mode (Copied from www.OlympusNDT.com[19])

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