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To cite this article: H.-C. SCHWARZER & W. PEUKERT (2004) TAILORING PARTICLE SIZE
THROUGH NANOPARTICLE PRECIPITATION, Chemical Engineering Communications,
191:4, 580-606, DOI: 10.1080/00986440490270106
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Chem. Eng. Comm., 191: 580 606, 2004
Copyright # Taylor & Francis Inc.
ISSN: 0098-6445 print/1563-5201online
DOI: 10.1080/00986440490270106
H.-C. SCHWARZER
Institute of ParticleTechnology,
Technische Universita«t Mu«nchen,
Garching, Germany
W. PEUKERT
Institute of ParticleTechnology,
Universita«t Erlangen-Nˇrnberg,
Erlangen, Germany
580
TAILORING PARTICLE SIZE 581
INTRODUCTION
Many properties of solid particles are not only a function of the materials
bulk properties but also depend on particle size and particle size
distribution (PSD), especially for sizes below 1 mm. Examples are optical
properties, melting point, and rate of dissolution. These property changes
arise from the increasing influence of surface properties in comparison to
volumetric bulk properties as the particle size decreases. Nanoscaled
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PHYSICAL CONCEPTS
Overview
The PSD of a precipitation process is the result of several parallel and
successive processes: nucleation, growth, and secondary processes such as
agglomeration, attrition, and breakage. In the case of nanoscaled parti-
cles the latter two are negligible due to low collision energies. Conse-
quently, nucleation, the formation of new particles; growth, the increase
of the particles’ characteristic length; and agglomeration, the combina-
tion of two or more particles to larger units have to be considered when
investigating precipitation. A chart of the precipitation process is depicted
in Figure 1 showing the various influencing parameters on the three
mentioned processes.
Nucleation and growth rates depend strongly on supersaturation, a
measure for the system’s thermodynamic offset from equilibrium. Due to
the highly nonlinear dependence of the nucleation rate on super-
saturation, it has a strong influence on the precipitated PSD. While at
high supersaturations a large number of particles are formed that remain
582 H.-C. SCHWARZER AND W. PEUKERT
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small since the available total mass is limited, fewer but larger particles
are generated at lower supersaturations. Both nucleation and growth
reduce supersaturation.
Unless a slow chemical reaction is involved, which is not the case in
the investigated precipitation of an inorganic and sparingly soluble salt
such as barium sulfate, supersaturation is ‘‘generated’’ through mixing on
the molecular scale, called micromixing. Micromixing is preceded by
macromixing, a flow field controlled reduction of segregation length
scales. Thus, the kinetics of micromixing can be a function of the mac-
romixing kinetics. It is a function of the turbulence intensity and the
specific power input, which determine the size of the smallest eddies and
thereby the length necessary to surmount through diffusion for molecular
mixing. Details on mixing can be found in Baldyga and Bourne (1999). In
addition, the flow field in the reactor controls not only the process of
mixing but also the rate at which particles collide with each other and
thereby the agglomeration rate, since particle-particle collisions are
assumed a prerequisite for agglomeration.
While the flow field can be considered as a process parameter that
can be altered and optimized according to specific needs, a completely
independent set of influencing parameters is given through the com-
position of the educt solutions. For example, the interfacial tension
that influences the nucleation rate is a function of ionic strength, the
particle’s surface charge, and thus the concentrations of the potential
determining ions and of macromolecule adsorption. These parameters,
which could vary strongly through a precipitation process, also
determine the particle interaction and thereby the agglomeration rate.
It can be concluded that precipitation is a complex system of parallel
and subsequent processes with various interacting and changing
parameters.
TAILORING PARTICLE SIZE 583
assumption of plug flow through the mixer, a mixing model using pressure
drop data, and detailed modeling of particle formation under consi-
deration of agglomeration was chosen in this work.
