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Wetting
Wetting
Jian Wang, Carlos A. Fuentes, Dongxing Zhang, Xungai Wang, Aart Willem Van
Vuure, David Seveno
PII: S0008-6223(17)30503-1
DOI: 10.1016/j.carbon.2017.05.055
Please cite this article as: Jian Wang, Carlos A. Fuentes, Dongxing Zhang, Xungai Wang, Aart
Willem Van Vuure, David Seveno, Wettability of carbon fibres at micro- and mesoscales, Carbon
(2017), doi: 10.1016/j.carbon.2017.05.055
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ACCEPTED MANUSCRIPT
Jian Wang1, 2,*, Carlos A. Fuentes2, Dongxing Zhang1, Xungai Wang3, Aart Willem
Van Vuure2, and David Seveno2
ABSTRACT
Physical adhesion between Carbon Fibres (CFs) and polymer matrices as well as the
formation of voids at the interface between these two materials are mostly controlled
the single fibre (microscale) to the fabric (macroscale) via the tow scale (mesoscale).
couples the effects of surface chemistry and geometry of the fibre assembly
wettability between tows composed of unsized and sized (T300) CFs. By comparing
* Corresponding author. Tel: +86 451 86281403. E-mail: wj8958@163.com (Jian Wang)
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their wettability at the micro- and mesoscale, we could quantify how the modification
1. Introduction
composites because of their superior mechanical properties [1, 2]. Nowadays, CFs are
widely used in many fields, from civil to industrial [2-5]. However, the final
not only on the intrinsic properties of the reinforcing CFs and polymer matrices, but
also on the adhesion between these components [6-10]. Moreover, during processing,
the wettability of CFs plays a crucial role in determining the quality of the final
composite interface. Good wettability between fibres and matrices leads to better
physical adhesion and fewer defects at the interface [9, 11]. Hence, various methods
However, the lack of good compatibility between CFs and resins is still a current
incomplete wetting at both single fibre and tow scales [18, 19] evidencing that .
During liquid molding processes, resin infiltration within CF tows and textiles is
determined not only by the wetting properties of the CF surface, but also by the fibre
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scales is essential.
The wettability of CFs with polymers can, for example, be revealed by measuring
contact angles made by liquid polymers or probe liquids on fibres. Typically, at the
the contact angles made by liquids around one fibre or multiple parallel aligned fibres
are obtained using the Wilhelmy balance method [12, 15, 16, 21, 22]., or at the
by optical methods [23]. A previous study [24] showed the difficulties of precisely
by optical methods [23]. It is however also very difficult to independently and reliably
evaluate the effects of surface chemistry and textile structure from the analysis of
drop shapes at the macroscale. CF tows are show an intermediate and interesting case
study, as their simple geometry, compared to fabrics, may not totally obscure the role
fibre, should ease the measurement of contact angles and provide for a representative
A CF tow can be considered as a porous medium; its wetting behavior is thus not only
dependent on the surface chemical properties of the fibres, but also on its pore
structure [25]. So far, to the knowledge of the authors, studies dedicated to wetting of
CF tows are not available. Furthermore, reports on the wettability of other fibrous
materials at the mesoscale are still limited [25-27]. In those studies, a fibrous material
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is considered as a bundle of capillary tubes, and the Washburn method [28] is used to
determine effective dynamic advancing contact angles assuming that its geometry
remains the same during the experiments. However, as shown by Rieser et al. [29, 30]
and their work on capillary-induced attraction between vertical cylinders, there exist
when a tow is partially dipped in a liquid, capillary forces, competing with the
bending stiffness of the fibres, are able to bend the fibres and trigger an elasto-
densification phenomenon which was also observed from arrangements of micro- [30]
and nanoscale [31] filaments, for instance CNTs, during the elasto-capillary self-
assembly process [32]. This inevitable aggregation can influence the reliability of
and hence, lead to incorrect estimation of the wettability of CF tows. Direct optical
[15, 25, 26, 33, 34] and the Wilhelmy methods are two other well-known approaches
used to measure contact angles on fibre shaped solid surfaces. The latter is mostly
used to accurately measure contact angles on dense solid (in cylinder or plate shape)
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tows composed of unsized CFs and sized (T300) CFs. The combination of these two
techniques provides a way to observe the aggregation of the tows and, thus, follow the
evolution of the tow perimeter, needed to calculate accurate contact angles according
to the Wilhelmy method. The optical technique also provides an independent way to
estimate the wettability of CF tows by analyzing the shape of the menisci formed
obtained from the Wilhelmy method. By comparing the wettability of the unsized and
T300 CFs at the micro- and mesoscale, we could finally quantify how the
mesoscale. Finally, the Cassie and Baxter [35] theory was applied to link the contact
2.1. Materials
sized CF tows named FT300-3000-40A (T300) purchased from Toray CFs Europe
S.A, respectively. The unsized CFs were produced at Deakin University from
commercial PAN precursor but skipping the sizing step. One T300 CF tow contains
3000 filaments with density of 1.76 g/cm3. The wetted T300 CF and unsized CF tows
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Before the wetting tests, the CF tows were washed in ethyl alcohol and dried at 80ºC
for 1h to obtain a clean surface by removing dust and grease without altering the CF
sizing. The tows were then cut into pieces (20 mm in length) and each piece was
clipped firmly into a holder that could be installed directly in the tensiometer.
