Extreme emulsification: formation and structure of nanoemulsions
Nanoemulsions are metastable dispersions of nanodroplets of one liquid that have been ruptured by shear in another immiscible liquid. The ruptured droplets are stabilized against subsequent coalescence by a surfactant. Because the nanodroplets do not form spontaneously, as they can in lyotropic “m...
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irk-123456789-1213142017-06-15T03:02:31Z Extreme emulsification: formation and structure of nanoemulsions Mason, T.G. Graves, S.M. Wilking, J.N. Lin, M.Y. Nanoemulsions are metastable dispersions of nanodroplets of one liquid that have been ruptured by shear in another immiscible liquid. The ruptured droplets are stabilized against subsequent coalescence by a surfactant. Because the nanodroplets do not form spontaneously, as they can in lyotropic “microemulsion” phases, the structure of nanoemulsions is primarily dependent on the history of the applied shear stresses relative to the interfacial restoring stresses. By applying extremely high shear rates and controlling the composition of the emulsion, we have been able to rupture microscale droplets down to diameters as small as 30 nm in a microfluidic process that yields bulk quantities suitable for commercial production. Following ultracentrifugal fractionation to make the droplets uniform, we study the structure of these emulsions using small angle neutron scattering (SANS) at dilute and concentrated volume fractions. We contrast the structure of a concentrated nanoemulsion with the structure factor of hard spheres at a similar volume fraction. 2006 Article Extreme emulsification: formation and structure of nanoemulsions / T.G. Mason, S.M. Graves, J.N. Wilking, M.Y. Lin // Condensed Matter Physics. — 2006. — Т. 9, № 1(45). — С. 193–199. — Бібліогр.: 17 назв. — англ. 1607-324X PACS: 82.70.Kj, 61.46.-w, 61.12.Ex DOI:10.5488/CMP.9.1.193 http://dspace.nbuv.gov.ua/handle/123456789/121314 en Condensed Matter Physics Інститут фізики конденсованих систем НАН України |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine |
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DSpace DC |
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English |
| description |
Nanoemulsions are metastable dispersions of nanodroplets of one liquid that have been ruptured by shear in
another immiscible liquid. The ruptured droplets are stabilized against subsequent coalescence by a surfactant.
Because the nanodroplets do not form spontaneously, as they can in lyotropic “microemulsion” phases,
the structure of nanoemulsions is primarily dependent on the history of the applied shear stresses relative to
the interfacial restoring stresses. By applying extremely high shear rates and controlling the composition of
the emulsion, we have been able to rupture microscale droplets down to diameters as small as 30 nm in a
microfluidic process that yields bulk quantities suitable for commercial production. Following ultracentrifugal
fractionation to make the droplets uniform, we study the structure of these emulsions using small angle neutron
scattering (SANS) at dilute and concentrated volume fractions. We contrast the structure of a concentrated
nanoemulsion with the structure factor of hard spheres at a similar volume fraction. |
| format |
Article |
| author |
Mason, T.G. Graves, S.M. Wilking, J.N. Lin, M.Y. |
| spellingShingle |
Mason, T.G. Graves, S.M. Wilking, J.N. Lin, M.Y. Extreme emulsification: formation and structure of nanoemulsions Condensed Matter Physics |
| author_facet |
Mason, T.G. Graves, S.M. Wilking, J.N. Lin, M.Y. |
| author_sort |
Mason, T.G. |
| title |
Extreme emulsification: formation and structure of nanoemulsions |
| title_short |
Extreme emulsification: formation and structure of nanoemulsions |
| title_full |
Extreme emulsification: formation and structure of nanoemulsions |
| title_fullStr |
Extreme emulsification: formation and structure of nanoemulsions |
| title_full_unstemmed |
Extreme emulsification: formation and structure of nanoemulsions |
| title_sort |
extreme emulsification: formation and structure of nanoemulsions |
| publisher |