Supersaturation
The driving force for nucleation and growth is supersaturation, a mea-
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sure for the system’s thermodynamic offset from its equilibrium. For the
investigated precipitation of barium sulfate from aqueous solutions of
barium chloride and sulfuric acid according to Equation (1),
H2 SO4 ! HSO
4 þH
þ
! SO2
4 þ2H
þ
ð3Þ
pffiffiffi
0:511 jzþ z j 1 ð0:06 þ 0:6 BÞ jzþ z j I
log g ¼ pffiffiffi þ 2 þBI ð4Þ
1þ 1 1:5
1þ I
jzþ z j
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
½Ba2þ ½SO2 4 dis
S ¼ g ð5Þ
KSP
½Ba2þ 0
R¼ ð6Þ
½SO2
4 0
Nucleation
According to Mersmann et al. (2000) and supported by the experimental
findings of Schubert (1998), homogeneous nucleation can be considered
the dominant nucleation mechanism at the studied high supersaturations.
According to Schubert (1998), the rates for homogeneous and hetero-
geneous nucleation are equal at a supersaturation of about 150 for bar-
ium sulfate. The nucleation rate of homogenous nucleation can be
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rffiffiffiffiffiffiffi !
pffiffiffiffiffiffiffiffiffi gCL 16p gCL 3 V2m
Bhom ¼ 1:5DAB ð KSP SNA Þ7=3 Vm exp
kT 3 kT ðnlnSÞ2
ð7Þ
Since the exponential term in the nucleation rate equation (7) is a third-
order function of the interfacial tension gCL , this parameter also exhibits
a strong influence on the nucleation rate. According to Mersmann (1990),
the interfacial tension can be calculated by the following equation:
1 rc
gCL ¼ 0:414 kT pffiffiffiffiffiffiffiffiffi In pffiffiffiffiffiffiffiffiffi ð8Þ
3 V 2 M KSP
m
Not only the rate at which new nuclei are formed but also the size of the
formed nuclei are highly nonlinear functions of supersaturations as well
as interfacial tension. Assuming that the size xC of the newly formed
particles is equal to the size of critical nuclei, Equation (9), which can be
found in Mersmann (2000), can be applied.
4 gCL Vm
xc ¼ ð9Þ
n kT ln S
Growth
According to Mersmann et al. (2000), growth at high supersaturations
can be considered diffusion controlled. Experimental data by Angerhöfer
(1994) as well as by Nielsen (1958) indicate a transition from integration-
controlled to diffusion-controlled growth for barium sulfate at a
TAILORING PARTICLE SIZE 587
derivation from the mass flux. The mass transfer coefficient is expressed
through the Sherwood number Sh and the diffusion coefficient DAB.
Activities are expressed through root of the solubility product times
supersaturation. At the surface equilibrium is assumed, i.e., S ¼ 1.
Supersaturations are used since two ion species, Ba2 þ and SO2 4 , con-
tribute to growth and both contributions interact through charging of the
particles; thus mean activities have to be applied when calculating the
difference.
pffiffiffiffi
@x Sh DAB KSP M S 1
G¼ ¼2 ð10Þ
@t rc x
dN b ðx1 ; x2 Þ
¼ coll N2 ð11Þ
dt W
interaction. Values larger than one account for repulsive interaction and
result in smaller agglomeration rates, i.e., the particles are more stable
against agglomeration. The total particle number concentration N is
related to the particle number density n(x) by the following equation:
Z 1
N¼ nðxÞ dx ð12Þ
0
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In literature there are many suggestions on how to calculate bcoll for the
different collision mechanisms: for Brownian motion a cause of particle
collisions the kernel proposed by Smoluchowski (1917), and given in
Equation (13) seems reasonable, while for collisions in highly turbulent
flows the kernel proposed by Saffman and Turner (1956) as given in
Equation (14) is used.