The main properties of the test liquids (n-hexane: Acros; Deionized water: Millipore
The method proposed by Qiu et al. [24] for measuring dynamic contact angles was
used in this study to characterize the wettability of unsized single CFs with deionized
K100SF (Krüss GmbH, Hamburg, Germany) was used to measure the forces exerted
on a single CF during the dynamic wetting test. The K100SF tensiometer has a
claimed weight resolution of 0.1µg with testing velocities ranging from 0.1mm/min to
500mm/min. During the measurements, the fibre is stationary and the vessel holder
moves up (advancing cycle) and down (receding cycle). A sketch of the apparatus is
shown in Figure 1.
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Since measuring accurate perimeters of thin fibres is important for calculating precise
contact angles, the wetted perimeters of single CFs were measured using n-hexane
(99.6%) as a perfectly wetting liquid. Once accurate and reliable fibre perimeters and
capillary forces are obtained, the dynamic contact angles at constant advancing and
where Fmeasured is the force detected by the microbalance, 𝐿𝑓 is the perimeter of the
fibre, 𝜃𝑑 is the dynamic contact angle. All tests were conducted in a monitored and
controlled environment (25°C, 65% relative humidity, and vibration isolation cabinet)
Four fibres were tested by this method in case of the unsized CFs (contact angles for
sized T300 fibres were taken from [24]. Each fibre was repeatedly dipped in and
withdrawn from the liquid vessel three times at a velocity of 3.6 mm/min to measure a
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series of dynamic advancing and receding contact angles. Qiu et al. [24] suggested
A Motic SMZ-171 microscope and Moticam (CMOS) digital microscopy camera was
used in combination with the tensiometer to capture in real time (every 500 ms)
images of the formation of the meniscus around the tows. This gave access to external
contact angles and the variation of the tow diameters at various wetting positions
The optical analysis followed a two-step procedure: first, the pictures were analyzed
with Tracker software [37] to determine the local tow diameter 𝑑 and meniscus height
𝑧 by locating the position of two contact points, as shown in Figure 2. The meniscus
height is defined as the average value of height differences between these two contact
points and the baseline. The contact angle is then calculated using the James equation
[38], which models the height of a static meniscus made by a liquid around a
cylindrical substrate:
𝑜
𝑧 ≈ 𝑟 𝑐𝑜𝑠 𝜃𝑒𝑥 𝑙𝑛 [( 4𝑎
𝑜
𝑟 1 + 𝑠𝑖𝑛 𝜃𝑒𝑥 ) ]
‒ 𝛿 Equation 2
where 𝑟 is the local radius of the tow, 𝑎 = 𝛾𝐿𝑉/𝜌𝑔 the capillary length of the probe
liquid (with 𝜌 the liquid density, and g the gravity acceleration), and the Euler
constant (𝛿 ≈ 0.58). This equation predicts the height of a meniscus around a single
fibre. This model is therefore not fully adapted to the tow geometry, but should
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𝑜
provide a good estimation of 𝜃𝑒𝑥. In the case of deionized water, 𝑎 = 2724 µm,
𝑟
therefore the bond number is 𝐵𝑂 = 𝑎 ≈ 0.11 for a T300 CF tow (r ≈ 300 𝜇𝑚). For
a fibre, Clanet et al. [39] reported that the relative error in the height using Equation 2
Figure 3 shows theoretical James profiles for 600 µm and 300 µm diameter fibres,
modelling the wetted T300 and unsized tows respectively. The theoretical radial
extension of the meniscus is 3060 μm, which is much less than half of the width of the
images (of typically 6000 µm). The whole meniscus is therefore captured by the
camera, i.e. the position of the baseline can be precisely detected. In addition, errors
in the contact angles caused by the detection of the contact line and baseline were
checked. If the local diameter of a tow was 600 μm, a variation of the meniscus height
or the CF tow diameter would have only a slight influence on the calculated contact
angle values (for contact angles ranging from 40o to 70o). An error of ±2 pixels (≈2%
of the height or diameter) involves an error in the contact angles of less than 0.4o, i.e.