Інститут фізики конденсованих систем НАН України |
| publishDate |
2006 |
| url |
http://dspace.nbuv.gov.ua/handle/123456789/121314 |
| citation_txt |
Extreme emulsification: formation and structure of nanoemulsions / T.G. Mason, S.M. Graves, J.N. Wilking, M.Y. Lin // Condensed Matter Physics. — 2006. — Т. 9, № 1(45). — С. 193–199. — Бібліогр.: 17 назв. — англ. |
| series |
Condensed Matter Physics |
| work_keys_str_mv |
AT masontg extremeemulsificationformationandstructureofnanoemulsions AT gravessm extremeemulsificationformationandstructureofnanoemulsions AT wilkingjn extremeemulsificationformationandstructureofnanoemulsions AT linmy extremeemulsificationformationandstructureofnanoemulsions |
| first_indexed |
2025-07-08T19:38:17Z |
| last_indexed |
2025-07-08T19:38:17Z |
| _version_ |
1837108823263805440 |
| fulltext |
Condensed Matter Physics 2006, Vol. 9, No 1(45), pp. 193–199
Extreme emulsification:
formation and structure of nanoemulsions
T.G.Mason∗1,2, S.M.Graves1, J.N.Wilking1, M.Y.Lin3
1 Department of Chemistry and Biochemistry, University of California – Los Angeles,
607 Charles E Young Dr. East Los Angeles, CA 90095 USA
2 Department of Physics and Astronomy, University of California – Los Angeles,
607 Charles E Young Dr. East Los Angeles, CA 90095 USA
3 Center for Neutron Research, National Institute of Standards and Technology,
Gaithersburg, MD 20899 USA
Received July, 18, 2005, in final form November 24, 2005
Nanoemulsions are metastable dispersions of nanodroplets of one liquid that have been ruptured by shear in
another immiscible liquid. The ruptured droplets are stabilized against subsequent coalescence by a surfac-
tant. Because the nanodroplets do not form spontaneously, as they can in lyotropic “microemulsion” phases,
the structure of nanoemulsions is primarily dependent on the history of the applied shear stresses relative to
the interfacial restoring stresses. By applying extremely high shear rates and controlling the composition of
the emulsion, we have been able to rupture microscale droplets down to diameters as small as 30 nm in a
microfluidic process that yields bulk quantities suitable for commercial production. Following ultracentrifugal
fractionation to make the droplets uniform, we study the structure of these emulsions using small angle neutron
scattering (SANS) at dilute and concentrated volume fractions. We contrast the structure of a concentrated
nanoemulsion with the structure factor of hard spheres at a similar volume fraction.
Key words: emulsion, nanoemulsion, droplet, nanoscale, rupturing, microfluidics, form factor, structure
factor, fractionation
PACS: 82.70.Kj, 61.46.-w, 61.12.Ex
1. Introduction
Emulsions are dispersions of droplets of a liquid phase in a different immiscible liquid [1–3]. Oil
droplets dispersed in water are known as “direct emulsions”, whereas water droplets dispersed in
oil are called “inverse emulsions”. Without shear, emulsions would never form, since the thermo-
dynamic lowest energy state of two immiscible liquids is simply a layer of the liquid having lower
density on top of a layer of the liquid having higher density. In order to create emulsions, shear must
be applied in a way that causes the droplets of one phase to stretch and rupture, through a capillary
instability, into smaller droplets. Stretching and rupturing the droplets is possible if the applied
shear stress is greater than the characteristic Laplace pressure scale, σ/a, where σ is the liquid-
liquid surface tension and a is the droplet’s radius. A surfactant, usually soluble in the continuous
phase, coats the surfaces of the newly formed droplets and provides a stabilizing repulsion between
droplet interfaces that strongly inhibits subsequent recombination, or coalescence, of the droplets.
Microscale emulsions can be commonly made in the kitchen using shear stresses generated by
whisks, spatulas, and blenders; mayonnaise is a common food emulsion of oil droplets in water sta-
bilized by egg protein. However, obtaining nanoscale emulsions having droplet diameters less than
100 nm with these methods is generally not possible since the applied shear stresses are too low.