2kT 1 1
bcoll;Brown ¼ ðx1 þ x2 Þ þ ð13Þ
3:nF rF x1 x2
rffiffiffiffiffiffiffiffiffi rffiffiffiffiffi
p 3 e
bcoll;turb ¼ ðx1 þ x2 Þ ð14Þ
8:15 nF
Z 1 exp jtotal ðaÞ
kT
W ¼ x da ð15Þ
0 ðx þ aÞ2
Mixing
As already mentioned, supersaturation is ‘‘generated’’ through mixing, a
process that occurs on scales from the mixer scale down to the molecular
level. The relevant mixing process for supersaturation generation is
micromixing, i.e., mixing at length scales below the Kolmogorov scale. If
micromixing is the only limiting mixing step, as it is in the deployed
mixer, its kinetics can be modeled by the Engulfment-Deformation-
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Diffusion model (EDD model) of Baldyga and Bourne (1999). Since this
model was originally derived for the situation of mixing a small volume
to a much larger volume, it had to be extended for equi-volumetric
mixing. Baldyga and Bourne propose an extension of their micromixing
model by introducing a ‘‘contact zone.’’ For the initial contact zone
volume fraction they assume a value that is proportional to the turnover
time of the eddies and thus unequal to zero. They also propose that
mixing does not start during that first turnover time, which equals
ln(2)/E, the engulfment parameter. This approach is notfeasible for the
coupling of mixing and population balance. In order to avoid this initial
condition, a different extension of the EDD model of micromixing also
based on the concept of a contact zone was derived.
The new as well as the Baldyga EDD model are based on volume
fractions X and assumes ideally mixed zones, one of solution A, one of
solution B, and the contact zone, which consists of a zone of solution A
and the mixing zone. For simplification these zones are called and
indexed with A, B, and the contact zone C, which consists of AC and the
mixing zone M. Thus XA þ XB þ XC ¼ 1 and XAC þ XM ¼ XC. The new
model assumes that XC increases when A is mixed with B, A is mixed
with C, or B is mixed with C. For an increases of M, it has to be mixed
either with B or with AC. In order to describe the rate of mixing, the
engulfment parameter E as in the original models by Baldyga and Bourne
is used. This parameter is a function of the specific power input, a
characteristic turbulence parameter that determines the Kolmogorov
scale and thereby via the Batchelor scale the necessary diffusion length.
Values for this parameter can either be taken from CFD simulations or
calculated from pressure drop measurements with averaging over the
mixer volume. Concentrations and the supersaturation in the mixing zone
can then be calculated via species balances. Using this model the fol-
lowing system of partial differential equations has to be solved:
rffiffiffiffiffi
e
E ¼ 0:058 ð16Þ
nF
dXc
¼ E ðXC XA þ XC XB þ XA XB Þ ð17Þ
dt
TAILORING PARTICLE SIZE 591
dXA XA
¼ E XC XA þ XA XB ð18Þ
dt XA þ XB
dXB XB
¼ E XC XB þ XA XB ð19Þ
dt XA þ XB
dXM XB
¼ E XC XB þ XA XB þ XM XAC ð20Þ
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dt XA þ XB
dXAC XA
¼ E XC XA þ XA XB XM XAC ð21Þ
dt XA þ XB
Population Balance
Since particle formation and mixing occur on similar time scales, that are
in the order of ms to ms, both processes have to be coupled in the model
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@nðxÞ
¼ Bhom ðS;gCL Þ fðxc ðS;gCL ÞÞ
@t
@ðGðS; xÞ nðxÞÞ
þ Bagglo ðn; xÞ Dagglo ðn; xÞ ð22Þ
@x
Z pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
3
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
3
x2 x
bð x3 l3 ; lÞ nð x3 l3 Þ nðlÞ
Baggl ðn; xÞ ¼ 2=3 dl ð23Þ
2 xc x3 l3
TAILORING PARTICLE SIZE 593
Z 1
Daggl ðn; xÞ ¼ nðxÞ bðx; lÞ nðlÞdl ð24Þ
0
volume fraction and its composition by controlling feed streams into the
mixing zone.
