Will - 2013
Will - 2013
Will - 2013
p
p
2b
S
A
p
The contact area A is a function of the contact depth h
c
, which
is defined as
h
c
5h
max
2e
F
S
h
max
is the maximal indenter displacement and S 5dF/dh the
contact stiffness at the beginning of unloading. S is determined
by fitting the unloading curve by the power law F5a h2h
p
m
,
where a and m are fitting constants and h
p
is the final depths of
the indent after complete unloading.
18
For the Berkovich
indenter tip used the geometry constant e is 0.75 and
A 24:5 h
2
c
The shape correction factor b for a Berkovich indenter is
unity.
18
With the knowledge of the Poissons ratio ration of the
sample t and the indenter t
i
and the modulus of the indenter
E
i
, the modulus of the sample E can be determined by
1
E
r
5
12t
2
E
1
12t
2
i
E
i
As polymers often are characterized by viscoelastic material
behavior, its influence on nanoindentation has to be considered.
The delayed viscoelastic material response results in a distortion
of the loaddisplacement curve.
17,19,20
In particular, because of
the gradually increasing deformation after loading and the grad-
ually decreasing deformation after unloading, the unloading
curve of a viscoelastic material is more convex than that of elas-
tic materials. This influences the resulting contact stiffness and
accordingly the determination of elastic modulus. The influence
of viscoelastic effects on the nanoindentation results can be
reduced by the insertion of a dwell time between loading and
unloading, by slow loading rates and by fast unloading
rates.
17,19
To check the impact of viscoelastic effects on the
results presented in this work, nanoindentation measurements
were performed with different loading rates between 2 and 10
mN/sec and with different dwell times between 0 and 20 sec.
Low loading rates and a dwell time of more than 2 sec ensure
undistorted, reproducible loaddisplacement curves, and reliable
modulus values.
The nanoindentation measurements were performed with a
NanoTest 600 nanoindenter (Micromaterials) and an indenter
in Berkovich geometry. The load-controlled mode was used
with loading and unloading rates of 2 mN/sec. In all measure-
ments a dwell time of 5 sec was inserted between loading and
unloading. Before analysis, the raw data of the loaddisplace-
ment measurement are corrected by the system compliance. To
determine the contact stiffness S, the unloading curve was fitted
with a power law between 0.8F
max
and F
max
. A Poissons ratio
of 0.35 is used.
21
Average modulus values were obtained by
investigating several comparable resin regions. All average values
are calculated from more than nine individual values. The
measurements were performed on plane surfaces of the polymer
samples, which were prepared by a grinding and polishing pro-
cess. Approximately 50 mm of the surface material was ablated
by this process.
During indentation compressive loading is applied to the sam-
ple surface. Therefore, the measured moduli should be corre-
lated with (macroscopically determined) compressive moduli.
For materials with pronounced tensile-compressive anisotropy
caution is recommended. For those cases comparing the moduli
measured by nanoindentation to macroscopically determined
tensile or flexural moduli might be error-prone.
The macroscopic mechanical testing was done with a Kappa 50
DS universal testing machine (Zwick). Tensile-compressive tests
in the elastic range were performed on dog bone-shaped resin
samples with 1 mm/min test speed. Tensile and compressive
moduli were determined for at least four specimens of each cur-
ing degree. The literature value for the macroscopic tensile
modulus of the completely cross-linked resin system is 2.89
GPa.
16,21
To our knowledge no literature data for the macro-
scopic compressive modulus exists. For comparable epoxy resin
systems different behavior of the compressive moduli is
reported. For some resin systems the compressive modulus
exceeds the tensile modulus by up to 50 %,
22,23
for others the
compressive and tensile moduli are comparable.
24
EXPERIMENTAL RESULTS AND DISCUSSION
In the following the thermo-physical and mechanical investiga-
tion of partially and fully cross-linked RTM6 epoxy resin sam-
ples is presented. First we describe the dependence of glass
transition temperature, density, and micro- and macromechani-
cal moduli on the curing degree. Then the influence of a sec-
ond, final curing cycle on the resin properties is investigated.
Dependence of Curing Degree on Isothermal Curing
Treatment
By isothermal heating cycles samples with defined partial curing
degrees between 55% and 95% are produced. Isothermal curing
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4340 J. APPL. POLYM. SCI. 2013, DOI: 10.1002/APP.39722 WILEYONLINELIBRARY.COM/APP
ensures comparable chemical reaction processes for all curing
degrees. The curing behavior is determined by an interrelation
of physical resin properties, e.g. the viscosity, and chemical reac-
tion kinetics, e.g. the progress of curing.
