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Supplementary Materials for

Free-standing liquid membranes as unusual particle separators

Birgitt Boschitsch Stogin, Luke Gockowski, Hannah Feldstein, Houston Claure, Jing Wang, Tak-Sing Wong*

*Corresponding author. Email: tswong@psu.edu

Published 24 August 2018, Sci. Adv. 4, eaat3276 (2018)


DOI: 10.1126/sciadv.aat3276

The PDF file includes:

Section S1. Descriptions of movies S1 to S10


Section S2. Sources of energy dissipation
Legend for Movies S1 to S10
Fig. S1. A schematic diagram showing a bead passing through a liquid membrane.
Fig. S2. Comparison of the relative magnitude of different energy terms.
Fig. S3. Theoretical dependence of E* on relevant parameters.
Fig. S4. Effect of mechanical perturbation frequency on the longevity of liquid membranes.
Fig. S5. Residual liquid on both hydrophilic and hydrophobic particles.
Table S1. Surface tension and density of different liquid membrane solutions.
Table S2. Liquid membrane mass and thickness characterization.
Table S3. Surface roughness measurements of various bead materials.
Table S4. Advancing angles of liquid membrane solution droplets on a flat surface.
Table S5. Reported inertial parameters for various organisms and particles.
References (27–40)

Other Supplementary Material for this manuscript includes the following:

(available at advances.sciencemag.org/cgi/content/full/4/8/eaat3276/DC1)

Movie S1 (.mov format). Large and small bead separation.


Movie S2 (.mov format). Particle filtration.
Movie S3 (.mov format). Insect retention.
Movie S4 (.mov format). Live insect retention.
Movie S5 (.mov format). In-film probe movement.
Movie S6 (.mov format). Particle transport.
Movie S7 (.mov format). Self-cleaning of liquid membranes.
Movie S8 (.mov format). Simulated surgery.
Movie S9 (.mov format). Liquid membranes as selective gas/solid barriers.
Movie S10 (.mov format). Liquid membrane longevity.
Section S1. Descriptions of movies S1 to S10

Movie S1. Large and small bead separation.


This video shows a liquid membrane retaining a small polytetrafluoroethylene (PTFE)
bead while allowing a large one to pass through.

Movie S2. Particle filtration.


This video shows how a liquid membrane can be used to separate a mixture of glass
particles according to their size. Here, the small glass particles are retained while the
large one passes through the membrane.

Movie S3. Insect retention.


This video demonstrates that insects (i.e., fruit fly, house fly, and mosquito) can be
retained within a liquid membrane at typical flight speeds. Here, dead insects were used
in order to control the impact velocity of the insect. The dead insects impact the liquid
membrane at speeds typical of their live counterparts.

Movie S4. Live insect retention.


This video demonstrates that live insects (i.e., fruit flies) can be retained within a liquid
membrane.

Movie S5. In-film probe movement.


This video shows a PTFE rod freely moving while embedded in the liquid membrane.

Movie S6. Particle transport.


This video demonstrates that small glass particles retained in the liquid membrane can be
transported within the membrane due to gravity.

Movie S7. Self-cleaning of liquid membranes. Our experimental setup involves a tilted
liquid membrane where contaminates (here, small sand particles) are passively removed
from the separation region by gravity, allowing the large particle to be collected. The
small particles are collected in the accumulation region and removed from the membrane
when the weight of the aggregate exceeds the capillary force exerted by the liquid
membrane (“aggregate removal”). Particles used here were sand (small particles) and
glass (large particles).

Movie S8. Simulated surgery.


This video shows a simulated surgery. Here, the membrane allows medical tools (i.e.,
scalpel and tweezers) and bovine flesh to pass through it while blocking dust particles (oil
based pink UV fluorescent powder, Slice of The Moon).

Movie S9. Liquid membranes as selective gas/solid barriers.


This video shows that a liquid membrane can be used to contain/divert fog (to simulate
and visualize gas sequestration) while allowing solid particles to pass through. This
property may be useful in solid waste/odor management.
Movie S10. Liquid membrane longevity.
Here we demonstrate that a liquid membrane can last for over three hours when
replenished, even when perturbed with a glass probe. Here, the period of probe oscillation
is 3.55 s; images were acquired at a rate of 1 frame/sec. A subset of these images were
used to generate this video (an effective acquisition rate of 1 frame per 63 s with a
playback frame rate of 5 frames/s). In total, 3042 probing cycles were completed to make
this video. The video duration was limited by camera memory rather than membrane
lifetime.
Section S2. Sources of energy dissipation

After a bead impacts a liquid membrane, bead-membrane interactions lead to energy


exchange and dissipation. As the bead travels through the membrane, it stretches the
membrane, converting some of the bead kinetic energy into film surface energy.
Furthermore, the liquid-solid interface may slide along the bead surface, leading to
energy dissipation due to membrane pinning. We investigate the significance of these
energy terms here (see fig. S1 for definition of variables).