In conclusion, it is expected that an increase in supersaturation by
increasing the educt concentration as well as more intense mixing will
lead to smaller particles. Furthermore, it is expected that agglomeration
can be reduced, controlled, and possibly even completely prevented by
increasing the molar ratio R. i.e., increasing the barium concentration in
the suspension. Hence, primary particle size and agglomeration can be
adjusted independently within certain ranges to meet PSD product
requirements.
EXPERIMENTAL RESULTS
Precipitation experiments, some of which have previously been published
by the authors (Schwarzer and Peukert, 2002), were carried out as con-
tinuous experiments in the apparatus shown in Figure 4, which was
designed and built in-house. Two pistons are moved in cylinders of high-
precision Duran glass by Schott Geräte GmbH using a stepping motor
and gear reduction in order to generate two constant volume flows for the
educt solutions. As educts, aqueous solutions of barium chloride Merck
101719, analytical grade, dissolved in deionized water), and sulfuric acid
(Merck 109912, Combi-Titrisol, diluted with deionized water) were used
and precipitated in the T-mixer, shown in Figure 5, which includes a
schematic drawing of the tubes in the interior.
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The T-mixer was designed and built in-house from stainless steel
(1.4571) with a circular mixing zone of 1 mm in diameter and 10 mm in
length. The feed tubes are 0.5 mm in a diameter and are positioned
opposite each other. In order to characterize the flow through the mixer,
a mixer Reynolds number is defined according to Equation (25) based on
the mixing zone diameter and the volumetric flow rate through the
mixing zone.
UMZ dMZ V_
Re ¼ ¼ ð25Þ
nF p=4 dMZ nF
Figure 5. Picture of the used mixer showing the tubes in the interior.
TAILORING PARTICLE SIZE 595
In the presented experiments, the mixer was deployed at flow rates ran-
ging from 0.1 mL/s to 12 mL/s, which correspond to Reynolds numbers
ranging from Re = 127 to Re = 15280. The flow through the mixer can
be considered turbulent, dominated by the impinging of the educts. The
upper limit of the applied flow rates is due to the pressure drop in
the mixing zone, which is about 14 bar at Re = 15280. At this flow rate,
the operational capacity of the mixers is larger than one cubic meter
of educt solution per day and more than 100 kg of nanoscaled barium
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sulfate particles.
During the experiments, the generated suspensions were collected in
empty tanks, the initial as well as the final collections were discarded, and
the remaining main part, which corresponds to steady-state conditions,
taken for analysis. The PSD was measured off-line using a commercial
device (UPA 150 by Microtrac) based on quasi-elastic light scattering.
During the experiments, the pressure drop was recorded and the mean
specific power input in the mixing zone calculated. In addition, trans-
mission electron microscopy (TEM) and dry samples were prepared.
As expected due to the use of dilute educts, no temperature change
was detected as result of the mixing. X-ray diffraction patterns (Cu Ka
radiation, PW 1732 by Philips Analytical) confirmed the b-BaSO4 mod-
ification of the formed particles and thereby their crystallinity. Rheolo-
gical measurements of the suspension after precipitation CVO 120 by
Bohlin Instruments Ltd showed only a minor and thus negligible increase
in viscosity compared to the educts.
Measured PSD from five precipitation experiments at different
Reynolds numbers, i.e., flow rates through the mixer, are presented in
Figure 6 as volume density distributions. The theoretic initial super-
saturation S ¼ 3375 and the molar ratio R ¼ 1.5 were kept constant in
these experiments. As can be seen, the measured mean particle sizes as
well as the sizes of the smallest particles decrease as the Re number and
thereby the pressure drop as well as the mixing intensity increase. Particle
sizes were confirmed by TEM pictures as well as through nitrogen
adsorption via BET surface area and pore size distribution (Nova 2000
by Quantachrome Corp.).
The reason for the observed decrease with increasing Re number is
the different dependencies of nucleation and growth rate on super-
saturation and the ‘‘generation’’ of supersaturation through mixing. With
increasing supersaturation, the nucleation rate increases stronger than the
growth rate and thus more and smaller (size of nucleus) particles are
formed, which grow until supersaturation is completely reduced. At
larger Re numbers, mixing is faster and thus higher levels of
supersaturation are generated.