12
In Figure 5 the cur-
ing degree as a function of the isothermal heating time is
displayed for two curing temperatures, namely the reduced
heating temperature of 135
C.
The curing degree is defined by the duration of isothermal
heating. With increasing heating time the curing degree
increases monotonically and for long heating periods saturates
at a defined maximum curing degree. At the standard heating
temperature of 180
C. At
higher heating times the curing degree approaches slowly to
the maximum value of 81%. The lower reaction rate for the
reduced heating temperature of 135
C. Additionally,
because of annealing at T
c
<T
g
, physical ageing of the nonequi-
librium glassy material with structural relaxation processes
starts. The molecular rearrangements result in a gradual
decrease of the specific enthalpy of the system, which can be
attributed to a decrease of free volume and/or a decrease in
molecular conformational energy with time and influence the
resins physical properties.
57
When cooling to room tempera-
ture, the sample stays in its glassy state and the structural rear-
rangements remain.
Figure 5. Dependence of curing degree on isothermal heating time for the
curing temperatures 135
C and 180
C.
Figure 6. Glass transition temperatures in dependence of curing degree
for a heating temperature of 135
C. As T
c
<T
g
at the end of cure, these sam-
ples are in the glassy state and ageing processes start. Because of
the vitrification a is limited to 95%.
Density and Modulus of Partially Cross-Linked Resin
Density changes during cross-linking of glassy thermosetting
network polymers are caused by different, partly opposing
effects. On the one hand, the increase of the covalent bond
fraction with increasing cross-linking causes volume shrinkage
and densification of the polymer. On the other hand the more
and more restricted packing of polymer chains because of net-
work formation results in a decrease of density with conver-
sion.
10,11
Besides, physical ageing during curing at T
c
<T
g
causes a volume decrease and thus a densification of the glassy
material because of structural relaxation processes.
57
Also an
emission of volatile specimen can occur, which causes a mass
loss of the sample.
9
Additionally, also the cooling process from
the end-of-curing state (rubbery or glassy) to the room tem-
perature state (glassy) influences the room temperature density
of the glassy thermoset. If the cooling process involves a long
cooling period within the rubbery state, an efficient chain
packing and a high density will result. In contrast, a long cool-
ing period within the glassy state allows only minimal molecu-
lar rearrangements and thus causes an inefficient chain
packing and a low density.
11
Dependent on the chemical struc-
ture of polymer and hardener and the processing conditions,
the individual contributions of the described effects determine
the final density of the glassy thermoset as a function of the
curing degree.
The density is directly correlated to the molecular structure of
the polymer, e.g. the crosslinking density and the molecular
weight. Therefore it is also closely connected to the modulus of
the resin sample, which is determined by the molecular struc-
ture, intermolecular forces, intramolecular forces, and relaxation
processes. For epoxy systems a similar behavior of modulus and
density is reported.
9
Figure 7. Schematic illustration of different physical states of resin system in dependence of curing degree and temperature.
Figure 8. Density of the partially and fully cross-linked polymer samples
(T
c
5135
C and 180
C and 180
C, respectively) in
dependence of curing degree, together with linear fit lines.
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WWW.MATERIALSVIEWS.COM WILEYONLINELIBRARY.COM/APP J. APPL. POLYM. SCI. 2013, DOI: 10.1002/APP.39722 4343
surface ageing of the polymers, as described in literature.
30,31
However, this description, which would result in an increased
surface modulus and surface density, cannot explain our experi-
mental results as will be explained in the following. As nanoin-
dentation probes the surface properties, the micromechanical
moduli would be affected by such surface degradation. In con-
trast, bulk properties as macromechanical modulus and density
should only be marginally influenced by an aged surface layer
and should show a smaller step in the transition region and
smaller values in the ageing regime. However, a similar relative
step height (defined as ratio between the step height in the
transition region and the total decrease between 55% and
76.5% curing degree) of micromechanical modulus (55.1%) and
density (50.0%) is observed. It is clearly higher than that of the
macromechanical moduli of 13.5%. Thus, the differences
between micro- and macromechanical testing cannot be caused
by surface ageing effects. The good agreement between density
and micromechanical modulus suggests that micromechanical
testing by nanoindentation is more sensitive to the molecular
arrangement of the polymer, in particular to the molecular
relaxations because of annealing, than macromechanical testing.
The mechanical testing conditions seem to allow an emphasis of
different modulus contributions, i.e. the molecular structure or
molecular forces.
Nanoindentation of polymer surfaces thus represents a very val-
uable tool for modulus and density investigation of polymers
with high lateral resolution that expands the possibilities of
macroscopic mechanical testing.
