TA Rheo Thermoset
TA Rheo Thermoset
TA Rheo Thermoset
Rheology of Thermosets
Rheological Testing of
Thermosetting Polymers
General Considerations the controlled influence of heat
and pressure over time. Thus,
Thermoset Polymer Uses thermosets build their final struc-
Thermoset polymers form the ture during processing, forming a
matrix in filled plastics and fiber- three-dimensional internal struc-
reinforced composites used in a tural network of highly crosslinked
diversity of products. These range polymer chains. And the final
from consumer items and auto product is insoluble and not ther-
body panels to advanced compos- mally reformable.
ites for printed circuit boards Elastomers share characteris-
(PCBs), aerspace structural tics of thermoplastics and
compo-nents such as the Space thermosets. Elastomers begin
Shuttle payload bay door and jet as thermoplastic polymers with
engine cowls and ducts, and ex- discrete chains that later develop
pensive, high-performance sports a network of covalent crosslinks.
equipment. Also, thermosets are However, elastomers are distin-
used extensively as adhe-sives, guished from thermosets by the
molding compounds, and surface fact that the crosslink network is
coatings, including protective sol- formed in a separate post-polyme-
der masks for PCBs. rization step called vulcanization.
Another factor distinguish-ing the
Thermosets versus Ther- three classes of polymers is the
moplastics and Elastomers glass transition temperature T g –
the temperature at which poly-
Thermoset polymers are distin- mers reversibly transmute be-
guished from elastomers and tween rubbery and glassy states.
thermoplastic polymers in several For elastomers, the glass transi-
ways. tion tempe-ature is below ambi-
Thermoplastics are processed in ent temperatures; for thermoplas-
the molten state, their final shape tics and thermosets, it is substan-
and internal structure established tially above ambiant.
by cooling, and they can be sof-
tened and reshaped by reapplica- Studying the Crosslinking
tion of heat and pressure. Also, Reaction
their polymer chains, whether lin-
ear or branched, remain di-screte The formation of a thermoset
after molding. Thermoset poly- crosslinked network is shown
mers usually go through three schematically in figure 1.
stages. In the A-stage, some-
times called a resole, the resin is Understanding of this pro-cess
still soluble and fusible. In the B- has been advanced substantially
stage, thermosets are nearly in- by use of rheological analysis –
soluble, but are still thermoplas- measurements of resin viscosity,
tic. They can, however, spend only shear modulus, and damping.
a rela-tively short time in the mol- More sensitive than even Fourier
ten state because the tempera- transform infrared spectroscopy
tures that promote flow also cause for measuring extent of cure,
the material to crosslink. The rheological testing has become
crosslinking reaction is accom- a vital supplement to DSC, chro-
plished in the final stages of po- matography, and wet chemical
lymerization – the C-stage – dur- analysis in thermoset polymer
ing molding of the product under re-search and develop-ment. The
reasons for this reside in the na-
AAN015
3 Rheology of Thermosets
6
10
G' 10
5 good performance, a lower glass
Moduli G', G'' [Pa]
4
But this does not necessarily
10
4
mean that a higher Tg indicates
10
Minimum viscosity overcure: The difference between
complete cure and overcure can-
10
3
10
3
not be detected by measuring T g.
80 100 120 140 160
Temperature T [C]
A higher glass transition tempera-
ture may result form exposure
later to temperatures above those
of cure or postcure. The glass
Figure 3: Measurement of the minimum viscosity and transition temperature can be
approximate gel point for a curing epoxy molding compound lower if the prepreg were cut and
1
Fourier Transfom Mechanical Spectroscopy of Viscoelastic Materials with Transient Structure
E.E. Holly, S.K. Venkataraman, F. Chambon and H.H. Winter, Journal of Non-Newtonian Fluid Mechanics, 27(1988)17-26
A.Franck 10/04 V1
6 Rheology of Thermosets
0
10
an attendant peak in the tan δ
curve.
Besides being a more accurate
method for measuring T g, DMRT
reveals much about the material
30 32 34 36 38 40 before and after the glass trans-
time t [min] ition because DMRT also meas-
ures the rubbery plateau modu-
lus. This is important because, at
Figure 4: The precise gel point of a curing resin is identified by high thermoset cure levels, the
the intersection of tan δ curves generated in several rubbery plateau modulus is more
simultaneous frequency sweeps sensitive than is Tg itself for de-
tecting, for example, small differ-
laid up in a high relative humid- ences in a thermoset polymer cure
ity. (This can be verified by level.
