REPORT 2
Rheometry of a CNF-loaded polymer: the effect of processing
conditions
Nicolas Hanine, Alessio Pirani, Sara Reda
Introduction
In this report, the rheological properties of epoxy resin filled with different
concentrations of carbon nanofibers (CNFs) are studied. Generally, the epoxy
polymer with and without the nanofibers exhibits shear thinning behaviour, a
viscoplastic behaviour.
Ultrasonication method is used to prepare CNF-epoxy nanocomposites, varying
the time of sonication in order to investigate its effect on mechanical properties.
Rheological behaviour of two different CNFs concentrations is studied at
different sonication times of the composites. Both concentrations exhibit a shear
thinning behaviour at the shear rate ranges investigated.
Shear-thinning
Shear-thinning behaviour (or pseudoplastic flow behaviour) is characterised by
decreasing viscosity with increasing shear rates [1], as shown in figure 1.
Figure 1. A typical shear-thinning curve. [2]
1
The two extreme regions are characterised by a constant trend, indicative of
Newtonian behaviour of the fluid. These regions are defined first Newtonian
region and second Newtonian region [2].
Shear thinning behaviour is related to the internal structures of samples: when
polymers undergo shear, for example, entangled chains of polymers change in
their shape and untangle themselves, thus resulting in less flow resistance and
shear-thinning flow behaviour [1].
Cross model
The Cross model is a commonly used model for a non-Newtonian fluid that
exhibits a shear thinning behaviour. The Cross model is represented by the
following empirical equation:
η0 −¿ η
η ( γ̇ )=η ∞ + ∞
¿
1+(k γ̇ )n
where η0 and η ∞ represent the asymptotic viscosity at zero and infinite shear
rate, k and n are two constant values [3].
This model is used in order to fit viscosity data for each sample and this fitting is
particularly good, as shown in the following.
Materials
Carbon nanofibers (CNFs) are promising materials in many fields, such as
photocatalytic, nanocomposites, energy devices, filtration, sensors, tissue
engineering, and drug delivery [4], due to their remarkable properties: tensile
strength of 3-7 GPa, tensile modulus of 300-600 GPa, thermal conductivity of
2000 W/mK [4].
Figure 3. SEM images of the CNFs used.
2
For this experiment, it is prepared a mixture between PRIME 27 Resin, which is
an epoxy resin, and CNFs with the concentration of 0.25 wt% and a mixture
between PRIME 27 Resin and CNFs with the concentration of 0.5 wt%.
The epoxy resin is usually used in industrial applications. It is a liquid clear and
colorless. PRIME 27 Resin has a density of 1.132 g / cm3 [5].
For this laboratory experience, two samples are prepared:
1. a mixture between PRIME 27 Resin and CNFs with the concentration of
0.25 wt%
2. a mixture between PRIME 27 Resin and CNFs with the concentration of 0.5
wt%.
Both composites are prepared using an analytical balance. For the first mixture,
10.007 g of Prime 27 resin are poured into a beaker and 0.0253 g of CNFs are
weighed on a weighing paper. For the second mixture, 10.200 g of Prime 27
resin are poured into a beaker and 0.0513 g of CNFs are weighed on a weighing
paper. Then they are mixed and placed into the ultrasonic bath to perform a
direct mixing.
The ultrasonication is the process of exposing the mixture to sound waves in
order to agitate the fibers and destroy the agglomerates, resulting in a uniform
dispersion of CNFs.
The higher the number of sonication cycles, the better the quality of the
dispersion: for this reason, for each concentration two measurements are
performed: one after 6 cycles of sonification and the other one after 12 cycles of
sonification, with an alternation between the two functions sweep and degas.
Each cycle has a duration of 15 minutes.
Each sample is poured on the plate of the rheometer. Then, the gap is set to 1
mm to perform the trimming and, after a rest time of 3 minutes, the
measurement is made.
The steps followed for both the concentrations are described by figure 4.
Figure 4. Steps followed for both the concentrations.
3
Instrumentation
The measurements are performed with Anton Paar MCR 302 rheometer, which is
described in the “Introduction to Rheology”. It is used a parallel-plate geometry
with a diameter of 50 mm.