In order to go beyond conventional emulsification methods into the realm of nanoemulsions,
it is necessary to apply extremely high shear stresses to cause violent stretching and rupturing
of the droplets. By equating the viscous stress of the driving shear with the Laplace pressure
∗Presenting author
c© T.G.Mason, S.M.Graves, J.N.Wilking, M.Y.Lin 193
T.G.Mason et al.
of droplets that no longer rupture in the shear flow, one can obtain the classic Taylor equation
for estimating the radius of the emulsion [2–4]: a ≈ σ/(ηcγ̇), where γ̇ is the shear rate and ηc
is the viscosity of the continuous liquid phase in which the droplets are dispersed. This formula
neglects the dissipative effects of viscosity, ηd, of the liquid inside the droplets. Since the shear stress
depends on a combination of the shear rate and the emulsion’s rheological properties, it is possible to
make nanoscale emulsions of strongly immiscible liquids without relying upon thermodynamic self-
assembly of nanoscale droplets in microemulsion phases [5,6]. Microfluidic and ultrasonic techniques
both produce the kind of extreme shear that is required to break emulsions down to diameters
below 100 nm [7–9]. Sub-micron emulsions are sometimes called “mini-emulsions”, and we define
“nanoemulsions” to be emulsions having diameters around 100 nm or less [10]. Because the sub-
microscopic droplet sizes make it difficult to observe the droplets and because very strong shear
is required to create them, nanoemulsions have been studied far less than conventional emulsions.
Moreover, since it is easier to visualize the rupturing of isolated droplets, most experiments have
avoided the complexity inherent in emulsification of concentrated emulsions at a droplet volume
fraction φ where droplet interfaces strongly interact.
We have developed a systematic procedure using a high-pressure microfluidic device to create
bulk quantities of oil in water nanoemulsions with diameters as small as 30 nm [10]. Although the
raw nanoemulsions have a peaked monomodal size distribution, as determined by dynamic light
scattering, we use ultracentrifugation to fractionate the droplets and make them more monodis-
perse. Once fractionated, the nanoemulsions are an excellent model system for investigating the
structure of concentrated dispersions of deformable droplets using small angle neutron scattering
(SANS) [11]. We contrast the structure of a concentrated nanoemulsion with the structure of a
concentrated suspension of uniform hard spheres, and we propose some simple, yet speculative,
explanations for the differences in the structure.
2. Experiment
Silicone oil (polydimethylsiloxane or PDMS) is first dispersed in an aqueous solution of the ionic
surfactant, sodium dodecylsulfate (SDS) using a crude blender to create microscale droplets. In this
first step, we create a premixed emulsion that has a controlled oil viscosity, ηd, oil volume fraction, φ,
and surfactant concentration, C. The premixed microscale emulsion is then used as the input feed to
a high-pressure, impinging-jet microfluidic device (Microfluidics). The microfluidic device is driven
by compressed air at a pressure, p, and creates a pulsed extensional shear flow with peak shear rates,
γ̇, in excess of 108 s−1. We typically process a volume of about 100 ml over less than a minute. Since
the flow in the steel microfluidic channel is spatially inhomogeneous, we then take this processed
emulsion and feed it back into the microfluidic device several times so that all of the droplets
experience the region of peak shear. The number of times the emulsion has been processed through
the device is the number of passes, N . By varying the air pressure, we can vary the peak shear
rate and the sizes of the ruptured droplets. We characterize the resulting volume-weighted radial
distribution, p(a), of the emulsion that has been diluted considerably to φ ≈ 10−5 using dynamic
light scattering (DLS) at 90 degrees. From this, we extract the volume-averaged radius, 〈a〉.
In order to further improve the uniformity of the size distribution, we use ultracentrifugal
fractionation [12]. In the earth’s gravitational field, the Brownian motion of the nanodroplets is so
strong that gravitational buoyant forces do not cause appreciable creaming, even over long time
scales. However, ultracentrifugation can produce such large effective gravitational acceleration that
the buoyant forces can overcome the Brownian motion. Ultracentrifugal fractionation is a simple
method that relies upon the differences in the creaming rates of small and large droplets when
the droplets experience a buoyant force due to the density difference between the oil and water.
This density difference is typically about 0.05 g/cm3, and depends on the molecular weight of the
oil. Since the Stokes drag force on a sphere is proportional to va, where v is the steady creaming
velocity, and the buoyant force is proportional to a3, the creaming velocity is proportional to
a2, so size separation can be efficient. We dilute the emulsion to φ = 0.1 and spin at 20,000
RPM for several hours using a swinging bucket rotor. The solid plug at the top of the centrifuge
194
Extreme emulsification: formation and structure of nanoemulsions
tube is extracted and split into sections, and similar sections from different tubes are recombined.
