Communication

Soft Robotics www.advmat.de

Covalent Bonding of Thermoplastics to Rubbers

for Printable, Reel-to-Reel Processing in Soft Robotics
and Microfluidics
Jay M. Taylor, Karla Perez-Toralla, Ruby Aispuro, and Stephen A. Morin*

describe a general procedure to covalently

The lamination of mechanically stiff structures to elastic materials is preva- bond a variety of commodity plastics to
lent in biological systems and popular in many emerging synthetic systems, silicone rubbers using a simple and scal-
such as soft robotics, microfluidics, stretchable electronics, and pop-up able method. When combined with laser
printing (or other printing technologies),
assemblies. The disparate mechanical and chemical properties of these
the bonding sites can be nonlithographi-
materials have made it challenging to develop universal synthetic procedures cally patterned enabling the direct fabri-
capable of reliably adhering to these classes of materials together. Herein, cation of microfluidic systems for liquid
a simple and scalable procedure is described that is capable of covalently handling and actuation with unique
laminating a variety of commodity (“off-the-shelf ”) thermoplastic sheets to form factors and capabilities (e.g., micro-
silicone rubber films. When combined with laser printing, the nonbonding channels with built-in optical filtering,
pressure-dependent geometries, thin,
sites can be “printed” onto the thermoplastic sheets, enabling the direct
multilayer architectures, and soft actua-
fabrication of microfluidic systems for actuation and liquid handling appli- tors with hinged articulation). In this
cations. The versatility of this approach in generating thin, multifunctional communication, we overcome limita-
laminates is demonstrated through the fabrication of milliscale soft actuators tions reported in previous silicone–plastic
and grippers with hinged articulation and microfluidic channels with built-in bonding demonstrations by directly
addressing the surface chemistry required
optical filtering and pressure-dependent geometries. This method of fabrica-
for bonding, thus producing necessary
tion offers several advantages, including technical simplicity, process scal- knowledge that may be leveraged in the
ability, design versatility, and material diversity. The concepts and strategies manufacture of advanced materials and
presented herein are broadly applicable to the soft robotics, microfluidics, composites. Together, the strategies we
and advanced and additive manufacturing communities where hybrid rubber/ report provide a new approach to micro-
plastic structures are prevalent. fluidic/soft actuator design and fabrication
that uses printing technologies that are
readily scalable and easily implemented
in numerous settings (e.g., factories and
Emerging and developed fields, such as soft robotics, stretch- research laboratories) instead of traditional photolithography
able electronics, and microfluidics, require the combination of and molding procedures.
mechanically stiff reinforcing elements (e.g., plastics, papers, The combination of hard support materials with soft elastic
metals, etc.) with soft elastic structures.[1–4] The contrasting materials, chemically or physically, is prevalent in many bio-
mechanical and chemical properties of these materials have logical systems[5] and is key to many emerging technologies
made it difficult to identify universal synthetic procedures (e.g., soft robotics)[1–4]; however, synthetic techniques appli-
applicable to the scalable manufacturing of these devices. We cable to the bonding of hard materials to soft materials remain
limited due to stark differences in stiffness and elasticity and
the chemical nature of the respective material types. A proto-
J. M. Taylor, Dr. K. Perez-Toralla, Prof. S. A. Morin typical example of the bonding of hard materials to soft mate-
Department of Chemistry
University of Nebraska–Lincoln rials relies on the formation of covalent SiOSi bonds
Lincoln, NE 68588, USA that arise when oxygen plasma-activated silicon oxide and sili-
E-mail: smorin2@unl.edu cone rubbers are brought into contact.[1,2] This method, which
R. Aispuro, Prof. S. A. Morin has driven the development of microfluidics, requires that the
Nebraska Center for Materials and Nanoscience contacting interfaces have free SiOH functional groups, and
University of Nebraska–Lincoln
Lincoln, NE 68588, USA
has thus been limited to a narrow class of materials. Recently,
reactions between reactive silanes and the surface of polymers
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201705333. have extended this strategy to the bonding of certain thermo-
plastics to silicones.[6–10] Despite numerous reports of this
DOI: 10.1002/adma.201705333 method, chemical understanding of the bonding process

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remains relatively vague, and this lack of understanding has
limited the utility and versatility, in terms of applications and
materials, of this approach.