Measurement Method
Flow curves, or viscosity curves, are obtained with rotational tests, that operate
with continuous rotation of the measuring system [6]. The rotational tests are
carried out in controlled shear rate (CSR) mode.
Flow curves are usually measured at a constant measuring temperature, i.e.
under isothermal conditions. The experiment is performed at 20°C.
The test is performed with 50 acquisition points on a logarithmic scale. For each
measurement a steady state as sampling mode, with a timeout time of 100 s, is
used.
All the samples are subjected to two measurements with different range of shear
rate: 10-2 s-1 ÷ 100 s-1 and 10-2 s-1÷ 1000 s-1.
During the measurement, the following data are recorded:
● Time [s];
● Torque [µN·m];
● Deflection Angle [mrad];
● Rotational Speed [1/min];
● Gap [mm];
The following table summarizes the type of test and the time of sonication for
each measurement.
Sample Ultrasonic bath Test
Neat Epoxy - Rotational
Epoxy + 0.25 wt% Short Rotational
CNFs
Epoxy + 0.25 wt% Long Rotational
CNFs
Epoxy + 0.50 wt% Short Rotational
CNFs
4
Epoxy + 0.50 wt% Long Rotational
CNFs
Table 1. Recorded data.
Matlab script
Data are imported and stored in dedicated arrays.
%***********************************
% data import
%neat epoxy
NE= readtable('Neat Epoxy-2.xlsx');
timeNE=NE.Time; torqueNE=NE.Torque; deflection_angleNE=NE.DeflectionAngle;
rotational_speedNE=NE.RotationalSpeed; gapNE=NE.Gap;
normal_forceNE=NE.NormalForce;
%Epoxy+CNF 0.25 _wt
E025L= readtable('Epoxy+CNF 0.25 _wt Long US-2.xlsx');
E025S= readtable('Epoxy+CNF 0.25 _wt short US-2.xlsx');
time025L=E025L.Time; torque025L=E025L.Torque;
deflection_angle025L=E025L.DeflectionAngle;
rotational_speed025L=E025L.RotationalSpeed; gap025L=E025L.Gap;
normal_force025L=E025L.NormalForce;
time025S=E025S.Time; torque025S=E025S.Torque;
deflection_angle025S=E025S.DeflectionAngle;
rotational_speed025S=E025S.RotationalSpeed; gap025S=E025S.Gap;
normal_force025S=E025S.NormalForce;
%Epoxy+CNF 0.5 _wt
E05L= readtable('Epoxy+CNF 0.5 _wt Long US-2.xlsx');
E05S= readtable('Epoxy+CNF 0.5 _wt short US-2.xlsx');
time05L=E05L.Time; torque05L=E05L.Torque;
deflection_angle05L=E05L.DeflectionAngle;
rotational_speed05L=E05L.RotationalSpeed; gap05L=E05L.Gap;
normal_force05L=E05L.NormalForce;
time05S=E05S.Time; torque05S=E05S.Torque;
deflection_angle05S=E05S.DeflectionAngle;
rotational_speed05S=E05S.RotationalSpeed; gap05S=E05S.Gap;
normal_force05S=E05S.NormalForce;
%*********************************************************
Geometry PP50
PP50 has a diameter of 50 mm. The conversion factors are obtained by the
relationships described in the “Introduction to Rheology”.
%*************************************************************
%geometry: PP50
R= 25*10^-3;
% Np=100;
5
Css=(4/(3*pi))*(1/R^3);
Csr= (4/3)*(pi*R)/(60);
%*************************************************************
Rheological parameters
Rheological parameters, such as viscosity, are calculated from the measured
values of torque, deflection angle and speed using conversion factors.