The process can be repeated until the desired degree of uniformity is obtained. The drawback of
repeating this process many times is that the volume of the emulsion is reduced by at least a factor
of two in each stage of the fractionation.
The small angle neutron scattering measurements have been carried out at the National Insti-
tute of Standards and Technology (NIST) in Gaithersburg, MD, USA. The neutron wavelength is
8 Å, and we load the nanoemulsions into 1 mm path length quartz banjo cells. Transmission mea-
surements indicate that only 1.5% of the neutrons are multiply scattered in the most concentrated
samples, so the scattering data are overwhelmingly dominated by single scattering. For concentrat-
ed φ, the emulsions are viscoelastic [13], so we use demountable cells to facilitate loading. The range
of wavenumbers, q, that we choose provides an excellent view of the important features relating to
the size and interdroplet structure in concentrated nanoemulsions. The intensity, I, as a function of
q is calculated by azimuthally averaging the measured intensities from the 2-dimensional neutron
array detector around the beam stop center position. We eliminate the data at the lowest q that are
affected by the beam stop, and the intensities are reported in absolute units through calibration
with known standards.
3. Results
We first present results relating to the production and fractionation of the nanoemulsions, and
then we describe structural studies of dilute and concentrated emulsions using SANS.
Figure 1. Average droplet radius, 〈a〉, as a function of the number of passes, N , of silicone
oil-in-water nanoemulsions having a fixed volume fraction φ = 0.2, surfactant concentration,
C = 116 mM, and oil viscosity ηd = 10 cP at the following driving air pressures, p: 40 (inverted
triangles), 60 (triangles), 90 (diamonds), 115 (squares), 130 (circles). The solid lines are fits to
〈a(N)〉 = 〈as〉[1 + g exp(−N/Ns)], as explained in the text.
We have investigated how the peak shear rate affects the droplet sizes for semi-dilute emulsions
that are subjected to the strong extensional shear flow. In figure 1, we show the average oil droplet
radius obtained from DLS as a function of the number of passes, N , for a set of different input
air pressures to the microfluidic device ranging from p = 40 psi to 130 psi. The composition of
the premixed emulsion is exactly the same in all cases: φ = 0.2, C = 116 mM, and ηd = 10 cP.
The average droplet radius decreases systematically as we increase the peak shear rate through
the driving air pressure. Moreover, as N increases, the average radius decreases initially, yet it
begins to saturate toward a constant value, 〈as〉, at the largest N we explore. To characterize the
decrease, we fit each 〈a(N)〉 at a particular pressure to the following empirical equation [10]:
〈a(N)〉 = 〈as〉 [1 + g exp(−N/Ns)] , (1)
where g is a dimensionless factor related to the ratio of the effective radius at low passes to 〈as〉 and
Ns is the characteristic number of passes where the exponential decrease component has fallen to
195
T.G.Mason et al.
1/e. The solid lines in figure 1 show that the fits provide an excellent description of the reduction in
〈a(N)〉 at all measured pressures. For all of the different pressures, the shape is not very different:
Ns ranges from 2 to 3 and g ranges from 1 to 2. At six passes the measured 〈a〉 are within 20% of
the saturation radii, so it is not possible to cause a significant reduction in 〈a〉 beyond N ≈ 6 with
this particular composition, regardless of the pressure. The origin of the reduction and saturation of
〈a(N)〉 remains speculative, yet one hypothesis, which is at least qualitatively consistent with our
results, is that the shear flow in the microfluidic device is both spatially and temporally varying.
This is due to the pulsing flow that drives the emulsion through the microchannels. The fluid
velocities must be lower near the walls, so only a fraction of the total volume of the emulsion
experiences the peak shear rate in any given pass. It is clear that higher shear rates yield the
smallest droplets. However, over the limited range of pressures we have studied, we find that 〈as〉
does not vary inversely with the pressure and, therefore, shear rate, as one might expect from
simple rupturing of isolated droplets in strictly controlled viscous shear flows. For an increase in
pressure of about a factor of three, we find only a reduction of about a factor of two in 〈as〉. The
origin of this deviation from the Taylor estimate may arise from the increasingly important role of
the dispersed phase viscosity as the droplets become smaller.