the effect is limited and will not significantly affect the contact angles measured.
Figure 2. In-situ observation of the meniscus formed between a T300 CF tow and
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a) b)
water.
Figure 3. Theoretical James profiles. a= 2724μm (typical of water) and 𝜃𝑒𝑥 = 40o; 50
Before each test, the tow sample was weighed to obtain its mass 𝑚𝑇𝑜𝑤. The real
volume of each CF tow (𝑉𝑓𝑖𝑏𝑟𝑒𝑠) can be calculated based on 𝑚𝑇𝑜𝑤 and the density of
CFs. If we assume that a CF tow has a perfect cylindrical shape during the wetting
test, the diameter of this cylinder can be measured with the camera and its total
volume (𝑉𝑇𝑜𝑡𝑎𝑙) calculated. Hence, the non-solid volume fraction of the CF tows
The K100SF Tensiometer was used to measure the forces exerted by the liquid on the
tows. During a test, the tows were slowly soaked in the liquid over a length of 1mm
and stopped at that position for 500s to make sure the external meniscus around the
tow reached a static configuration. The vessel was then moved down until complete
withdrawal from the liquid bath. The weight of liquid left in the tow was finally
measured. The forces exerted on the tows were detected continuously every 200ms by
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the microbalance during the whole procedure (including approaching, wetting and
withdrawing from the liquid bath). Six samples were tested for both unsized and T300
CF tows. As illustrated in Figure 4, capillary wicking in the inter-fibre space and the
formation of a meniscus around the tow are taking place quasi instantaneously when
the tows contact the liquid [33]. The detected forces combine the weights of the
imbibed liquid inside the tow and the meniscus formed around the tow. As to which
process dominates is further investigated by analyzing the force data following the
𝑓
Figure 4. (a) Schematics of a meniscus formed around a CF tow, 𝜃𝑒𝑥 is the external
The modified Washburn equation defining the flow of liquid penetrating through a
fibrous medium [40] was used to characterize the internal structure of a CF tow
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2
(𝑐𝑟)𝜖2(𝜋𝑅2)2 𝜌 𝛾𝐿𝑐𝑜𝑠 𝜃𝑎
2
𝑚 (𝑡) = [ 2 ] 𝜂
𝑡
𝜌2𝛾𝐿𝑉𝑐𝑜𝑠 𝜃𝑎
=𝐶 𝜂 𝑡 Equation 4
where 𝑚 is the mass of liquid above the liquid level, 𝜃𝑎 the effective advancing
contact angle, 𝜂 the viscosity of the liquid and t time (s). 𝐶 is a constant accounting
for the tortuous path of the flow in the real system, 𝜖 is the relative porosity and 𝑅 the
inner effective radius of the measuring tube. Pucci et al. [26, 41] determined in this
way dynamic effective advancing contact angles during capillary rise inside CF tows
positioned in a container. Pucci et al. assumed that the interaction between the fibres,
the container wall, and the liquid may be neglected; therefore, the forces detected by
the tensiometer could be considered as simply the weight of liquid rising and
penetrating the pores in-between the fibres. If we assume that the geometry and
content of pores is constant, i.e. the fibers fibres are immobile, 𝐶 can be determined
[26, 40, 41] by using a perfect wetting liquid like n-hexane. Since n-hexane is able to
dissolve the sizing on the surface of T300 CFs, we carried out the n-hexane test after
the water wetting test. Hence, the internal contact angle measurements included two
steps: the first one (with water) to collect the force data for contact angle calculations
and the second one (with n-hexane) to obtain the constant 𝐶. It is worth noting that a
clip sample holder was used here instead of a container. Hanging the tow
perpendicularly at one end and leaving the other end free, makes it possible to
As described in section 2.2, the weight of the external meniscus around a tow
measured by the tensiometer can be analyzed by the Wilhelmy method. The weight of
liquid (𝑊𝑟) left inside the tow after complete withdrawal from the water bath was
subtracted from the total measured forces to account for the effect of water up-take. It
is assumed that this force characterizes the volume freely accessible to water inside
the tow, i.e. the tow porosity. As already reported from single capillary tube wetting
experiments, it is known that an external meniscus takes much less time than an
internal one to reach equilibrium [42]. Therefore, although the external meniscus did
already reach its static configuration at the beginning of the test, the liquid still kept
wicking through the tow until the inter-fibre space was fully filled by the liquid.