%************************************************************
for i=1:52
tauNE(i)=(Css*torqueNE(i)*10^-3);
shear_rateNE(i)= (Csr*rotational_speedNE(i))/(gapNE(i)*10^-3);
viscosityNE(i)= tauNE(i)/shear_rateNE(i);
tau025L(i)=(Css*torque025L(i)*10^-3);
shear_rate025L(i)= (Csr*rotational_speed025L(i))/(gap025L(i)*10^-3);
tau025S(i)=(Css*torque025S(i)*10^-3);
shear_rate025S(i)= (Csr*rotational_speed025S(i))/(gap025S(i)*10^-3);
viscosity025L(i)= tau025L(i)/shear_rate025L(i);
viscosity025S(i)= tau025S(i)/shear_rate025S(i);
tau05L(i)=(Css*torque05L(i)*10^-3);
shear_rate05L(i)= (Csr*rotational_speed05L(i))/(gap05L(i)*10^-3);
tau05S(i)=(Css*torque05S(i)*10^-3);
shear_rate05S(i)= (Csr*rotational_speed05S(i))/(gap05S(i)*10^-3);
viscosity05L(i)= tau05L(i)/shear_rate05L(i);
viscosity05S(i)= tau05S(i)/shear_rate05S(i);
end
%***************************************************
Flow and viscosity curves
The different curves are plotted.
%***************************************************
% flow curve and viscosity curve
% neat epoxy
figure (1)
semilogx(shear_rateNE, viscosityNE,'k')
grid on
xlabel('shear rate (1/s)'); ylabel('viscosity (cP)'); title('Viscosity curve of
neat epoxy');
figure (2)
plot (shear_rateNE, tauNE,'k')
grid on
xlabel('shear rate (1/s)'); ylabel('shear stress (Pa)'); title ('Flow curve of
neat epoxy')
% Epoxy+CNF 0.25 _wt
figure (3)
semilogx (shear_rate025L, viscosity025L,'r')
hold on
semilogx (shear_rate025S, viscosity025S,'b')
grid on
xlabel('shear rate (1/s)'); ylabel('viscosity (cP)'); title('Viscosity curve of
epoxy+CNF 0.25 wt');
6
legend ({'Epoxy+CNF 0.25 _wt Long US-2','Epoxy+CNF 0.25 _wt short US-
2'},'Location','best');
figure (4)
plot(shear_rate025L,tau025L,'r')
hold on
plot(shear_rate025S,tau025S,'b')
grid on
xlabel('shear rate (1/s)'); ylabel('shear stress (Pa)'); title ('Flow curve of
epoxy+CNF 0.25 wt')
legend ({'Epoxy+CNF 0.25 _wt Long','Epoxy+CNF 0.25 _wt short'},'Location','best');
% Epoxy+CNF 0.5 _wt
figure (5)
semilogx (shear_rate05L, viscosity05L,'r')
hold on
semilogx (shear_rate05S, viscosity05S,'b')
grid on
xlabel('shear rate (1/s)'); ylabel('viscosity (cP)'); title('Viscosity curve of
epoxy+CNF 0.5 wt');
legend ({'Epoxy+CNF 0.5 _wt Long','Epoxy+CNF 0.5 _wt short'},'Location','best');
figure (6)
plot(shear_rate05L,tau05L,'r')
hold on
plot(shear_rate05S,tau05S,'b')
grid on
xlabel('shear rate (1/s)'); ylabel('shear stress (Pa)'); title ('Flow curve of
epoxy+CNF 0.5 wt')
legend ({'Epoxy+CNF 0.5 _wt Long','Epoxy+CNF 0.5 _wt short'},'Location','best');
%**************************************************************
% neat + short
figure (7)
semilogx(shear_rateNE, viscosityNE,'k')
hold on
semilogx (shear_rate025S, viscosity025S,'r')
semilogx (shear_rate05S, viscosity05S,'b')
grid on
xlabel('shear rate (1/s)'); ylabel('viscosity (cP)'); title ('Viscosity curve with
different concentration of CNF','Short sonication')
legend ({'Neat epoxy','Epoxy+CNF 0.25 _wt short','Epoxy+CNF 0.5 _wt
short'},'Location','best');
% neat + long
figure (8)
semilogx(shear_rateNE, viscosityNE,'k')
hold on
semilogx (shear_rate025L, viscosity025L,'r')
semilogx (shear_rate05L, viscosity05L,'b')
grid on
xlabel('shear rate (1/s)'); ylabel('viscosity (cP)'); title ('Viscosity curve with
different concentration of CNF','Long sonication')
legend ({'Neat epoxy','Epoxy+CNF 0.25 _wt Long','Epoxy+CNF 0.5 _wt
Long'},'Location','best');
%*****************************************************************
7
Normal force curve
Normal force curves of different samples are plotted.
