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AN003

Thermosets and Structural Adhesives


revised by A. Franck, TA Instruments Germany
Keywords: hot melts structurak adhesives, thermosets, cure, Tg., cure cycle, gel point

Structural adhesives are usually thermosetting


polymers. Generally applied to the surface as low
viscosity, reactive liquids, their viscosities increase
rapidly as they polymerize and crosslink in the joint
to form a rigid, high strength bond. Therefore,
knowing the viscosity as a function of cure time
and cure temperature is important for establishing
optimum cure conditions.

Log o, *,Goo

INTRODUCTION
liquid

solid

*
G

Thermoset polymers form the matrix in filled


plastics and fiber-reinforced composites used in a
tc
Reaction time
diversity of products. These range from consumer
items and auto body panels to advanced composites
Figure 2: Measurement of the viscosity of a curing resin in a
for printed circuit boards, aerospace structural steady shear and a dynamic oscillatory test
components, and expensive, high-performance
THE CROSSLINKING REACTION
sports equipment.
In order to build a chemical network, one of the
monomers has to be two-functional and one threefunctional. (figure 1). The formation of a crosslinked
network can be followed , measuring the viscosity
as a function of time and temperature as shown in
figure 2. As the network structure builds, the
viscosity increases due to the growing resistance to
the flow. Near the gel point, the steady viscosity
increases rapidly and becomes un-measurable
eventually the stiffening sample breaks. In contrast
an oscillatory measurement of the resins viscosity
can be made as the reaction proceeds through the
gel point - and beyond- until the resin becomes a
stiff solid.

Figure 1: Schematical representation of structural


development during thermoset curing for the reaction of a
dimer with a trimer

The time/cure mode is an efficient way to


generate viscosity profiles of a curing thermoset
polymer. The viscosity profile yields the initial
viscosity, minimum viscosity, approximate gel point,
and optimum heating rate of a thermoset during
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in the time scale of the developing gel (figure 4).


Because tan is independent of frequency at the
gel point, the curves pass through a single point and
unam-biguously define the instant the gel forms as
shown in figure 5.

10

10

Moduli G', G'' [Pa]

10

10

G'
G''
*

approx. gel point


5

10

10
4

10

Complex viscosity * [Pas]

Temperature ramp 5 C/min

EFFECT OF HEATING RATE


Figure 6 shows viscosity versus reaction time at
several heating rates for a typical epoxy structural
adhesive. With increasing rate, the viscosiy
minimum does not only occur earlier, it is also lower.
This is significant for example in a lamination
process, the resin viscosity must be low enough to
wet the embedded fibres uniformly, but not so low
to cause excessive bleeding at the laminate edges
or in the en-capsulation of integrated circuits by
transfer-molding The viscosity must not be too high
to damage the fragile fibres

Minimum viscosity

10

10
80

100

120

140

160

Temperature T [C]

Figure 3: Measurement of the minimum viscosity and


approximate gel point for a curing epoxy compound

Equilibrated stoechiometry
6

EFFECT OF MOISTURE

10

PDMS r=1

tc

(data Winter & Chambon)


tc +6

10

tc+2

tc-2

tc-6
,

Frequencies
1 rad/s

4 rad/s
, 16 rad/s

8
,

10

0.5

t-t c log A

10

10

G'
G''

-6
-2
0
+2
+6

+2
+1
0
-1
-2

tan

Moduli b G', b TG'' [Pa]

10
4

10

Precise
Gel Point

,
,

10

-4

10

-3

10

-2

10

-1

10

10

10

10

10

10

10

10

10

25

Frequency A+ aT [rad/s]

30

35

40

Reaction Time [min]

Figure 4: Frequency sweeps measuring G and G at any


point in time during cure

Figure 5: The gel point identified by the intersection of tand


curves generated from the simultaneous frequency sweeps

curing. Data obtained on a curing epoxy compound


are shown in figure 3. This information can then be
used to develop a production cure cycle.
[Pas]

Frequency = 10 rad/s
Initial temperature = 50C

1E+03

3C/min 2C/min

Viscosity

The crossover point of the storage and loss


modulus curves (Figure 3) is a good estimate of the
gel point of a curing thermoset. But it is only an
estimate, because, as the gel network structure
forms, the modulus changes. So unless measurements on the gelling system are made fast enough,
the exact gel point will be obscured by changes in
the modulus. The reason is, that the instant of
gelation thge modulud of the critical gel exhibits
power law behaviour and tan becomes frequency
independent for a briefmoment ( G ~ G~ a n) .
This point can be found by making several
simultaneous frequency measurements to obtain tan

1E+04

1E+02

1000

1E+01

1E+00
0

1C/min

2000

3000

4000

5000

6000

Time t [s]
Figure 6: Measurement of the viscosity profile of an epoxy
resin as a function of the heat-up rate

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Viscosity * [Pas]

10

10

10

10

water acts briefly as a plasticizer and the viscosity


decreased to a lower minimum than that of the good
resin, which was drier. When pressure was applied
to the resin during impregnation of the glass cloth,
the low viscosity resulted in resin migration and
poor adhesion of the resin to the cloth.

good resin
resin with higher moisture content

Moisture, even in low concentration, causes large


changes in the rheological and chemical behavior
of adhesives. Figure 7 shows the change in the
reaction profile due to moisture. These data can be
used to predict, for example, bond layer thickness
and cycle times in printed circuit board laminations.

