1.

Introduction

It is widely accepted that many of the most pressing issues facing humanity can be addressed
using carbon-based nanomaterials. They have extraordinary mechanical, thermal, and electrical
characteristics, as well as remarkable structure,[1, 6]
and have attracted and motivated
researchers focusing on fundamental studies and the diversity of applications, including in
energy, sensors and medicine[1, 7]. In addition, others factors, for example, the simplicity of
preparation, and the outstanding properties of each generation of the materials, have attracted
increasing attention from industry[8]. Solid carbon nanomaterials can be formed as bulk phases,
like diamond or molecular, as fullerenes[9] and carbon based nanomaterials can be zero, one,
two, or three dimensions as fullerene*[1, 10]
, nanotubes[1, 11]
, graphene[11], and diamond[1],
respectively.
Before 1985, graphene and diamond were the known allotropes of carbon[12]. This changed
when H. Kroto and colleagues discovered a novel type of carbon nanomaterial, known as
fullerenes, using mass spectrometry with a peak corresponding to the exact mass of 60 carbon.
They ascribed this to the formation of 60 carbon atoms arranged on a curved surface, like a
soccer ball[12]. They named it buckminsterfullerene due to its resemblance to the geodesic
domes designed by R. Buckminster Fuller (American architect). They, subsequently
discovered a variety of fullerenes with more and fewer number of carbon atoms, starting from
eighteen to hundreds of carbon atoms,[13] with some of them shown in Figure 1. Fullerenes
became available as solid materials in the early 1990s, generated through the resistive heating
of graphite[14].

Figure 1. Examples of Fullerene structures [1].

1
1.1.Fullerene C60
Fullerene C60, now referred to as Buckyball, or C60, as chemists prefer. It is a popular molecule
with its stunning symmetry, having sp2 carbon atoms arranged on a curved surface, at the
vertices of a truncated icosahedron. Fullerenes in general are exceptional materials among
carbon based materials, due to their unique properties, for example, optical and optoelectronic.
These characteristics arise from their extended conjugated - interaction, and this alone has
attracted much research for a number of applications[7]. Figure 2a shows that 12 pentagonal
and 20 hexagonal rings form fullerene C60 in spherical like (60 single bonds and 30 double
bonds giving 90 covalent bonds (see Figure 2b))[15], and these rings sit at the vertices of an
icosahedron, meaning no two pentagonal rings are next to each other [13]. The average distance
of C-C bond is approximately 0.146 nm and for C=C is 0.141 nm based on the NMR
measurement, and the diameter of fullerene C60 is 0.708 nm[16].

Figure 2. (a) The structure of fullerene C60[17], and (b) its the extended covalent and bonds [15].

It is noteworthy that both increasing temperature, as well as pressure, can affect the shape of
C60, as well as forming inter-fullerene covalent bonds, which can also occur when exposed to
[18]
UV irradiation . In the absence of covalent inter-fullerene bonds, C60 can self-assembly
into different crystal shapes which is important in enhancing its properties, as explained below.

1.1.1. Assembling Fullerene C60

Crystallising fullerene C60 into different shapes is effective in promoting its electronic and
optical properties.[19]. In addition, controlling the self-assembly of fullerene C60 has played a
crucial role in increasing the surface area of the material[5]. A variety of methods have been
developed for crystallising fullerene C60, such as slow evaporation, drop drying and
liquidliquid interfacial precipitation (LLIP)[19]. These methods provide libraries of micro-
and/or nano- sized structures with different dimensions and morphologies (1D, 2D and 3D)
depending on the method[19, 20]
and the choice of solvent[20]. The selective solvent
crystallization is discussed below.

2
 1.1.1.1. The choice of solvent

With their remarkable shapes, fullerenes can cooperate with solvents in interesting ways that
deliver novel knowledge about solute-solvent interactions[21]. The interaction between
fullerenes and solvents can be summarised into two aspects of the geometry of the fullerene.
The first aspect is the molecular surface area, which is the surface available for single molecule
to interact with the solvent and then the volume of the molecular cavity created in the solvent
during the interaction[21]. In short, the choice of solvent plays a vital role, not only for
assembling fullerenes, but also in terms of solubility of the molecule[20]. Fullerene C60, in
general, is essentially insoluble/sparingly soluble in water and polar solvents[22], whereas it
has appreciable solubility in non- polar solvents, as shown in Table A1 in the Appendix [21].
For aromatic solvents, the solubility of C60 in mesitylene is less than in benzene, toluene, and
xylenes, whereas it is more soluble in xylenes flowed by toluene and benzene respectively [21].
Moreover, fullerene C60 can crystallise into a face centered cubic (fcc) strucutre, which has
relatively large interstitial sites which can be occupied by solvent molecules[23] The different
solvents will not only affect the shape of the fullerene C60 assembled particles but also their
dimension[20] which will be further discussed below.