%*****************************************************************
% normal force
figure (9)
plot (shear_rateNE,normal_forceNE,'k');
grid on
xlabel('shear rate (1/s)'); ylabel('normal force (mN)'); title ('Normal force of
neat epoxy');
figure (10)
plot (shear_rate025L, normal_force025L,'r')
hold on
plot (shear_rate025S, normal_force025S, 'b')
grid on
xlabel('shear rate (1/s)'); ylabel('normal force (mN)'); title ('Normal force of
epoxy+CNF 0.25 wt');
legend ({'Epoxy+CNF 0.255 _wt Long','Epoxy+CNF 0.255 _wt
short'},'Location','best');
figure (11)
plot (shear_rate05L, normal_force05L,'r')
hold on
plot (shear_rate05S, normal_force05S, 'b')
grid on
xlabel('shear rate (1/s)'); ylabel('normal force (mN)'); title ('Normal force of
epoxy+CNF 0.5 wt');
legend ({'Epoxy+CNF 0.5 _wt Long','Epoxy+CNF 0.5 _wt short'}, 'Location','best');
%************************************************************
8
Results and Discussion
Neat epoxy
For neat epoxy, the flow curve is obtained by plotting shear stress versus shear
rate and the viscosity is calculated and plotted (figure 5).
Figure 5. Flow curve (left) and viscosity curve (right) of neat epoxy.
The neat epoxy is a polymer so one would expect a shear thinning behaviour.
Instead, it behaves as a typical Newtonian fluid with a constant value of viscosity
in the shear rate range of 1-100 s−1 . Newtonian flow behaviour means that the
measured viscosity is independent of the shear rate.
At low shear rate, we meet reliability problems of the acquired data: it is because
the values of torque are lower than 1 μN ∙m (the minimum torque is 10 nN ∙ m)
(table 2).
POINT TORQUE
NO. [ΜN·M]
1 0.2677
2 0.31912
3 0.40751
4 0.50912
5 0.65565
9
6 0.82945
7 1.0282
8 1.3084
Table 2. Measured torque.
The normal force is obtained by the load cell that translates the mechanical
action exerted by the sample on the plate into a force.
It can be noted an unexpected trend at high values of shear rate, greater than
100 s-1.
Indeed, from figure 6 it can be observed that normal force values undergo a
sharp decrease: it is due to a non-optimal contact between the sample and the
plates probably caused by either sample spillage or unsuitable geometry.
Therefore, we can conclude that the obtained values are unrealistic and thus we
witness false shear thinning.
Figure 6. Normal force curve of neat epoxy
Epoxy resin with CNFs
Next, loading CNFs above a critical concentration, one observes a shear thinning
behaviour, typical for filled polymer suspensions [1]. The viscosity of the filled
epoxy system increases significantly with increasing CNF concentration [7], as in
figure 7.
10
Figure 7. Viscosity curve of samples with short sonication (left) and long sonication
(right).
In figure 7 it can be observed the viscosity curves of the samples with different
concentration of CNFs and different number of sonication cycles in the ultrasonic
bath. The two figures show that the addition of 0.25 wt% of CNFs causes a
considerable increase in viscosity when compared to neat epoxy resin. In the
examined range of shear rate, there is a change from the Newtonian behaviour
of the neat epoxy resin into a shear-thinning behaviour of the filled samples, as
typically happens to suspensions containing nanofillers.
When shear stress is applied, the fibers align parallel to the flow direction and
they are no longer randomly oriented as they were in case of optimal dispersion
at rest (figure 8).
For this reason, the fibers will slide more easily along each other and the
viscosity, intended as sample’s resistance to flow, will be lower [1].
Figure 8. Fibers in a suspension: randomly arranged at rest (left), under shear, they
orient in the direction of shear (right). [1]
The high aspect ratio of CNFs causes network formation that inhibits the
polymer chain mobility, thus confining the epoxy resin and increasing the
macroscopic viscosity. Under the application of shear, the agglomerates are
11
destroyed, therefore the liquid is free to move again, thus resulting in the shear
thinning behaviour [1].