Figure 2. Average droplet radius, 〈a〉, as a function of length, L, along the solid plug of con-
centrated emulsion after ultracentrifuging a silicone oil-in-water emulsion at 20,000 RPM for 3
hours. Small and large L correspond to the bottom and top of the plug, respectively.
As an example of the size separation that can be obtained from additional ultracentrifugal
fractionation after microfluidic emulsification, we present the average radius of the droplets as a
function of length, L, along one of the solid plugs that we have extracted from the top of the
tube in figure 2. The composition of the emulsion before centrifugation has been set at φ = 0.1,
ηd = 10 cP, and C = 58 mM. As the emulsion is spun at 20,000 RPM, a solid plug forms at the top
of the centrifuge tube, and essentially no droplets are remaining in the aqueous solution below. At
the top of the plug, we find larger droplets that have creamed rapidly, and at the lower part of the
plug, we find smaller droplets that have taken longer to cream. The range of average droplet radii
shown in the plot is rather small, from about 60 nm to about 120 nm, since the unfractionated
nanoemulsion exciting the microfluidic device is not very polydisperse.
In figure 3, we show the form factors, F (q), of several different nanoemulsions that have been
ultracentrifugally fractionated three times, measured using SANS. All of the data shown are for
φ 6 0.01 so that interference effects from neighboring droplets is minimal and the scattering is just
related to the Fourier transform of a sphere, averaged over the droplet size distribution. At low q,
a flat plateau is visible. Toward higher q, there is a primary shoulder providing the characteristic
droplet size, and a secondary shoulder at even higher q is visible. The evidence of the primary
and secondary shoulders indicates that our emulsions are quite uniform. Except for the smallest
droplets, the minimum in F (q) expected between the two shoulders for perfectly monodisperse
spheres is largely smeared out due to the droplet polydispersity, and, to a lesser degree, by the
width of the neutron wavelength distribution. The solid lines in figure 3 are fits to the data using a
model of hard spheres [14] having a polydisperse Schulz distribution. The smallest polydispersity
196
Extreme emulsification: formation and structure of nanoemulsions
Figure 3. Form factor, F , as a function of wavenumber, q, for three different silicone oil-in-water
nanoemulsions after ultracentrifugal fractionation. The intensities of the top and middle curves
have been multiplied by 104 and 102, respectively, to make them easier to view. Solid lines are
fits to a Shultz distribution of polydisperse hard spheres, and the results of the fit give the
following average radius, 〈a〉, and polydispersity, δa/〈a〉: 20 nm at 13% (squares), 27 nm at 16%
(inverted triangles), and 33 nm at 21% (circles).
that we observe is 13%, corresponding to the smallest droplet radius of 〈a〉 = 20 nm. This is
definitive proof that we have obtained bulk quantities of a very uniform dispersion of nanoscale oil
droplets in water. The smallest nanoemulsion we have observed with SANS has 〈a〉 = 15 nm.
Figure 4. Structure factor, S, as a function of dimensionless wavenumber, qa, for nanoemulsion
droplets having 〈a〉 = 75 nm at a droplet volume fraction, φ = 0.46 (solid circles). The solid line
is the theoretical prediction for disordered hard spheres using the Percus-Yevick approximation
at φ = 0.45. The peak for nanoemulsion droplets is much weaker and occurs at higher qa than
the peak for hard spheres.
In addition to examining the form factor of dilute nanoemulsions, we have also used SANS
to study the structure of a concentrated nanoemulsion. In figure 4, we show the structure factor,
S(qa), of a nanoemulsion having 〈a〉 = 75 nm, φ = 0.46, and C = 10 mM. This structure factor has
been obtained by dividing the measured intensity, I(qa), of the emulsion at φ = 0.46 with the form
factor, F (qa), obtained at dilute φ. The two dimensional scattering pattern shows a ring, indicating
that the overall droplet structure is not crystalline, but is disordered, as in a glass [15]. At the
lowest qa, S(qa) is much less than one, indicating that droplets are repelled from their neighbors.