Hence, the force data detected after the full wicking process were used to calculate
𝑓
𝐹𝑚𝑒𝑎𝑠𝑢𝑟𝑒𝑑 ‒ 𝑊𝑟 = 𝐿𝑡𝑜𝑤𝛾𝐿𝑉cos 𝜃𝑒𝑥 Equation 5
𝑓
where 𝜃𝑒𝑥 is the external contact angle obtained from the force measurement, 𝐿𝑡𝑜𝑤 is
In addition, the volume fractions of fluid retention, 𝑓𝑟, for each sample can be
𝑊𝑟
V𝑟 𝜌
𝑓𝑟 = V =V Equation 6
𝑟 + V𝑓𝑖𝑏𝑟𝑒𝑠 𝑟 + V𝑓𝑖𝑏𝑟𝑒𝑠
where V𝑟 is the volume of fluid in the tow, 𝑊𝑟 the weight of the liquid retention,
Four samples of unsized single CF were tested with both water and n-hexane by the
method described in section 2.2. The forces versus positions curve of a typical
The exact capillary force can be evaluated from the last two cycles by subtracting the
pre-force [24] measured before contact is established between the fiber and the liquid.
Figure 6 shows the distribution of the dynamic contact angle results. An average
advancing contact angle of 79.0 ± 4.8° was obtained, i.e. unsized single CFs are, as
expected, more hydrophobic than the T300 single CF, which showed a static
advancing contact angle with deionized water of 65.8 ± 2.9° [24]. Similarly, the
receding contact angle of unsized single CF with an average value of 41.7 ± 7.1° is
significantly larger than the one obtained for the T300 CF fibre with values between
20° and 0° [24]. The measured receding contact angle value of unsized CF in water is
somewhat smaller than the value reported by Bismarck et al. (56.3 ± 3.1°) [43].
Moreover, all the values of contact angles followed Gaussian distributions indicating
the reliability of the comparison between the two surfaces (see figure 6Figure 6).
Testing CFs with a tensiometer means that per sample two millimeters in length can
be evaluated. This gives a detailed view on the wetting process and already permits to
evaluate how heterogeneous fibre surfaces are. However, it is still a small scale
analysis. Forced wetting experiments like the ones performed by Blake et al.[44] or
Vega et al.[45], adapted to CFs would give access to a higher scale analysis as, in
principle kilometers of fibres can be tested (steady state process). An advanced optical
set-up would however be required (thin fibres dipped and withdrawn from a wetting
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Figure 5. Typical measured forces versus position (mm) curves for an unsized single
CF in water.
Figure 6. Distributions of dynamic contact angle values (unsized CFs with water).
when the tows were partially immersed vertically into water. At the free end, the loose
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water. A cylindrically shaped yarn was formed rapidly. Once in contact with water,
important to note that this kind of deformation, starting at the free end of CF tow,
changes its pore structure and wetted perimeter during the wetting test. This is not
directly detectable by the tensiometer, which only measures the resulting forces.
obtained by the Wilhelmy method. This is why we combined the tensiometric method
Figure 7. Images of CF tows captured before (a), side view, (b), bottom view), during
(c), side view and right after the wetting test (d), bottom view.