1.1.1.2.Methods for crystallisation fullerene C60

1.1.1.2.1. Conventional methods

Recently there have been many papers focused on developing methods of controlling the self-
assembly of fullerenes. Indeed, each method can provide one or more different shapes,
depending on the conditions. As an example, slow evaporation can produce C60 nanorods as
reported by Wang et al.[24]. Evaporating a solution of C60 at room temperature can afford
specific structures grown on a substrate, for example, silicon or glass, with C60 dissolved in m-
xylene affording the aforementioned nano-rods. After evaporation, nano C60 rods with diameter
range from 50 nm to hundreds of nano-meters (average 200 nm) with an average length 100
m are obtained, as shown in Figure 3a[24]. Colin and co-workers used this method to
fabricate needle-like microstructures of C60 into with diameter and length of approximately 20
m and 200 m, respectively, as shown in Figure 3b[25]. In addition, Geng et al. formed C60
[26]
nanowires from a solution of C60 dissolved in 1,2,4-trimethylbenzene. This involved
controlled slow evaporation with a range of width of 100 nm to 500 nm and 200 m to 1000
m in length, which is shown in Figure 3c[26]. The nanowires here have a novel shape, with

3
each composed of two nanobelts joined along the growth direction as a V-like, as shown in
Figure 3c. Moreover, after heating the products to 900 C (nanowires), they transformed into
carbon nanofibers[26].

Figure 3. Microscopic images for different preparations of self assembled C60 obtined from different
solvents using the slow evaporation method. (a) Self-assembled C60 nanorods (C60m-xylene) grown on
silicon [24], (b) Needle like C60 from evaporation a solution dichloromethane at room temperature over
4 days[25]. (c) Low magnification SEM image of C60 nanowires with the top inset a TEM image of the
V-shaped and nanobelts within each nanowire[26].

Another method used for fabricating C60 2D nanostructures is vapour solid (VS) evaporation.
This method just requires a powder of C60 which is vaporized at a high temperature and
condensed, under different conditions, including the choice of inert gas, temperature, pressure,
[27]
and substrate, with the process usually carried out a tube furnace . Shin and co-workers
have used this method to fabricate disc like structures of self assembled C60 [3]. Here C60 powder
was placed in the middle of a quartz tube, with the tube furnace aligned horizontally, and the

Figure 4. Schematic diagram showinf the principle of the vapour-solid (VS) reaction apparatus [27].
The inset SEM images of fullerene C60 disks like obtained from vapour solid (VS) process under
optimum parameters, temperature 650 C, flow gas rate 100 sccm (Ar). The left and right insets are for
3D C60 crystals obtained on Si and SiO2 substrates, respectively [3].
material condensed on highly oriented pyrolytic graphite (HOPG) supported on a Si wafer,
positioned close to the end zone of the furnace, as shown in Figure 4. The optimum operating
parameters were T= 650 C and 100 sccm of Ar (see inset Figure 4)[3]. In addition, Shin and
co-workers established that the nature of the substrate can affect the yield of a particular
structure. For instance, when Si and SiO2 was used as a substrate, only a few C60 disks

4
randomly observed, and mostly inhomogeneous shaped 3D generated, as shown in in the inset
of Figure 4 [3].
Another method which can also produce C60 organised into different structures is drop drying.
Here a C60 solution is dropped onto a substrate (solid) and left to dry at room temperature[20]
with the overall involving three steps. Firstly, C60 is mixed with an organic solvent and then
ultra-sonicated for a specific time (typically 30 minutes) to
facilitate dissolution. Any undissolved C60 is remove via
filtration[20] with different concentrations of the fullerene then
prepared for dropping a small amount onto a solid substrate.
Finally, depending on the type of solvent, the solvent
evaporation time may take only a few minutes or up to three
days[20]. Park and co-workers used this drop drying method to
gain acces to different self-assembled C60 arrays. As mentioned
earlier, not only the choice of method can change the
morphology of self-assemble C60, but also the choice of solvent
Figure 6. Schematic
[20]
. Park and co-workers established a strong relationship showing the precipitate
area between C60 solution
as the lower phase and the
anti-solvent in the upper
phase.