-1

10

50

100

150

200

Temperature T [ C]

10

Excessive water content in an epoxy resin can


cause a plasticizing effect, lubricating the polymer
and causing a decrease in viscosity. Figure 7 shows
a comparison of the viscosities measured during
cure for both a good and a bad performing resin
samples during impregnationg a woven glass cloth.
The bad resin did not adhere to the cloth but instead
was flowing through the weave. The results show
that the bad resins viscosity peaked at approximately 100 oC but then decreased to a minimum
which was below that of the good resin.

Viscosity * [Pas]

Figure 7: Viscosity as a function of temperature for a good


and a bad (excess moisture) sample

10

at mold temperature:
Sample A
Sample A + 1% Znst.
sample B
at barrel temperature:
sample A
sample A + 1% Znst.
sample B
4

10

10

12

cure time t [min]

Modulus G' [Pa]

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l
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llllll llllll
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)
lllll
l
'l
'
'l
1E+08 ll
l

1E+07
-150 -100

-50

50

100

$
150

200

tan

At the boiling point of water, some of the excess Figure 9: Effect of Zn-stearat on the viscosity profile during
moisture evaporated, leaving voids in the material cure at barrel and mold temperature
and causing the resins viscosity to rise. But as the EFFECT OF CURE TEMPERATURE
temperature increased further, the remaining excess
Beyond the gel point, the modulus increases to
give the adhesive its ultimate strength. Adhesive
strength is evaluated from dynamic modulus
1E+11
1E+01
measurements as a function of frequency and
temperature. Figure 8 shows the dynamic elastic
93C
modulus G and tan versus temperature. For 3
l
135C
1E+10
1E+00
l
ll
l
ll l
different cure temperatures of 93, 135 and 350 oC,
l
l
l
l
l
l
l
l
l
l
l
ll
350C
l
ll ll
ll
ll
l
ll
ll
ll
the Tg of the cured epoxy resin shifted from 130oC
l
ll
ll
ll
l
l
ll
ll
ll
ll
ll
l
l
ll
l
l
ll
ll
l
l
l
l
ll
'
l
l
l
l
ll
l
l
l
l
1E+09
l
l
1E-01
'l lll
ll
l
to over 250oC.
lll
lll
l l l
EFFECT OF ADDITIVES
1E-02

1E-03
250

Temperature T [C]

Figure 8: The extent of the cure of a thermoset as a


function of the curing temperature shows in Tg

The ideal injection molding thermoset (RIM)


needs to be highly stable at a low viscosity level at
the screw barrel temperature, yet cure rapidely upon
entering the mold.
Figure 9 shows a simulation of the cure behavior
of two phenolic compounds at two different
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temperature (Tg) can be evaluated to determine the


degree of cure. The storage modulus, G (amount
of energy stored in a material), is a measure of each
samples stiffness. Curing agents not only affect the
rate of change of the polymers viscosity, but also
its physical properties by increasing the crosslinking density and as such the performance of the
final product

100

Frequencz 1Hz
10

0.1
1E8

-150

-100

-50

50

100

150

200

250

300

0.01

CURE BEHAVIOR OF COMPOSITE


PREPREGS

1E-3
350

Temperature T [C]

Figure 10: Effect of different curing agents on the


mechanical properties of the final product

temperatures, the barrel and the mold temperature.


Compound A showed fast curing in the mold and
made a good final part, but had too high a viscosity
at the barrel temperature. The compound B injected
well with low shear heating, but cured slower. The
addition of 1% of Zn stearate to compound A
lowered the viscosity at the barrel temperature to
the one of coumpound B, but without significantly
affecting the cure time.

The resin in many structural adhesives is also


used as matrix material in fiber reinforced
composites. Dynamic mechanical testing is a
valuable characterization technique for composite
matrix resins. Rheological analysis of the neat resin

200

Simulations of the viscosity under varies cure


conditions provides the necessary data in process
design: barrel temperature, nozzle size and effect
of shear heating
EFFECTS OF VARIOUS CURING AGENTS
ON EPOXY RESIN

10

10

10

10

Temperature
Neat Resin
Prepreg

180
160
140

Azelaic acid & BOMA


BOMA
DDM
BTDA

1E7

Temperature T [ C]

1E9

tan

Storage Modulus G' [Pa]

1E10

Viscosity * [Pas]

1E11

120
100
80

10

-1

10

-2

60
40

Test Frequency 10 rad/s


20
0

50

Cure time t [min]

Figure 11: Viscosity profile of composite (prepreg) and the


neat resin during cure

Epoxy resin used in printed circuit boards (PCBs)


requires sufficiently rigidity during exposure to high
end-use temperatures (approximately 140 C), and
soldering temperatures (approximately 250C).
When exposed to high operating temperatures, the
PCBs may became dimensionally unstable, resulting
in a defective product and material waste when not
formulated correctly.

to predict processing characteristics of glass and


graphite reinforced composites has become a
standard procedure in product development of
advanced composites.

Figure 11 compares results for the cure of a


graphite prepreg and neat resin using parallel plate
fixtures in a oscillatory rotational rheometer. Note
Using different curing agent, an increase of the that, although there are large differences in
maximum continuous use temperature by increasing minimum viscosity, cure times are identical.
the glass transition (Tg) was obtained under the
CONCLUSIONS
same curing conditions. DMA measurements as a
function of temperature (ASTM D 4065), shown in
Dynamic mechanical measutrements of thermoFigure 10, were performed on the final samples setting adhesives can give valuable information
Sample 4 was found to be the most efficient, about their curing behaviour, including minimum
increasing the Tg to over 270 C, higher than both viscosity and gel point, glass transition temperature
the end-use temperature and the soldering tem- and degree of crosslinking
perature The peak in tan or glass transition
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A more comprehensive discussion of this topic is available from TAI in Understanding Rheological TestingThermosets.