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Figure 8 shows the curves used to determine the effective internal advancing contact
angles for the T300 CF tow according to the Washburn approach. Figure 9 shows
images captured during the test. As shown illustrated in Figure 7 section 3.2, the free
end of the CF tow aggregates when touching fluid (in case the contact angle is smaller
than 90°) and an external meniscus is formed very fast, hence there is a weight jump
at the start, which is mainly due to the formation of external menisci [42]. This first
part cannot be used to determine the tortuosity factor 𝐶 (n-hexane test). The next part
of the curves could be fitted with straight lines in reasonable agreement with the
tow with n-hexane and water were significantly different. The tow immersed in n-
hexane packed less densely than in water, so there were larger pore spaces to take up
liquid for n-hexane. This leads to an overestimate of the weight of imbibed water and
tows, the calculation of effective contact angles via the Washburn equation resulted in
calculate the water contact angle, a value of 84.5° is obtained. This is 18.7 ± 2.9°
higher than the static advancing contact angle of a single T300 CF with water.
Previous studies [46, 47] also found larger contact angles calculated from the
Washburn equation than the one measured directly on smooth surfaces of the same
propose another approach, where we focus on the external contact angle of the fluids
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Figure 8. Square of the mass of water and hexane intake versus time in T300 CF tows.
Figure 9. Images of T300 CF tows captured a) during the n-hexane wetting test and b)
Table 2 shows the non-solid volume fraction of the CF tow samples and the volume
(volume based) and 2.4.2 (weight based). For T300 CFs, there is a good agreement
between the non-solid volume fraction and the volume fractions of fluid retention
calculated independently by using the force method and the optical method. This
agreement indicates that the porous space inside the tow was fully filled by water,
validating at the same time the fluid retention correction method. According to the
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optical observation, the 20 mm long tow samples were totally wetted after each test,
indicating that the equilibrium capillary rise height in the tortuous path is greater than
the length of the fibres and that water infiltrated the whole sample throughout. For the
unsized CFs, the agreement is still acceptable taking into consideration the standard
deviations. As the unsized CF tows are thinner than the T300 CF tows, the
measurements of the non-solid volume fraction and fluid retention become highly
sensitive leading to larger deviations from one sample to the other. The
hydrophobicity of the unsized tow may also prevent the tow to be completely filled by
water with the volume increase of the tow P being larger than the picked up water
Table 2. Volume fractions of non-solid and volume fractions of fluid retention for
As is shown in Figure 10, three successive steps may be identified when the tows are
forms that is characterized by a drop in contact angle from 90° to 76° (unsized CF
tow) and 63° (sized CF tow) within the first 200ms (not monitored neither by
tensiometer nor by camera). Then, a longer period is observed (~100s for T300 CF
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tows and ~60s for unsized CF tows) corresponding to the time needed for water to
completely fill the tow, both in the longitudinal and transverse directions throughout
the fibres. During this period, the external contact angle keeps on decreasing as water
first wets a composite substrate made of fibres and air, air being then progressively
replaced by water. The advancing contact angles made between the water meniscus
and the wetted fibres then reach their static values. Pictures taken at 10s, 20s and 100s
(Figure 11) illustrate how the contact angle progressively attains its static value during
the second period. Finally, after 100s, a steady slight decrease of the contact angles
was found for both T300 and unsized CF tows. This behavior was attributed to the
evaporation of water. It is identified by a decrease of the liquid height during the test.
comparing the position of the contact line (pinned) and baseline. Figure 12 confirms
that the visible contact line was pinned during the entire third stage while the baseline
was decreasing very slowly and evenly. Hence, at the beginning of the third stage
(from 100s to 200s), external contact angles have had enough time to reach to their
static configuration and the effect of water evaporation on the contact angle during
these 100s (from 100s to 200s) was small. Figure 12 also shows that the height of the
baseline decreases around 5 pixels, which involves an error on the contact angle
values less than 1.5°. Consequently, the static advancing contact angles were
calculated by averaging the external contact angles obtained during the first 100s of
the third stage (from 100s to 200s). After this time, the effect of water evaporation
becomes large enough to transform the static advancing contact angle into a receding
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one.
Figure 10. External water contact angles versus time (t) for the T300 and unsized CF
tows. The black and blue dashed lines show the contact angles obtained from the
force method and the red and green solid lines are those obtained from the optical
method. The static advancing contact angles were calculated by averaging the angles
obtained from 100s to 200s (in-between the two vertical dotted red lines).
Figure 11. Evolution of the water meniscus around a T300 CF tow. Pictures were
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taken at 10s, 20s, 100s and 500 after the tow contacted water. The dotted red line
gives the position of the contact-line (left contact point) after 10s, the green one the
position of the baseline after 10s and the blue one the position of the baseline after
500s.