Here, we elucidated the chemistry of the bonding of (3-ami-
nopropyl)triethoxysilane (APTES) to the surfaces of oxidized
thermoplastics and silicones enabling laminants with unprece-
dented mechanical properties capable of supporting demanding
applications in soft robotics and microfluidics. We used
attenuated internal reflectance Fourier transform infrared
spectroscopy (ATR-FTIR) and T-peel adhesion tests in these inves-
tigations: (i) ATR-FTIR spectroscopy for monitoring changes in
surface-functional groups throughout the bonding process and
(ii) T-peel tests for assessing the bonding strength between a
variety of commodity plastics and silicones. In particular, we
demonstrated that the studied silicones and thermoplastics
were bonded together via strong covalent interactions, contrary
to previous reports, which attributed adhesion to hydrogen
bonding or ionic interactions.[9–11] Importantly, the thermo-
plastic/silicone bonding achieved following this approach was
stronger than the polymer matrix of the silicone rubber (failure
in mechanical tests was mainly cohesive not adhesive)—a prop-
erty that enabled the use of this chemical bonding procedure
in pneumatic actuation and microfluidics at the required oper-
ating pressures (which can exceed 1000 kPa).
Using this chemical understanding, we were able to extend
the generality of this technique to a large number of material
combinations with bonding strengths capable of supporting
applications in soft robotics and microfluidics. Specifically, fol-
lowing a rapid, nonlithographic patterning procedure, which
used laser printing, we laminated Mylar transparencies onto
silicone elastomer films enabling the fabrication of soft robotic
and microfluidic devices with unique form factors following
a workflow applicable to reel-to-reel processing for large-scale
production. This method of fabrication offers several advan-
tages, including technical simplicity, process scalability, design
versatility, and material diversity. We believe these results
will be relevant to a variety of fields, such as soft robotics and
microfluidics (as demonstrated directly herein), and also a
range of fabrication techniques including advanced and addi-
tive manufacturing (e.g., in generating hybrid silicone–plastic
structures), and pop-up fabrication strategies for creating poly­
mer-based microstructures (e.g., those incorporating thermo-
plastic sheets).[2,12]
Most commodity plastics are designed to be chemically inert
and require targeted chemical treatments to modify their sur-
faces with desired functional groups.[11,13] One popular chem-
ical modification strategy is to “siliconize” their surfaces with
reactive silanes, yielding a surface that can be further derivat-
ized with trichlorosilane vapors.[11,13,14] These vapors typically
have polar or nonpolar head groups and were used widely to
make antifouling surfaces or plastics with better biocompat-
ibility for surgical tools or implants.[13] Recently, researchers
have used this chemistry to bond siliconized surfaces to pre-
molded, oxidized silicones as a method to fabricate microflu-
idic devices.[6–10] In this process, researchers demonstrated that
amino silanes worked best and that it is the amino-terminated
end that interacts with the polymers surface[9]; however, the
chemistry of this interaction was not clearly defined. This lit-
erature suggested that the bonding mechanism proceeded
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through noncovalent interactions (i.e., hydrogen bonding and
ionic interactions), presumably because covalent bonding
between amines and organic acids typically requires additional
chemical coupling reagents,[15] which were absent in all these
demonstrations. Recently, however, amidation coupling reac-
tions involving APTES and polyethylene terephthalate (PET) in
aqueous solutions at room temperature were shown to occur
rapidly and without any additional coupling reagents.[14] In
these reactions, the primary amine group on the APTES
mole­cules reacted with the ester groups on the PET surface,
linking them together through the formation of an amide
bond. We believed this precedent provided a basis for a clear
chemical understanding of the thermoplastic/silicone bonding
procedures described in previous reports and designed our
experimental approach with it in mind.[6–10] We leverage the
experiences and capabilities gained through our previous inves-
tigations of the surface-chemical derivatization and mechanical
modification of polydimethylsiloxane (PDMS) surfaces in the
controlled assembly and rational manipulation of liquids and
solids.[16] We also drew on our experience in the development
of nontraditional microfluidic fabrication strategies using sili-
cone rubbers.[17]
We chose to use silicone rubbers (mainly PDMS) and com-
modity polymers in the investigations presented because each
offers unique advantages: silicone rubbers represent a diverse
class of elastomeric polymers that come in many formulations
with mechanical properties that can be easily tuned for tar-
geted applications in microfluidic and soft robotic devices[1,3];
commodity thermoplastics are easy to process, widely avail-
able, chemically inert, transparent, and inexpensive.[11,13] Fur-
thermore, these thermoplastics are also processable following
standard reel-to-reel manufacturing techniques. For lab-scale
demonstrations of patterned plastic/silicone bonding, we lever-
aged standard laser printing, which is directly compatible with
commercial PET (Mylar) transparencies. Though other printing
methods (e.g., screen printing and contact printing)[18] would
also work, the quick, precise, and CAD-friendly process of laser
printing was invaluable to the reported demonstrations. We
focused on microfluidics and soft robotic applications, herein,
because the designs and functions offered by these technolo-
gies have use in many areas including chemical synthesis and
analytics, medical diagnostics, and the manipulation of deli-
cate/hard to handle materials.[1,3]
We used a materials testing system to perform T-peel tests
to determine the bonding performance of different commodity
polymers and different bonding procedures. We oxidized the
polymer surfaces using two different methods: O2 plasma, which
is the most common procedure, and ultraviolet-ozone (UVO,
generated by a mercury arc lamp with deep UV wavelengths,
λ = 185 and 254 nm), which is more convenient and scalable.