The irregularity of density and modulus observed in the transi-
tion region is a particular feature of our partially cross-linked
samples, which to our knowledge is not described in literature
so far. It is caused by the specific isothermal curing cycles,
which allow a transition from rubber to glassy state during cur-
ing. This transition influences the properties of the partially and
fully cross-linked thermosetting samples even in the glassy state
after cooling down to room temperature and represents a
promising effect for defined adjustment of physical resin prop-
erties. The relatively high moduli above the step within the
transition region are typical for much lower cross-linking
degrees and could be advantageous during further curing treat-
ments or processing.
Investigation of Partially/Finally Cured Resin Samples
All partially cross-linked resin samples are submitted to a sec-
ond, final curing cycle at 180
C and 212.4
C. As the glass
transition temperature of all partially cured samples lies below
180
C. Therefore this
Figure 10. Curing degrees of partially and fully cured resin samples and
corresponding partially/finally and fully/finally cured samples.
Figure 11. Glass transition temperatures of partially and fully cured resin
samples and corresponding partially/finally and fully/finally cured
samples.
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4344 J. APPL. POLYM. SCI. 2013, DOI: 10.1002/APP.39722 WILEYONLINELIBRARY.COM/APP
sample stays in its glassy state during final curing and only little
increase of curing degree and glass transition temperature is
possible. The resulting 94/100-sample exhibits a curing degree
of 96% and a glass transition temperature of 217
C, which are
slightly higher than the values obtained by combined partially
and finally curing.
Figure 12 shows the micromechanical moduli of the partially/
finally and fully/finally cured resin samples, in comparison with
the corresponding values of the partially or fully cured samples.
For all partially cured resin samples a decrease of modulus with
final curing treatment at 180
C, final curing
takes place at T
c
<T
g
. This results in an annealing process with
structural relaxations and the corresponding increase in modu-
lus of the 94/100-sample. A not negligible mechanical mismatch
of moduli of 0.25 GPa between the 94 and 94/100 samples is
observed. A combination of fresh resin with completely cured
resin and following final curing, e.g. for joining, thus is not
favorable. Also CFRP processing steps, which involve a thermal
impact on a conventional fully cross-linked resin sample, e.g.
the application of functional layers, will cause a change of
mechanical properties in the heated resin regions. The resulting
embrittlement of the surface regions can weaken the CFRP
component.
SUMMARY
Partial cross-linking of tetra-functional thermosetting RTM6
epoxy resin retains particular chemical reactivity of the polymer
and marks a promising way for new curing and processing
routes for CFRP production, e.g. the development of energy
efficient curing cycles, joining of CFRP components or applica-
tion of functional layers. A second final curing step guarantees
the complete cross-linking of the resin.
Knowledge of the interrelation between basic thermo-physical
and mechanical properties of the partially and finally cross-
linked resins is necessary to develop specifically adapted curing
cycles for different applications. With this objective the investi-
gation of curing degree, glass transition temperature, density,
and micro- and macromechanical modulus of partially and
finally cured RTM6 epoxy resin samples in the glassy state was
performed. The results show a significant dependence of the
physical properties on the curing history and the curing degree.
Density and modulus show on the one hand a decrease with
increasing curing degree that is caused by the cross-linking reac-
tion of epoxy resin and hardener and the built-up of a three-
dimensional network. On the other hand an irregularity in the
so called transition region between 74% and 79% curing degree
is observed, which can be correlated to the transition from rub-
ber to glassy state during the thermal treatment. The resulting
ageing in the glassy state is connected to structural relaxation
processes, which enhance the density and modulus of the poly-
mer. The step-like irregularity of physical properties is a typical
feature of samples manufactured with our isothermal, low tem-
perature curing cycle and demonstrates the options of adapted
curing treatments for defined adjustment of physical properties.
The relatively high modulus and density above the step is typi-
cal for resins with much lower curing degrees and offers new
possibilities, e.g. for joining of partially cross-linked and fresh
resin parts. After final curing of the partially cross-linked resins,
the resulting curing degree, glass transition temperature and
Figure 12. Micromechanical moduli of partially and fully cured resin sam-
ples and corresponding partially/finally and fully/finally cured resin
samples.
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modulus are similar to that of a conventional fully cured sample
and only negligible mismatch of the thermo-physical and
mechanical properties exists.
The investigations demonstrate the impact of the thermal his-
tory on the basic physical properties of tetra-functional epoxy
resins systems and the wide field of potential applications of
partially cross-linked epoxy resin systems.
ACKNOWLEDGMENTS
Thanks to G unter Obermeier and Andreas Monden for valuable
scientific contributions.
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