Fig. S1. A schematic diagram showing a bead passing through a liquid membrane.
Several variables used throughout our discussion are shown.

Surface energy change due to film stretching

As the bead passes through the membrane, the membrane stretches, increasing the surface
energy. As this occurs, the bead-film contact line may slide along the bead surface, thus
changing the boundary conditions of the membrane over time. We anticipate that this
contact line motion is a function of the dynamics and geometry of the system, as well as
the advancing contact angle of the membrane on the bead surface. In an effort to make a
rough estimate of the maximum membrane stretching and thus the maximum change in
surface area of the membrane, we simplify our system by assuming that the membrane-
bead contact line remains fixed to the equator of the bead. Since the bead is traveling at
relatively low speeds and existing work (13) has shown that beads impacting films at low
Weber number (𝑊𝑒) generate catenoid surfaces (i.e., minimal surfaces), we assume that
in all of our experiments the membrane is approximately a minimal surface at each
moment in time as it stretches. Since a minimal surface has a mean curvature 𝜅 of zero
everywhere on the surface, the pressure difference Δ𝑝 across the membrane interfaces
should be approximately zero (based on the Young-Laplace equation, Δ𝑝 = 2𝛾𝜅) so we
ignore energy losses due to drag arising from film movement. The minimal surface
formed by two concentric circular boundaries is a catenoid, a surface that can be
represented as the surface of rotation (about the y-axis) of the following equation
𝑦 (S1)
𝑥 = 𝑎 cosh (𝑎)

where 𝑎 is a constant.

Since we assume (1) that the film remains attached to the bead at the equator and (2) the
membrane is a catenoid (with boundaries at the ring and at the bead equator), we
approximate the maximum film stretch area to be the area of the catenoid formed when
the liquid membrane is tangent to the equator of the bead at the bead-film contact line.
Any further stretching would mathematically allow membrane-bead intersection, which is
non-physical. The boundary conditions associated with these assumptions are

𝑥(𝑦max ) = 𝑅𝑓
𝑥(𝑦 = 0) = 𝑅𝑏

𝑑𝑥
| = 0
𝑑𝑦 𝑦=0

where 𝑅𝑓 is the film radius, 𝑅𝑏 is the bead radius, and 𝑦max is the vertical distance
between the film and the bead center associated with the maximum membrane stretch
area.

Solving equation S1 using the above boundary conditions, the catenary associated with
our maximal stretching conditions is

𝑦
𝑥 = 𝑅𝑏 cosh (𝑅 ) (S2)
𝑏

and the maximum stretch distance is

𝑅
𝑦max = 𝑅𝑏 cosh−1 (𝑅𝑓 ) (S3)
𝑏

The surface of revolution about the y-axis of this shape (i.e., a catenoid) has an area
𝐴cat (which accounts for the two sides of the film) given by

𝐴cat = 𝜋𝑅𝑏2 (sinh 𝜙 + 𝜙) (S4)

𝑅
where 𝜙 = 2 cosh−1 (𝑅𝑓 )
𝑏

We consider the maximum change in surface energy to be the difference between the
surface energy of a film with area 𝐴cat and that of the flat annular film (inner radius 𝑅𝑏 ,
outer radius 𝑅𝑓 ) at bead impact. The maximum surface energy change is thus given by
𝐸𝑠 = 𝜋𝛾𝑅𝑏2 [sinh 𝜙 + 𝜙] − 2𝜋𝛾(𝑅𝑓2 – 𝑅𝑏2 ) (S5)

where 𝛾 is the surface tension of the liquid membrane.

Friction (pinning) when film slides along bead

As the liquid membrane contact line slides along the surface of the bead, energy may be
lost due to friction. This energy can be captured by the pinning energy. The pinning force
is given by Furmidge (27)

𝐹𝑃 = 2𝛾𝜋𝑅(𝛼)(cos𝜃𝑅 − cos𝜃𝐴 )

where 𝑅(𝛼) = 𝑅𝑏 sin𝛼 and 2𝜋𝑅(𝛼) is the perimeter of the film-bead contact line when
the contact line is at an angle 𝛼 from vertical (fig. S1). Since work is force multiplied by
distance, we can calculate the energy dissipated as the film moves from different values
of 𝛼 as follows
𝛼2
𝐸𝑃 = ∫ 2𝛾𝜋𝑅𝑏2 sin𝛼 ⋅ (cos 𝜃𝑅 − cos 𝜃𝐴 )𝑑𝛼
𝛼1