The substrates were then submersed in a 1% aqueous APTES
solution.[14] In a typical bonding process, we oxidized the ther-
moplastic under UVO or plasma oxidation and then submersed
the plastic in an APTES solution for 20 min. We then put the
treated plastic into conformal contact with an oxidized PDMS
film, and then we mildly heated the structure to help drive the
condensation reaction resulting in bonding of the two pieces
(Figure 1A–F). We tested several different polymers comparing
bonding performance for the two oxidation methods used and
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Figure 1. Lamination procedure and surface spectroscopy. A–C) The
commodity polymer was oxidized with either O2 plasma or UVO and then
immersed into a solution of APTES to aminate the plastic. D) PDMS was
also oxidized. E) The two materials were combined and heated in an oven
bonding the plastic to the silicone rubber. G) ATR-FTIR spectra of the
polymer throughout the bonding process, with the corresponding peaks
highlighted by symbols defined in the provided table. A spectrum for neat
APTES was included for reference.
found that UVO was broadly applicable to all plastics tested
(Figure S1, Supporting Information), including those where
plasma was ineffective (e.g., polystyrene and PET) and that
overall UVO consistently provided higher average peel tough-
ness values (i.e., in five out of the eight cases, the difference in
peel toughness was significant at a 95% confidence, Figure S1D
in the Supporting Information). Generally, failure for the UVO-
treated polymers was cohesive, occurring within the PDMS
layer and not at the adhesive interface, indicating that the
bonding was generally not the limiting factor in the mechanical
performance of the laminated structures. We found that adhe-
sion was weak and failed for all plastics that were not treated
with APTES following oxidation and that peel toughness was
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an order of magnitude lower when liquid silicone prepolymer
was cross-linked in contact with the plastic films (Figure S2
in the Supporting Information). We attributed the enhanced
bonding of UVO (in terms of strength and material diversity) to
the cleavage of the CC backbone associated with UVO, in par-
ticular the λ = 185 nm line, leading to surfaces with higher den-
sities of surface carboxylic acid and ester groups as compared
to plasma treatment—a characteristic critical to the bonding
chemistry described below. These results are consistent with
multiple reports on the chemical effects of UVO on commodity
polymers and the expected functional groups.[19]
Using UVO as the method of oxidation, we tracked the
bonding process using ATR-FTIR in the wavenumber range of
2000 to 500 cm−1 on a polyethylene (PE) substrate (Figure 1G).
We used PE substrates because PE has a simple IR spectrum,
which made it easy to track the surface-chemical changes asso-
ciated with the bonding process (i.e., the appearance of amines,
amides, etc. in the spectra). The ATR-FTIR spectrum of native
polyethylene has two doublets representing CH bends and
stretches (Figure 1G; black trace). Following oxidation, a third
peak (between 1740 and 1700 cm−1), which corresponded to
a carbonyl (CO) stretch, was present (Figure 1G, red trace).