Figure 9. Epoxy resin confined in CNFs agglomerates. [8]
Viscosity increases as CNFs concentration increases [7], indeed we can observe
that the viscosity of the sample with 0.50 wt% concentration is higher than the
viscosity of the sample with 0.25 wt%.
In all cases, it can be observed that increasing the shear rate, the measured
viscosity tends asymptotically to the value of the neat matrix (resin).
The effect of sonication time on viscosity is also investigated (figure 10).
Figure 10. Viscosity curve of epoxy with 0.25 wt% of CNFs (left) and with 0.5 wt% of
CNFs (right).
In this case, the figures show the shear thinning behaviour of the samples with
same concentration but different sonication time in the ultrasonic bath. In both
cases, we can observe that an increase in sonication time results in an increase
in viscosity.
Indeed, a long sonication time results in a greater quality of dispersion of fillers
12
having higher aspect ratio, thus promoting a greater number of interfaces
between epoxy resin and CNFs that causes an increase in viscosity.
Cross model fitting
Data are fit with Cross model: the values of η0 , η ∞, k and n, obtained by the fitting,
are reported in the following table. It can be noted high R square values that
confirm the good quality of the fitting.
Samples R-square η0 η∞ k n
Epoxy+CNF
0.25wt%
0.9905 2123 654.2 5.459 0.6638
Short
Epoxy+CNF
0.25wt%
0.988 4782 669.2 8.109 0.6862
Long
Epoxy+CNF
0.5wt%
0.9951 9264 796.9 8.847 0.8736
Short
Epoxy+CNF
0.5wt%
0.9888 1.782e+04 916.1 7.857 1.044
Long
Table 3. Parameters of Cross model.
Normal force
13
The values of normal force are analysed (figure 11).
Figure 11. Normal force curves of samples with short sonication (left) and long
sonication time (right).
As it can be observed in the graphs, at the same shear rate, the normal force
acting on the sample with 0.5 wt% concentration is smaller in modulus than the
normal force acting on the sample with 0.25 wt% concentration.
In fact, the fibers exert an antagonistic action against the centrifugal force since
they keep the polymer bound to themselves, thus hindering the sample from
spilling. Therefore, the sample with higher fiber concentration fights the
centrifugal force more decisively: therefore, it limits the contact loss between
sample and plates and the normal force is lower in modulus.
References
[1] Anton Paar. “Internal structures of samples and shear-thinning behaviour”.
www.anton-paar.com.
[2] Pinzhi Liu, Jie Lu, Hualong Yu, Ning Ren, Frances E. Lockwood, and Q. Jane
Wang. “Lubricant shear thinning behavior correlated with variation of radius of
gyration via molecular dynamics simulations”. The journal of chemical physics.
2017, 147, 084904.
[3] Scott C. Hauswirth, Christopher A. Bowers, Christopher P. Fowler, Pamela B.
Schultz, Amanda Dye Hauswirth, Timothy Weigand, Cass T. Miller. “Modeling
cross model non-Newtonian fluid flow in porous media”. Journal of Contaminant
Hydrology,Volume 235, 2020, 103708.
[4] Alaa Mohamed, Chapter Eight – “Synthesis, Characterization, and
Applications Carbon Nanofibers”. Editor(s): Srinivasarao Yaragalla, Raghvendra
14
Mishra, Sabu Thomas, Nandakumar Kalarikkal, Hanna J. Maria, Carbon-Based
Nanofillers and Their Rubber Nanocomposites, Elsevier, 2019, Pages 243-257.
[5] Gurit. “PRIME™ 27” technical datasheet.
[6] Anton Paar. “Basic of rheology”. www.anton-paar.com.
[7] Jiahua Z., Suying W., Jongeun R., Mahesh B., Gang L., Zhanhu G. “In situ
stabilized carbon nanofiber (CNF) reinforced epoxy nanocomposites”. J. Mater.
Chem. 2010 ,20,4937-4948.
[8] Roey Nadiv, Ricardo M.F. Fernandes, Guy Ochbaum, Jing Dai, Matat Buzaglo,
Maxim Varenik, Ronit Biton, István Furó, Oren Regev. “Polymer nanocomposites:
Insights on rheology, percolation and molecular mobility”. Polymer. Elsevier.
2018.
15