between the shape of the

solvent and the final structure
of self-assembled C60. Figure
5 a-f shows the influence of the
choice of solvent in shape of
crystallization C60. For
Figure 5. SEM images of C60 crystals obtained by the drop drying instance, n-hexane as a one
method using different solvents. (a) Hexagonal disks shaped from
tetrachloromethane (CCl4), (b) wires like from m-xylene, (c) dots dimension solvent can form
like from hexane and at low magnification 500 nm in the inset
C60 in zero dimension dots and
shows clearly the surface, d) hexagonal disks like from tin
tetrachloride (SnCl4), and their shape affected and the surface 1 D wires can be obtained from
became rough due to exposure the sample to air (e) and (f) wires
like obtained via using 1,3-dichlorobenzene and mesitylene [15]. C60 solution of two dimension
solvents, for example, m-
xylene, 1,3-dichlorobenzene, or mesitylene. Two dimension disks can be produced from C60
solution of carbon tetrachloride as a 3 D solvent [20].Finally, a common method for controlling
the shape of C60 involves liquid/liquid interfaces precipitation (LLIP). Here two solvents that

5
are immiscible and are good and poor for solubilising fullerene C60, and the growth and
nucleation of the C60 particles can be controlled by the optimized volume ratio of the solvent
(good) to an anti-solvent (poor). The self-assembly process can be summarised in three steps.
Firstly, C60 is dissolved in a suitable solvent and then the anti-solvent is added, for example
isopropyl alcohol (IPA)[28] and methanol[2] . Ultra-sonication can then be used to facilitate the
nucleation and formation of C60 crystals for different times[19, 29]. Finally, an interface area
forms between the two phases with the C60 solution as the bottom phase and the anti-solvent
as the top phase[28] as shown in Figure 6. This method has been used to produce libraries of
fullerenes (C60 and/or C70) crystals, including whiskers, cubs, disks, and flowers in micro and
or nano-size, depending on the experiment conditions [30]. For example, Miyazawa and Hotta
fabricated C60 nanowires, with C60 dissolved in toluene and IPA containing a small amount of
water H2O (< 2.5%) as the anti-solvent. The authors studied the influence of the solvent ratio
on the product, establishing that C60 nano-whiskers grew longer above a critical diameter, for
an optimum volume ratio of 1:1 (C60 in toluene to IPA) (see Figure 7 a-e [30]).
Shrestha and co-workers reported the use of the LLIP method for the synthesis of C60 rods.
Here methanol (anti-solvent) was added to a saturated solution of C60 in mesitylene, resulting
in the formation of C60 nano-rods like at the interface of the two liquids, as shown in figure 7
[2]
f . In 2009 Miyazawa and co-workers established that adding IPA or tert-buty1alcohol
(TBA) to a saturated C60 solution in benzene, toluene and CCl4 resulted in number of 2 D C60
[4]
crystals, namely rhombi, hexagons and polygons as shown in Figure 7 (g-i) . In addition,
they established that rhombi and polygons can be transformed to 1 D nano-rods by exposing
them to water with the nano-hexagons unaffected in the presence of water. The reason given
for this transformation is that the metastable nano-rhombi, which possess a strained mixed
crystalline structure meta-morphosize into the more stable short nano-whisker (nano-rods)
probably through stimulation by some additional hydrophobic interaction between C60
molecules upon contact with water [4]. Shrestha and co-workers studied the effect of mixing
two good solvents on the structure of self-assembled C60 and compared with the use of a single
solvent ((i.e. one experiment having two solvents (poor solvent added to the solvated C60 in a
good solvent, and then another good solvent will add to solvated C60 and good solvent system)),
[5]
which is shown in Figure 7 . They mixed two solutions of C60, one in CCl4, the other in
benzene, ratio 3:7, with IPA resulting in 2D sheets of assembled C60, as shown in Figure 7 j.
The sheets are approximately 5 m across and their thickness increases from 800 nm to 1 m
upon increasing the ration of CCl4 to benzene to be 1:1 (Figure 7 k) [5]. Increasing the ratio to
7:3 afforded a porous structure on the surface of hexagonal sheets, with an average size of ~