While the initial liquid membrane motion may be more of a wrapping than sliding
motion, we assume a sliding motion from 𝛼1 = 0 to 𝛼2 = 𝜋 (possibly leading to an
overestimate of 𝐸𝑃 ), leading to

𝐸𝑃 = 2𝜋𝛾𝑅𝑏2 (cos𝜃𝑅 − cos𝜃𝐴 ) (S6)

Relative magnitude of different energy terms

The kinetic energy of a bead at impact is approximately

4 (S7)
𝐸𝑢𝑏 = 𝜌𝑏 𝑔𝐻 ( 𝜋𝑅𝑏3 )
3
where 𝜌𝑏 is the bead density, 𝑔 is the magnitude of the acceleration due to gravity, and
𝐻 is the height above the membrane from which the bead was dropped, assuming all
potential energy is converted to kinetic energy. According to Equations S5, S6, and S7
and our experimental conditions, 𝐸𝑃 /𝐸𝑢𝑏 << 1 but 𝐸𝑠 is comparable to 𝐸𝑢𝑏 (fig. S2).
We thus conclude that, for our experiments, 𝐸𝑃 is negligible and define 𝐸 ∗ as

𝐸 (S8)
𝐸∗ = 𝐸 𝑠
𝑢𝑏
Fig. S2. Comparison of the relative magnitude of different energy terms. The relative
magnitude of different energy terms (𝐸𝑆 and 𝐸𝑃 ) compared to the kinetic energy (𝐸𝑢𝑏 ) at
bead impact with the liquid membrane for (A) glass, (B) polytetrafluoroethylene (PTFE),
and (C) polystyrene (PS) beads.
Fig. S3. Theoretical dependence of E* on relevant parameters. Here we plot ln𝐸 ∗
analytically, assuming we are dropping a glass bead (𝜌𝑏 = 2500 kg/m3) into the
membrane from height 𝐻. The plots on the right panels show a zoomed-in region of the
plots on the left panels for 0.01< 𝑅𝑏 /𝑅𝑓 < 0.1. (A, B) Influence of 𝑅𝑓 on 𝐸 ∗ : ln𝐸 ∗ as a
function of 𝑅𝑏 /𝑅𝑓 at a fixed drop height 𝐻 and surface tension 𝛾. The inset in (A) shows
a dimensional x-axis for clarity. Here we see that increasing 𝑅𝑓 should lead to an increase
in 𝑅𝑏,cr (the maximum value of 𝑅𝑏 where bead retention will occur) when all other
parameters are held constant. (C, D) Influence of 𝛾 on 𝐸 ∗ : ln𝐸 ∗ as a function of 𝑅𝑏 /𝑅𝑓 at
fixed 𝑅𝑓 and 𝐻 for different 𝛾. Here we see that increasing 𝛾 leads to an increase in 𝑅𝑏,cr
when all other parameters are held constant. (E, F) Influence of 𝐻 on 𝐸 ∗ : ln𝐸 ∗ as a
function of 𝑅𝑏 /𝑅𝑓 with a fixed 𝑅𝑓 and 𝛾 for different 𝐻. Here we see that an increase in
𝐻 leads to a decrease in 𝑅𝑏,cr when all other parameters are held constant. These
relationships only hold if the weight of the bead does not exceed the capillary force
acting on the bead.

Fig. S4. Effect of mechanical perturbation frequency on the longevity of liquid


membranes. (A) A plot showing the longevity of the liquid membrane with respect to
the perturbation frequency. Each data point represents the measured longevity of a single
liquid membrane. The longevity 𝐿 of the liquid membrane is normalized with respect to
the maximum longevity of the membrane at 0 Hz, 𝐿0,max . In this experiment, external
perturbations took place using a Pasco Mechanical Wave Driver oscillating vertically at
an amplitude of ~3 mm. The driver was connected to a metal plate with an array of
circular cutouts 2 cm in diameter. Liquid membranes were applied to the holes. (B, C)
Response of the liquid membrane to different forcing frequencies. Liquid membranes
lasted ~1 second at 55 Hz, but lasted significantly longer at 85 Hz, suggesting that
membrane lifetime depends on the perturbation frequency. The liquid membranes used
here were comprised of 7:3 ratio by volume of deionized water and glycerol and a 8.5
mM concentration of sodium dodecyl sulfate. The scale bars each represent 1 cm.
Fig. S5. Residual liquid on both hydrophilic and hydrophobic particles. Residual
liquid on both hydrophilic and hydrophobic particles after liquid membrane detachment
and self-healing. The liquid membrane is composed of 7:3 volume ratio of water and
glycerol, and 8.5 mM of sodium dodecyl sulfate.
Table S1. Surface tension and density of different liquid membrane solutions. The
average surface tension and density (with standard deviations) were calculated from 5
independent measurements.