At higher qa, the structure factor exhibits a small nearest-neighbor peak, indicating that there is a
small degree of correlation of the centers of neighboring droplets. However, the peak value of S for
nanoemulsions is much lower than that of perfectly monodisperse hard spheres at essentially the
same φ (see figure 4). Presumably, nanoemulsions stabilized by ionic surfactants would interact
through Debye-screened repulsions, not hard repulsions, so it is not surprising that the experiment
197
T.G.Mason et al.
does not match the prediction. However, the nature of the shift in the q value associated with
the peak remains mysterious. The differences between the two plots are not yet well understood
theoretically, yet it is unlikely that the residual polydispersity of the droplets could account for all
of the differences in the magnitude and positions of the peaks [16].
4. Discussion
Microfluidic production can be used to produce silicone oil-in-water nanoemulsions that have
radii down to about 15 nm. Due to spatially inhomogenous flow in the microfluidic device, multiple
passes of the emulsion are generally required to cause all droplets to experience the region of highest
shear and, thus, to obtain a more uniform distribution of smaller droplets. Through dilution and
centrifugation of the nanoemulsion, it is possible to independently control φ and C. Moreover,
ultracentrifugal size fractionation is effective in creating nanoemulsions having polydispersities
approaching 10%. After emulsification and fractionation, the nanoemulsion can be manipulated
to alter the composition without changing the droplet sizes. Thus, we have demonstrated that
controllable model systems of deformable nanoscale droplets for scientific studies are possible in
bulk quantities without relying upon swollen lyotropic micellar phases. The nanoscale droplets are
stable, robust, and long-lived, provided the molecular weight of the oil is large enough to prevent
coarsening of the droplet sizes through the diffusive transport of oil molecules from one droplet
to another through the continuous aqueous phase. It is possible to make nanoscale droplets of oils
having viscosities as high as 1000 cP, although the smallest droplets are generally obtained with
lower viscosity oils. Thus, nanoemulsions represent the extreme limit of metastable liquid droplet
dispersions. We believe that it is possible to make stable droplets having radii smaller than 10 nm
through extreme emulsification, although we do not expect to reach 2 nm, corresponding to the
radius of a surfactant micelle. Exploring the limits of extreme emulsification remains an interesting
frontier in soft condensed matter physics.
Likewise, the structure of concentrated nanoemulsions is also intriguing. At dilute φ, where
droplets are well separated from their nearest neighbors, the droplets are spherical. Since the
screening length is only a few nanometers, the charged droplets do not repel strongly except a very
short distances between the interfaces. Thus, the neutron scattering pattern of nanoemulsions can
be well understood in the same manner as a dilute dispersion of hard spheres, and the form factor
of polydisperse hard spheres can be used to fit our data nicely. However, the deformability of the
droplets in nanoemulsions can affect the structure at higher volume fractions approaching the glass
transition. The glassy disorder can lead to a peak in the structure factor that is not as pronounced
as in disordered hard spheres at higher concentrations. Polydispersity alone cannot account for this
difference between liquid droplets and hard spheres, and it is possible that the droplet deformability
is beginning to alter the scattering as the droplets reach concentrations at which they begin to
deform. This deformation may cause a reduction in the extent of spatial correlations of the centers
of the droplets that would be seen in S(qa). More work, both experimental and theoretical, is
needed to establish the structure of deformable objects that are quenched to high volume fractions
where they both jam [17] and deform.
5. Conclusion
We have introduced nanoemulsions as metastable droplet dispersions resulting from extreme
emulsification, and we have presented some initial structural measurements of fractionated na-
noemulsions using small angle neutron scattering. Nanoemulsions are interesting model systems of
deformable droplets that are part of the growing array of nanoscale materials. As a model system,
concentrated nanoemulsions are particularly interesting for exploring the average structure of bili-
quid foams. Potential applications in pharmaceutical products, in which control over droplet size
and polydispersity is important, appear to be promising.
198
Extreme emulsification: formation and structure of nanoemulsions
Acknowledgements
We thank Dr. John McTague for supporting this research through the McTague Career Devel-
opment Chair at UCLA. We thank NIST for the NG–7 SANS beam time.
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Received July, 18, 2005, in final form November 24, 2005
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PACS: 82.70.Kj, 61.46.-w, 61.12.Ex
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