6
200 nm (see Figure 7 l). The size and number of these porous increased on increasing the
volume ratio of to 8:2, becoming ~ 400 nm in size at 9:1 as shown in Figure 7 m and n,
respectively. In the
absence of CCl4 (just
C60 in benzene and
IPA), nano-whiskers
[5]
formed, Figure 7O .
Moreover, the shape
and dimension of self-
assembled C60 can be
effected by the
concentration of C60 in
the stock solution[31]. Li
and co-workers
generated C60 3 D
flower-like
arrangement of prisms,
with the diameter and
length of the prism
increased with

. SEM images of different structures of LLIP

self-assembled C60 atNano-whiskers
different decreasing C60 solution
Figure 7. magnifications, using the method. (a-e)
formed by adding C60 in toluene to IPA with using different volume ratios, as shown in Figure 7
1:7, 1:5, 1:3, 1:1 and 3:1 respectively [28]. (f) C60 nanorods formed by mixing
C60 in mesitylene and methanol [2]. (g-i) Rhombi, hexagon and polygon p-r. The volume ratio
structures obtained by adding TBA to C60 in toluene, IPA to CCl4 and between solvent and
TBA/benzene, respectively [4]. (j-n) 2D sheets formed by adding IPA to
variety of volume ratio between CCl4 and benzene, and nano-whiskers anti-solvent (as in C60
formed in the absence of CCl4 [5]. (p-r) Increasing length and diameter of
prisms with decreasing the stock solution and fixing the volume ratio in toluene and ethyl
between IPA/C60 toluene. (s and t) Increasing prism material by decreasing acetate can affect the
the volume ratio of IPA to C60 toluene/Cll [5]. (u) Nano-whiskers formed
between C60 in benzene and TBA. ( v, w and x) Flower like strucutres growth and nucleation
obtained in the presence of different amounts and types of surfactants [16].
process. Li and co-
workers established
that the length of the prisms increased with decreasing the volume ratio of ethyl acetate to the
solution of C60, which are shown in Figure 7 s and t[31].
In the LLIP method the presence of surfactant can change the structure of the self-assembled
C60. In 2013, Shrestha and co-workers reported the synthesis of flower like 3 D structures using

7
surfactants [19], and in the absence of surfactant self-assembled C60 nanotubules like are formed
at the interface between TBA and a saturated solution of C60 in benzene. Their diameter and
length are about 1.5 m and 10 m, respectively, as shown in Figure 7 u [19]. Nevertheless, in
the presence of surfactants ((diglycerol monolaurate (C12G2), cetyltrimethylammonium
bromide (CTAB), and cetyltrimethylammonium chloride (CTAC)) solutions with different
volume ration 0.01, 0.1, and 1.0% to TBA, 1 D C60 tubules was transferred into 3D flower
like structures. Fixing the volume ratio to 5:1 for TBA to C60 in benzene with higher
concentration of surfactants (1.0%), resulted in little control over the growth of the particles,
whereas for decreasing the concentration of surfactants (0.01%) uniform C60 flower like
[19]
strucutres resulted Figure 7 v, w, and x . Thus
there is a direct proportionality between the
concentration of surfactant in TBA and the
dimensions of C60 crystals. For example, 0.1% C12G2,
gave C60 microcrystals ~3.45 m in diameter and ~
28 m in length compared to 1.0 % C12G2
affording~ 1.2 m diameter and ~ 10 m in length
structures. This relates to the excess surfactant being
adsorbed, circumventing crystal growth of C60
particles. Figure 8. Schematic highlighting the effect of
surfactants on the shape of particles formed on
In 2016 Shrestha and co-workers studied the LLIP crystallizing C60 [6].
method with respect to the influence of surfactants by
mixing them in the C60 solubilising solvent [7] , which is shown in Figure 8. rather than in the
anti-solvents, as in their previous work [19]. They, firstly, fabricated C60 crystals in the absence
of surfactant as summarised in Figure 9a, resulting in tube-like structures, ~ 747 nm in
diameter and ~ 4.8 m in length (IPA and C60 in ethylbenzene (EB)). Adding 1.0 % of
diglycerol monolaurate (C12G2) and 0.1 % of diglycerol monomyristate (C14G2)) to EB,
resulted in self assembled C60 konpeito-like structures at the interface between IPA and EB [7].
However, C60 Konpeito-lik structures were only obtained by adding 1.0% of both surfactant