retesting after drying the sample,
since the effect is reportedly re- Also called the a transition, the
versible.) And formulation errors glass transition is associated with
can shift the glass transition tem- crank-shaft motion of major chain
perature up or down. segments. Other transitions, des-
ignated as b, g, etc. in order of
To understand the inadequacy of descending temperature of occur-
Tg alone as a performance gauge, rence, arise from vibrations and
what Tg is must be understood. rotations. Material toughness and
The glass transition is a tempera- impact resistance correlate with
ture-induced morphological the magnitude of tan δ at the sec-
change in a polymer between a ondary (β, γ) peaks.
brittle, glassy state and a viscous,
rubbery state. The glass transi- For many materials, as the dy-
tion temperature Tg is the tem- namic oscillatory frequency is
perature at which this transition increased, transitions occur at
occurs. higher temperatures. Also, some
transitions shift different amounts,
Because the material ex-periences depending on their degree of fre-
a substantial change in rigidity in quency dependence. This helps
a short span of temperatures, locate some transitions in
the glass transition is a key fac- multiphase resin systems (such
tor in deciding the use-fulness as those modified by addition of
of a polymer. So, merely know- elastomers or thermoplastics) if
ing the temperature at which it one component is more fre-
occurs (all that DSC and TGA quency-dependent than another.
provide) is not enough. The Shifts in the glass transition tem-
modulus must be measured as perature and the b peak can indi-
a function of temperature as well. cate the effect of compounding or
This is accomplished most ef- process changes on product per-
fectively using dynamic me- formance. In general, the tem-
chanical rheological testing . perature of the secondary transi-
In the course of measuring the tion shifts more than does the
AAN015
7 Rheology of Thermosets
A.Franck 10/04 V1
8 Rheology of Thermosets
Gel Point
1
10
The gel point is the temperature
or time at which the first set of
0 1000 2000 3000 4000 5000 6000 covalent bonds connects across
time t [min] the sample (the onset of a three-
dimensional network) and the
molecular weight becomes infi-
nitely large. The gel point is im-
Figure 5: Measurement of the viscosity profile of a curing
portant in determining the time
thermoset resin as a function of heat-up rate
and temperature at which pres-
sure should be applied.
Pressure is needed during lami-
nation to squeeze the plies to-
gether, and timing is critical: Sub-
stantial pressure must not be ap-
plied until after the minimum vis-
cosity has been reached, else the
resin will bleed excessively at the
edges; but it must be applied be-
Isothermal cure at different temperatures fore the gel point to assure ad-
10
6 equate compaction.
10
5 TGDDM + DDS 100/30 Pressure is used also to control
outgassing of volatile by-products
4
10
173 C
generated in some thermoset
3 165 C polymer reactions such as those
10
involved in the manufacture of
viscosity η* [Pas]
152 C
10
2 143 C polyimides.
129 C
10
1
Excessive pressure must be
0
avoided during the lamination of
10
circuit boards that include an ox-
-1
10 ide-prepreg interfacial treatment
since sme oxides are fragile and
-2
10
can be crushed, causing dela-
-3
10
mination.
3 4
10 10
time t [s]
Optimum Heating Rate
Viscosity η* [Pas]
on the viscosity profile.
100 2
10
80
Isothermal Scans
60
1
40
10 Once the minimum visco-sity and
gel point have been determined,
20
a series of isothermal scans
0 0
10 should be run at temperature in-
0 1 2 3 4
tervals beginning with the mini-
Time t [hours] mum viscosity temperature and
continuing up to the gel point tem-
perature in intervals of about 10°C.
These scans can be made quickly
Figure 7: A thermoset resin production cure cycle in which on the ARES since it can can
hydraulic pressure is induced in the resin to reduce gas record one data point a second.
bubble nucleation in the cured matrix This information will help in de-
ciding the time and temperature
at which to impose isothermal
holds during the process. An iso-
thermal hold at minimum viscos-
ity extends the time the resin will
remain near the minimum viscos-
ity and determines the dimen-
sions of the processing window.
The time at or near the minimum
viscosity is a key factor in con-
trolling overall flow and avoiding
problems such as bulk porosity.
A second hold near the gel point
Temperature ramp 2 C/min is sometimes used to eli-minate
Test frequency 10 rad/s surface porosity. Typical isother-
mal scans are shown in figure 6.
Using the Viscosity
Profile
G', G'' [Pa]
Temperature T [°C]
cepts such as ”gas diffusion con-
120
trol.”
100
Diffusion control reduces gas bub-
80 ble nucleation in the curing ma-
trix by inducing hydraulic pres-
60
sure in the resin during the gas
40 volatilization stage of the cure
cycle. Figure 7 shows a typical
0 50 100 150 200
matrix resin cure cycle incorpo-
Time t [min]
rating diffusion control, superim-
posed on the viscosity profile.