Figure 7 shows TEM pictures of barium sulfate nanoparticles pre-
cipitated at S ¼ 4405 and R ¼ 3 and mixing conditions corresponding to
596 H.-C. SCHWARZER AND W. PEUKERT
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pictures. TEM diffraction patterns showed that the primary particles are
monocrystalline. It is difficult to reach a conclusion on agglomeration
from these pictures since cluster formation during TEM sample pre-
paration (i.e., drying) is very likely. In any case, agglomeration at R ¼ 3
could not have been strong, or single primary particles would not have
occurred.
Reproducibility checks for S ¼ 2275, R ¼ 1.5, and Re ¼ 1270 showed
that the standard deviation of the volume-weighted mean particle size
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sponding to Re ¼ 1270.
With decreasing barium excess, i.e., decreasing value of R and thus
decreasing stability factor W, larger PSDs are measured, confirming that
agglomeration can play a major role in precipitation and confirming the
necessity to stabilize against agglomeration in nanoparticle precipitation.
From PSD-time measurements it was found that for R ¼ 1.5 the change
in mean particle size was below one nanometer per minute in a motionless
suspension (Brownian mechanism). Thus stabilization at R 1.5 can be
considered complete for the purposes of this investigation. The arrows in
the chart for the plot of R ¼ 1 indicate that the real PSD of that
experiment is out of the used device’s measurement range and that
therefore the real plot is shifted to some extent in the direction of the
arrows. Figure 9 clearly shows that slight changes of the suspension
composition have a strong effect on the resulting PSD.
SIMULATION RESULTS
The PSD of precipitation is calculated by solving the population balance
equation coupled with the extended EDD model of micromixing
numerically using the Galerkin-h-p method implemented in the com-
mercial software PARSIVAL1 by CiT GmbH. The flow through the
mixer is assumed to be plug flow, allowing a 1-D spatial resolution in the
simulations. Furthermore it is assumed that macromixing is much faster
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for three different levels of specific power input. Two conclusions can be
drawn from this figure: mixing time scales vary strongly with changing
power input and mixing is — for the investigated supersaturations— not
as fast as particle formation. Thus mixing has a strong influence on the
kinetics of precipitation processes and thereby on the PSD, which is
consistent with experimental findings.
Additionally, it is interesting to note that the complete reduction of
supersaturation is the faster the higher the initial value. This effect can be
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Figure 11. Calculated influence of agglomeration in the mixing zone as a function of the spe-
cific power input e on the volume-weighted mean particle size for different agglomeration
mechanisms and different stability factors W.
TAILORING PARTICLE SIZE 601
Figure 12. Calculated evolution of particle size distribution including nucleation, growth,
and turbulent agglomeration for S ¼ 3375, R ¼ 1.5, e ¼ 104 W/kg, and W ¼ 1.
602 H.-C. SCHWARZER AND W. PEUKERT
power input, the deviation of this plot from the plot for ‘‘no agglo-
meration’’ decreases as the specific power input increases, i.e., at decreas-
ing specific power inputs.
Figure 12 shows an example of the evolution of the PSD calculated
for a specific power input of e ¼ 104 W/kg, S ¼ 3375, R ¼ 1.5, and W ¼ 1,
including nucleation, growth, and turbulent agglomeration. As can be
seen, the shape as well as the position of the PSD changes in less than one
millisecond from the size of the nuclei, which is, according to Equation
(9), in the range of one nanometer up to several hundred nanometers.
After 10 microseconds sizes between 1 to 10 nanometers are reached, and
after 100 microseconds the particles sizes are in the range of 10 to 30
nanometers. Sizes in the range of 60 to 300 nanometers are reached after
one millisecond. By that time, supersaturation is completely reduced and
only agglomeration contributes to changes in the particle size distribu-
tion. The width of the PSD increases because of two reasons. First,
particles are formed at different points in time, and thus the PSD con-
tains young and small particles as well as older and larger particles. This
effect increases with time until supersaturation is reduced completely.