8
 types to EB whereas 0.1% produced non-
uniform shapes of C60 crystals, as shown in
Figure 9 b and c. This again established that
increasing the concentration of surfactants,
promotes the interaction between molecules of
C60, solvents, and surfactants.
The key feature of the processing of C60 crystals
using this method is the reduction in solubility
[7]
of C60 in the presence of an anti-solvents .
Change in frabrication temperature can also
affect the growth and the structure of assembled
C60. Masuhara and co-workers observed that C60
formed rods at the interfacial area between C60
in m-xylene and IPA [32], as shown in Figure 9 d.
Smaller C60 rods were obtained at -15 oC and
longer rods were obtained at 40 oC. Interestingly
Figure 9. SEM images of different shapes of self
assembled C60 using the LIIP method. (a) C60 they became longer with a smaller dimeter at 60
rods grown by the addition of EB to C60 in o
C with further reduction in dimeter at 80 oC, as
benzene in the absence of surfactants. (b and c)
In the presence of 0.1% and 1.0% respectively Figure 9 e-h [32].
[6]
. (d) C60 rods obtained by adding IPA to C60 in
m-xylene. ( e, f, g and h) Change of shape by Another method of formation of C60 particles is
varying the temperature from -15 C, 40 C, 60 the direct of growth into vertical structures, as in
C to 80 C [31].
the formation of C60 micro-tubes, reported by
Cha and co-workers. This involved injecting IPA < 0.05 mL/min from the bottom into a C60
solution in toluene through an Anodic Aluminum Oxide substrate (AAO) [33]. An important
note here is that the flow rate of anti-solvents needs to be optimized, otherwise crystal growth
occurs in the C60 solution rather onn the substrate. At the optimum conditions (flow rate = 0.02
mL/min), aligned C60 micro-tubes with a hexagonal cross-section cover the entire surface of
the AAO membrane substrate, as shown in Figure 10, approximately 500 m in length with
their outer diameter and thickness ranging from 10 to 30 m and 1 to 3 m, respectively [33].

9
In general, all these methods have the ability to self-assemble C60 in a library of structures
(morphologies, shapes, and
dimensions). However, They
also have some limitations, such
as increasing the materials waste
[34]
, high level risk in using toxic
[35]
reagents, and low yield .
Moreover, the use of surfactants
Figure 10. Schematic of vertical growth of C60 tubes. SEM
images shows the side view of the tubes and the top and bottom contaminates the surface of the
inset shows the morphology of the inner tube structure [34].
crystals, and their removal is
inherently difficult. As such their
[36]
presence can affect their properties and applications . Processing time to collect the final
product is also an issue, especially where the evaporation is slow [37]. In addition, it takes one
[2]
week for LLIP processing, increasing two weeks for specific conditions, such as low
[38]
temperature , and up to three days for
the drop drying method [20]. Another issue
is that the final self assembled C60
material can have included solvent,
requiring heating as a down stream
process for its removal[39].
1.1.1.2.2 Continuous flow fabrication
of materials
Recently continuous flow processing, as
a type of process intensification (PI), has
attracted the attention of researchers in
different fields. This relates to the
benefits of IP in overcoming the
challenges. Continuous flow devices
have unique features and capabilities,
including high yield, safety, inexpensive,

Figure 11. Schematic of (a) a spinning disc processor high efficiency of mixing, mass and heat
(SDP) and (b) a rotating tube processor (RTP) [43]. transfer, and control in the shape and size
of particles [35, 40]. These advantages as applied to thin film microfluidics platforms are a result
of generating high shear stress within the dynamic films on surfaces, as in spinning disc