[SDS] (M) Surface Tension (mN/m) 3


Density (kg/m )

.0000 72.1 ± 0.4 1001.5 ± 3.2


.0019 60.2 ± 0.3 997.7 ± 5.8
.0026 55.0 ± 0.2 991.5 ± 2.9
.0037 48.9 ± 1.2 987.7 ± 9.6
.0045 48.4 ± 0.3 994.9 ± 7.5
.0053 44.8 ± 0.4 990.8 ± 6.4
.0062 41.6 ± 0.2 991.0 ± 9.6
.0071 39.4 ± 0.2 985.9 ± 12.6
.0079 36.8 ± 0.3 974.5 ± 11.2
.0087 35.6 ± 0.2 966.6 ± 3.6
.0096 35.4 ± 0.2 971.2 ± 12.3
.0106 35.6 ± 0.1 965.2 ± 1.9

Table S2. Liquid membrane mass and thickness characterization.

Ring Radius (cm) [SDS] (M) Film Mass (mg) Thickness (μm)

1.5 0.0104 47.9 ± 5.5 ~70


1.27 0.0087 20.2 ± 6.5 ~40
Table S3. Surface roughness measurements of various bead materials. Surface
roughness measurements of various bead materials used in our experiments. Note that the
scan area denotes the projected area of the scan region.

Material 𝝃 (μm) Scan Area Manufacturer


(μm × μm)
Glass (sphere; soda lime) 0.301 ± 0.019 836 × 836 Cospheric
Glass slide (flat; borosilicate) 0.002 ± 0.000 836 × 836 VWR
PTFE (sphere) 1.082 ± 0.033 836 × 836 McMaster-Carr
PTFE (flat) 0.702 ± 0.197 836 × 836 McMaster-Carr
PS (sphere) 2.225 ± 0.036 773 × 773 Cospheric
PS (flat) 0.650 ± 0.006 836 × 836 McMaster-Carr

Table S4. Advancing angles of liquid membrane solution droplets on a flat surface.
All advancing angle measurements for polytetrafluoroethylene (PTFE) and polystyrene
(PS) were taken using a drop volume addition and subtraction method. The advancing
angles of water and 10.6 mM SDS solution on glass were measured to be < 10∘ .

θA(o)

[SDS] (M) PTFE PS


.0000 129.2 ± 1.7 97.2 ± 1.8
.0019 119.3 ± 3.8 83.4 ± 2.1
.0026 111.8 ± 3.8 78.9 ± 2.7
.0037 118.0 ± 1.2 71.3 ± 3.8
.0045 108.2 ± 7.1 72.3 ± 1.2
.0053 116.8 ± 0.6 65.4 ± 2.5
.0062 102.8 ± 1.4 60.2 ± 3.0
.0071 101.9 ± 5.2 64.0 ± 0.9
.0079 101.8 ± 8.0 57.4 ± 2.9
.0087 94.8 ± 0.3 61.6 ± 1.9
.0096 95.3 ± 1.4 53.3 ± 1.4
.0106 87.8 ± 5.0 50.8 ± 2.1
Table S5. Reported inertial parameters for various organisms and particles.
Reported inertial parameters for various organisms and particles, as well as their 𝐸 ∗ value
assuming 𝑅𝑓 = 1.5 cm and 𝛾 = 35.6 mN/m. If mass data was unknown, 𝐸𝑢𝑏 was
calculated using the organism/particle volume, assuming a spherical geometry with
radius equal to half the characteristic size. House fly measurements were conducted in-
house using 10 dead house flies purchased from Dead Insects (deadinsects.net). The
average measured size (distance from top of head to bottom of abdomen) and mass of
these house flies are 5.5 ×10–3 m (standard deviation of 0.6 ×10–3 m) and 1.4 ×10–6 kg
(standard deviation of 0.3 ×10–6 kg), respectively.

Organism/ Characteristic Speed (m/s) Mass (kg) Density 𝑬𝒔


Particle Size (m) 3 𝐥𝐧 ( )
(kg/m ) 𝑬𝒖𝒃

pollen 3.1 ×10–5 (28) 4.01 ×10–2 (29) - 1435 (28) 11

dust 5 ×10–5 (29) 7 ×10–2 (30) - 1550 (31) 9

fruit fly 3 ×10–3 (32) 2 ×10–1 (33) 3.04 ×10–7 (34) - 6

mosquito 3 ×10–3 (35) 1.18 (36) 2 ×10–6 (35) - 1

gnat 1.68 ×10–3 (37) 3 (38) 1 ×10–4 (38) - 1

house fly 5.5 ×10–3 2.7 (39) 1.4 ×10–6 - 1

honey bee 1.1 ×10–2 (40) 7 (38) 8 ×10–5 (38) - -4

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