The second reason is that turbulent agglomeration enhances the
agglomeration of large particles relative to the agglomeration of smaller
ones as can be seen in Equation (14).
Figure 13 shows a comparison of simulation and experimental results
for S ¼ 3375, R ¼ 1.5, and W > 100. Both curves agree fairly well con-
sidering the various assumptions that have been made and the uncer-
tainties within the used barium sulfate specific data. It is especially
noticeable that the applied concept of using the extended EDD model of
micromixing in combination with pressure drop measurements to
describe micromixing seems appropriate. The mixing effect is qualita-
tively predicted correctly. From the combination of simulation and
experiment it can be concluded that for specific power inputs larger than
about 104 W/kg the mixing process does not have an significant influence
on the resulting particle size. However, compared with Figure 10 it is
clear that the mixing process at e ¼ 104 W=kg is about as fast as super-
saturation reduction. Only if the mixing is much faster than
supersaturation reduction, i.e., at about e > 106 W=kg for the investi-
gated case, can mixing be considered ideal.
TAILORING PARTICLE SIZE 603
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Figure 13. Comparison of experimental and simulation results for S ¼ 3375 and R ¼ 1.5
plotted as a function of the specific power input e.
CONCLUSIONS
Nanoparticle formation was investigated experimentally as well as
numerically using continuous barium sulfate precipitation in a T-mixter.
First, it was shown that the generation of barium sulfate nanoparticles by
precipitation is possible. Two important aspects were found that strongly
determine the resulting PSD: mixing and agglomeration. The faster the
mixing on the molecular scale (i.e., micromixing), the smaller the formed
primary particles. Agglomeration has to be suppressed by stabilization,
or particles sizes well in the mm range would occur on time scales in the
order of milliseconds, depending on turbulence intensity. The precipita-
tion process was simulated by coupling an extended version of the EDD
model of micromixing one-dimensionally with the population balance
equation. Both simulation results and experimental findings agree fairly
well. It is important to state that no model parameters were adjusted to fit
experimental data.
Simulations of the precipitation process led to new insights into the
kinetics of the process. It was found that the time scales of precipitation
depend strongly on the effective supersaturation, i.e., on educt con-
centrations. Usual time scales for the reduction of supersaturation under
604 H.-C. SCHWARZER AND W. PEUKERT
NOMENCLATURE
a distance between particle surfaces, m
Bagglo birthrate of agglomeration, m4 s1
Bhom nucleation rate, m3 s1
dMZ diameter of mixing zone, m
DAB diffusion coefficient, m2 s1
Dagglo death rate of agglomeration, m4 s1
E engulfment parameter, s1
fðxC Þ function describing the density distribution of nuclei
G linear growth rate, m s1
I ionic strength, kmol m3
k Boltzmann constant (1:381 1023 ), J K1
Kdis:2 dissociation constant, kmol m3
KSP solubility product, kmol2 m6
M molecular weight, kg kmol1
n(x) particle number density of size x, m4
N total particle number concentration, m3
NA Avogadro’s number ð6:023 1026 Þ, kmol1
R molar ratio
Re Reynolds number
S supersaturation
Sc concentration-based supersaturation
Sh Sherwood number
T temperature, K
t time, s
uMZ flow velocity through mixing zone, m s1
Vm molecular volume, m3
V_ volumetric flow rate, m3 s1
W stability factor
x particle size, m
xC size of critical nucleus, m
X volume fraction
zþ ; z: ionic charge of cations or anions
[] concentration, kmol m3
Greek letters
bcoll agglomeration kernel, m3 s1
gCL interfacial tension, J m2
TAILORING PARTICLE SIZE 605
g activity coefficient
e specific power input, W kg1
jtotal ðxÞ total particle-particle interaction potential, J
rC density of particles, kg m3
rF density of fluid, kg m3
n dissociation number
nF kinematic viscosity of fluid, m2 s1
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