10
processors (SDP) and the rotating tube processors (RTP), as shown in Figure 11. In addition,
they can directly translate the process into scalable continuous flow technology, as well as
[34]
adopting eco-friendly strategies associated with green chemistry . Figure 11 shows the
schematic of an SDP where has a rapidly rotating disc horizontally (y-axis). Here liquids are
delivered close to the centre of the disc via jet feeds with centrifugal acceleration forming thin
films depending on the rotational speed, typically 0.3 up to 3 krpm. The residence time of a
finite volume of liquid on the disc depends on the size of the disc, viscosity of the liquid, and
flow rate of the liquid [41-43]. On the other hand, the RTP allows control of the residence time
with intense shear in the thin film, as for the SDP, imparted at high rotational speeds. The
rotating tube in the RTP is aligned horizontally (x-axis) [34]. Centrifugal acceleration is directly
proportional to the rotational speeds in the SDP and RTP, so is the film thickness, depending
on the speed as well as the height of a ridge at the end of the tube and the viscosity of the liquid.
In the RTP, liquids can be injected through a number of jet feeds allowing injection of more
than one liquid into the platform, Figure 11. In the RTP, the residence time can be governed
by the flow rates and the length of the tube [34]. Both the SDP and RTP have proved their ability
[44]
for chemical synthesis and the fabrication of materials with nanoscale dimensions .
However, the controlled synthesis of carbon based nano-materials in the SDP and RTP, and
[34]
the high cost of construction of such equipment has limited their application in this area .
Recently, the novel continuous flow vortex fluidic device (VFD) was developed in Prof. Colin

Figure 12. Schematic of the VFD processing.

L. Rastons research group, in overcoming these limitations and opening up new processing
capabilities under continuous flow. The VFD generates a controllable mechanoenergy in

11
dynamic thin films using a rapidly rotating glass tube, which is able to uniformly disperse
carbon-based materials [45]. Figure 12 illustrates the general setup for VFD processing. It can
operate under two different modes, confined and continuous flow. For the former, a rapidly
rotating tube opened at one end generates intense shear force in thin films for a finite sub-
millilitre amount of a liquid, with the tube tilted at different angles. The latter is different only
in that the reagents are injected into the inclined rapidly rotating tube via jet feeds. In both
devices, SDP and RTP, the angle is fixed (SDP = 90 and RTP = 0), so the resident time is
dependent on the flow rate ( ); however, in the VFD, not only flow rate but also the angles and
rotational speeds (), which can
change (from 0 up to 90 and speeds
up to 10 krpm ), offer a variety of
conditions leading to control share
stress [34]. At high in continuous
flow operations, the thickness of
the thin film is 200 m; this
[46]
value depends on , and .
The VFD has a number of other Figure 13. (a) Schematic of VFD processing where two jet
remarkable applications, feeds deliver solutions into the bottom of the tube. (b) An
image of the solution. The upper is C60 in toluene and the
including controlling chemical bottom is water. (c) A SEM images of resulting C60
[47, 48] nanotubes [52].
reactivity and selectivity ,
[45]
slicing carbon nano-tubes without the need for harsh chemicals , and probing the structure
[49, 50] [51]
of self-organised systems , including protein folding . Vimalanathan and co-workers
reported the formation of C60 nanotube using the VFD, as summarised in Figure 13 [52]. Here
the VFD is effective in controlling the growth and nucleation of fullerene C60 in the absence of
harsh chemicals and surfactants. Remarkably, under high shear in the VFD, water acts as an
anti-solvent, even though the two solvents (water and toluene) are immiscible. Water
effectively reduces the solubility of C60 with the nucleation and growth of C60 nanotube (see
Figure 13(c)). A variety of conditions were investigated including the volume ratios (C60 in
toluene: H2O), flow rate, tilt angle and rotational speeds, in optimising the formation of the
tubes of assembled C60 which have a hollow core, 100400 nm in diameter, and microns length
[52]
.

In general the self-assembly of C60 strongly depends on the choice of solvent as well as the
method of fabrication, as discussed above. However, with the advantages of the use of

12
continuous flow processing compared to the conventional (batch) methods, there is scope for
controlling the growth of fullerene arrays in a novel way, beyond the pioneering work by
Vimalanathan and co-workers. This is the basis of the research undertaken herein, for the
hypothesis, can shear stress in the VFD reduce the solubility of fullerene C 60, in allowing the
nucleation and growth of nano-materials without the need to add an anti-solvent or surfactant?
The shear stress in the VFD is a form of mechanical energy such that the chemistry is not
limited by diffusion control under laminar flow with a move towards transient turbulent and
turbulent flow [53].

13