Figure 12. Positions of the contact points and base line versus time (t) curves for a
T300 CF tow. The contact line points on both side of the meniscus as exemplified in
Figure 11.
Force and diameter versus time (t) curves obtained from a typical test in water with
a T300 CF tow are shown in Figure 13. We started to measure forces before the tow
contacted the water and stopped measurements 10s after the tow was completely
withdrawn from the water. Meanwhile, the evolution of the tow diameters was
measured by optical observation over the whole testing time. As shown in Figure 13,
a force was measured after the tow was withdrawn from the liquid bath (post-force).
The same phenomenon can be observed in each test. Since there was no external
meniscus around the tow at that moment, the value of this post-force was considered
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to be the weight of water left within the tows (𝑊𝑟) due to wicking. During the
forces (wicking action) and the external forces (formation of the meniscus around the
tow). To estimate the apparent contact angles made by the meniscus around the tow,
the force associated with external wetting must be independently measured. Hence,
𝑊𝑟 should be subtracted from the total measured force to eliminate the effect of water
up-take on the external contact angles measurements. Then the external contact angles
Figure 13. Measured force (red line) and diameter (black line) versus time (s) for a
As discussed in the last section, there are three stages during the whole test, which can
also be identified in Figure 13. A significant jump of the force at the moment of
contact represents the sudden formation of the external meniscus. The diameter of the
CF tow drops from 745μm to 590μm at the same time and slightly fluctuates due to
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the elasto-capillary effect. Then for the second stage, a slow and gradual increase of
the force can be observed. This behavior was attributed not only to a decrease of the
external contact angles, but also to the gradual water imbibition into the tow both in
the longitudinal and transverse directions. Afterwards, from 80s until the end of the
test, the force leveled off showing only a slight increase, due to the contact angle
decreasing as a result of water evaporation and pinning of the contact line (see figure
11Figure 11).
As shown in Figure 14, comparison between the results obtained from the force and
optical methods for both unsized and T300 CF tow shows good agreement indicating
that the combination of the force and optical methods successfully quantifies the
effects of deformations and water up-take within the CF tows on the external contact
angles. Figure 15 shows the average results obtained for the T300 and unsized CF
tows (external static advancing contact angles calculated during the first 100s of the
third period of each test). Moving from an unsized CF to a T300 CF, the static
advancing contact angle decreases by 13.2±5.6°. The external contact angle around
modification of CFs, larger contact angle changes can be observed at the mesoscale
than at the microscale, which indicates that the wettability of CFs at the mesoscale is
not only affected by the surface chemistry properties but also by the structure of the
tow.
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Figure 14. External menisci formed after 200s and comparisons between the external
contact angles obtained at this moment by the force and optical methods for the
Figure 15. Comparison of static advancing contact angles between unsized CF tows
and T300 CF tows with water (static advancing contact angle of T300 single CF is
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3.5. Relationship between the static contact angles at micro- and mesoscales
The difference in static advancing contact angles between single CFs and CF tows
indicates that the wettability of CFs changes when moving from the microscale to the
mesoscale. As CF tows are considered to be porous media, the surfaces around them
can be recognized as a composite surface made of CFs and air or fluid, respectively
before and after contact with the fluid. As shown in Figure 16 a) and b), the contact
line around the CF tow is not straight, which confirms that the external contact angle
(after contact with the fluid). The Cassie law [48] is a widely used model[34]
the contact angle corresponding to the minimum free energy configuration, which is
expressed in terms of the contact angles for each pure substrate. According to the
𝑓𝑖 = (1 ‒ 𝑓𝑠) represents the fraction of air/water interface with then θi = 180°. Here,
as the tows are infiltrated by water, air is replaced by water so that fi is the fraction of
water/water “interface” with 𝜃𝑖 = 0°. (such that (1 ‒ fs) is the water/water fraction),
𝜃𝐶𝐵 is the calculated “average” external contact angle around a CF tow. 𝜃𝑠 is the
contact angle on the single CF, which was measured in Section 3.1. θi is the
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arrangement and the area fraction of pores (P’) at the cross-section is equal to the
Where 𝑑' characterises the distance between two CF filaments, 𝑆𝐶𝐹𝑠 is the cross-
sectional area of the CFs in a triangularly packed cell, 𝑆𝑇𝑜𝑡𝑎𝑙 is the total area of this
triangular cell. Hence, 𝑑' can be calculated by substituting r and P into Equation 8.