Product Development
Figure 9: A graphite-epoxy production cure cycle
Viscosity profiles are used to
great advantage in ther-moset
product development to evaluate,
for example,
• new or different resin
formulations
280
260
to a phenolic injection molding
240
compound. The zinc stearate low-
220
ered the viscosity considerably at
200
Press Molding Cycle the barrel temperature without af-
180
fecting cure time.
-50 0 50 100 150 200 250 300 350 400 450
Process Development
Time t [min]
and Control
300 Developing Production Cure
Temperature T [°C]
Cycles
250
A dynamic mechanical viscosity
profile provides the rheological
Post cure cycle
200
data needed to construct a pro-
duction cure cycle. Figure 9
0 50 100 150 200 250 300 350 400 450 500 550 shows a typical cure cycle deve-
Time t [min] loped for a graphite/epoxy lami-
nate.
Figure 10: The cure and post-cure cycles for a polyimide resin Developing Post-Cure Cycles
AAN015
11 Rheology of Thermosets
Viscosity η* [Pas]
3
600 10
typical post-cure cycle in a circu-
lating air oven for a polyimide resin
400 B-stage advanced 10
2
composite used for a jet engine
component is shown in figure 10.
200 10
1
Quality Control
The cure step is the most critical
0
0 10 element in ther-moset process-
0 20 40 60 80 100 120 140 160 180
ing. Accordingly, maintenance of
Time t [min]
strict quality control standards on
the incoming materials, the
prepreg especially, is important.
Figure 11: B-stage resin advancement alters the viscosity Two areas of major concern are
profile of a curing thermoset resin degree of resin advancement and
the effects of moisture.
Prepreg Advancement
cycle.
viscosity η* [Pas]
600
10
Tests on prepreg samples imme-
diately prior to use can quickly
1 400
identify advancement level differ-
ences so that adjustments can be
0.1 200 made to the cure cycle. Figure
11 shows viscosity profiles of an
epoxy resin at three different lev-
0.01
0 20 40 60 80 100 120 140 160 180 200 els of minimum viscosity and the
time t [min] reaction rate (reflected in the slope
of the viscosity curve during the
isothermal hold), and the sooner
Figure 12: Viscosity profiles of a dry epoxy resin and the gelation occurs.
same resin after extended storage in a high humidity
A.Franck 10/04 V1
12 Rheology of Thermosets
Moisture Effects
tan δ
Modulus G'
tan δ testing before use, moisture-re-
0.03
lated cure problems can be
0.02 avoided, or at least minimized.
The effects of moisture are often
0.01 reversible, so the material may be
1E10 salvaged by drying before curing.
-200 -100 0 100 200 300 400 Figure 12 shows the viscosity pro-
Temperature T [°C] files of a dry epoxy resin and the
same resin after extended stor-
age in a high humidity.
Figure 13: Temperature sweep on a cured epoxy-graphite Evaluating Product
composite. The glass transition is manifested in a sudden and Performance
considerable decrease in the storage modulus with an
attendant peak in the tan δ curve Key factors in thermoset polymer
product performance are the
cured resin’s modulus and glass
transition temperature. The dy-
namic moduli (G’, G” or E’, E”)
are measured directly on solid
samples with or without fiber re-
inforcements at a selected fre-
quency as a function of tempera-
ture. And from these measu-
rements tan δ is automatically
calculated. The glass transition is
detected as a sudden and con-
siderable decrease in the storage
1E10
1 modulus and an attendant peak
in the tan δ curve. The symbol T g
denotes the temperature at which
this transition occurs.
1E9
0.1 Figure 13 shows the tan δ and
storage modulus curves, the
G' [Pa]
Tan δ
1E9
1 Figure 15 shows the effect on the
glass transition temperature of
tan δ
0.1 going from a low to high tempera-
1E8
ture and then repeating the test
Azelaic acid & BOMA
as the sample cools, using a
0.01
1E7 BOMA cured and a cured plus postcured
DDM
BTDA
sample of PMR-15 polymimide.
1E-3
-150 -100 -50 0 50 100 150 200 250 300 350 Figure 16 shows the effects of
Temperature T [°C] various curing agents on the glass
transition temperature of an epoxy
resin.
Figure 15: Temperature sweeps are an effective means for The data in figures 14 through 16
detecting the effects of different curing agents on the were obtained in bending and tor-
viscoelastic properties of thermoset resins sion. Figure 15 shows the glass
transition temperature as a func-
tion of cure level measured in ten-
sion following the procedure out-
1
lined in ASTM D5026.
9
10
Curing Temperature
Modulus G' [Pa]
93 °C
135 °C
tan δ
350 °C 0.1
8
10
0.01
7
10
-200 -150 -100 -50 0 50 100 150 200 250 300
o
Temperature T [ C]
A.Franck 10/04 V1
Keywords: thermopsets, processing, elasticity, cure, viscosity, performance, gel point, vitrification,
glass transition