Then, Figure 16 d) depicts the cell of the outermost layer of CFs exposed to air. The
adjustable contact angle. A similar model has already been successfully applied for
nanofibre yarns [25]. Therefore, the solid to water fraction 𝑓𝑠 can be calculated by:
𝑑𝑠 𝑑𝑠
𝑓𝑠 = 𝑑 = Equation 9
𝑠 + 𝑑𝑖 𝑟 + 𝑑'
Finally, 𝜃𝐶𝐵 can be evaluated using Equations [7]-[10]. The calculated values of 𝜃𝐶𝐵
(Table 3) are close to our experimental results shown in Figure 15 for both the T300
and unsized CF tows. Therefore, the contact angles of CFs at the meso- and
microscales can be linked by using the Cassie–Baxter model and a known non-solid
volume fraction. Besides, this model also describes how the structure of the tows
(porosities or distances between two CF fibres) can influence the wettability of the
Table 3 Calculated external contact angles (𝜃𝐶𝐵) and the parameters used for
calculation
Type of CF Non-solid
volume 𝜃𝑠 𝑑' (μm) 𝑓𝑠 𝜃𝐶𝐵
tow fraction, P
T300 CFs 54 ± 3% 65.8 ± 2.9° 1.4 ± 0.2 65 ± 3% 51.9 ± 2.5°
Unsized CFs 46 ± 15% 79.0 ± 4.8° 1.0 ± 0.6 76 ± 11% 67.4 ± 6.5°
Figure 16. a) Picture showing the contact-line between water and a T300 CF tow.
(with liquid in between the CFs) c) Schematics of pore areas in a cross-sectional view
perpendicular to the tow axis, where r is the radius of CF and 2d is the distance
between two filaments d) Cell of the outermost layer of CFs exposed to air, where 𝜃𝑠
4. Conclusion
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This study aims at characterizing the wettability of unsized and T300 CFs
single CFs was first studied by precisely measuring dynamic contact angles and then
comparing them with the wettability of single T300 CFs (from previous work). The
static advancing contact angle of water on unsized single CFs at a low test velocity
(3.6 mm/min) is 79.0 ± 4.8°, which indicates that the unsized CFs are more
hydrophobic then the T300 CFs (contact angle 65.8 ± 2.9°). The receding contact
angle of water on unsized CFs (41.7 ± 7.1°) is significantly larger than the one
measured for the T300 CFs, with a value between 0° and 20°.
infiltration of the tows. The Washburn method has first been used to interpret the
microscopy analysis confirmed that the CF tows immersed in n-hexane were less
densely packed than in water, which causes an incorrect evaluation of the tortuosity
constant. It suggests that the calculation of effective internal advancing contact angles
via the Washburn method is not suitable in the case of free hanging CF tows.
However, the combination of the force method and optical analysis permitted to better
characterize at the same time the non-solid volume fraction of the tow and the
external contact angles. This innovative method provided consistent results between
the externally optically observed contact angle and the contact angle obtained from
the Wilhelmy force, by correcting for the absorbed liquid. For wetted T300 CF tows,
the non-solid volume fraction is 54 ± 3% and the external contact angles are 46.0 ±
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6.1° (force method) and 48.8 ± 3.2° (optical method) respectively; and for the unsized
CF tow, the non-solid volume fraction is 46 ± 15% and the external contact angles are
65.1 ± 3.5° (force method) and 64.0 ± 3.4° (optical method) respectively. The effect
of surface sizing on fibre wettability at mesoscale was therefore assessed, which will
enable better prediction and optimization of adhesion between a given polymer matrix
and CF tows.
Moreover, contact angles of CFs at meso- and microscales have been successfully
linked by using the modified Cassie–Baxter model. By taking into account that the
observed tow contact angle is determined by the fraction of solid surface versus
imbibed liquid surface (for the wetted tow, and very likely by the surface fraction of
solid surface versus air for the un-wetted tow), the solid contact angle can be obtained
and this contact angle appeared to be very close to the contact angle measured at the
microscale. The wettability of CF tows can thus be predicted from the contact angle
Acknowledgments
This work was partially supported by the Interuniversity Attraction Poles Programme
(IAP 7/38 MicroMAST) initiated by the Belgian Science Policy Office. J. Wang was
also supported by the China Scholarship Council scholarships during his stay at KU
Leuven.
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