We viewed this peak as evidence for the formation of surface
acids, esters, or ketones, consistent with the functional groups
expected after oxidation.[19] We treated the surface with APTES
and observed three additional stretches: one peak consistent
with SiOR stretch modes (centered at 1050 cm−1), and
two indicative of amide stretches and bends (peaks between
1630 and 1550 cm−1), referred to as amide I and amide II bands
(Figure 1G; blue trace). Following treatment with APTES, the
thermoplastics have surface triethoxy groups/silanol groups
capable of bonding with surface silanol groups on oxidized
silicones (Figure 1E,F), which were observed in a separate
ATR-FTIR study and that were expected to be present based on
previous investigations (Figure S3 in the Supporting Informa-
tion).[1] We believe these spectroscopic data indicate that the
bonding process proceeded through amide bond formation and
emphasize that these understandings, namely the critical role
of UVO-induced carbonyl production (which yielded organic
acids, ketones, and esters for reaction with the primary amines
of the APTES linker as discussed above for PET),[14] make this
technique general to a wider range of polymers while simulta-
neously improving the reliability of the bonding performance
in terms of strength and reproducibility (Figure S1 in the
Supporting Information). In previous reports, such perfor-
mance metrics were a limitation for practical use of this
bonding strategy.[6–10] Moreover, the ability to access com-
modity polymers, including those directly compatible with
laser printers, expands the range of potential applications and
processing options.
As a simple, but powerful, application of these expanded
capabilities, we nonlithographically patterned fluidic pathways
onto transparency films, which come as prepackaged PET
sheets, by passing them through a standard office laser printer
after a cleaning step and prior to oxidation (Figure 2A–C).
The toner from the laser printer masked areas of the PET
surface from reacting with UVO and APTES and thus pre-
vented bonding to PDMS in desired regions. When we passed
air through the nonbonded region of the laminated films, the
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Figure 2.  Soft robotic actuators. A,B) Schematic of soft actuator fabrica-
tion where a printed design was bonded to an Ecoflex film using the
described bonding procedure. C) Schematic illustrating actuation that
occurred when the chamber of the device was pressurized with air.
D–F) Optical images of a serpentine actuator, demonstrating a 2D to 3D
transformation when pressure was increased from 0 to 700 mbar.
G–L) Creasing the thermoplastic-controlled actuator motion: (left column)
schematic of actuator and creasing location/direction, (middle column)
optical image of the actuator at 0 mbar with annotations showing crease
location/direction, (right column) optical micrograph of the actuator at
700 mbar. M) Schematic illustration and optical image sequence (from
left to right) of a pneumatic-enabled enclosure transitioning from an
open state to a closed state. N) Schematic illustration and optical image
sequence (from left to right) of pneumatic-enabled opening of a creased
polyhedral cell. All scale bars are 1 cm.
silicone above the toner separated and formed a channel. We
could then inject different fluids (air, oil, water, etc.) into the
channel. This procedure formed the basis of our new approach
to the fabrication of microfluidic systems (for pneumatic actua-
tion and liquid handling). While previous studies were limited to
silicones with premolded channels of relatively simple designs
(straight or serpentine) due to the weaker bonding strength and
associated lower operating pressures (e.g., less than 450 kPa),
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we generated silicone–plastic bonding with mechanical dura-
bility that could access operating pressures exceeding 1000 kPa,
thus enabling the direct bonding of silicone films to plotted
transparency sheets without the need for premolding chan-
nels. To illustrate this approach, (i) we designed an array
of microfluidic systems using CAD software, (ii) printed
the designs directly onto transparency sheets (Figure 2A),
and (iii) bonded the transparency sheets to a silicone film using
the procedure described above (Figure 2B,C). We focused on
two types of microfluidic technologies: (i) pneumatic milliactu-
ators for soft robotic applications and (ii) microscale liquid han-
dling systems for lab-on-chip applications.
To begin, we explored this bonding approach in the fabri-
cation of soft robotic actuators, which are particularly chal-
lenging to the laminated structures (the interface is mechani-
cally deformed during actuation), that have not been previously
accessible following existing bonding schemes (e.g., those
based on plasma activation, Figure S4 in the Supporting Infor-
mation). Specifically, by bonding soft silicone rubber films
(Ecoflex, Young's Modulus of 0.26 MPa) to transparency sheets
plotted with unique channel designs, we could rapidly generate
actuators of different geometries and motions. When pressur-
ized with air using pneumatic lines, a pocket of air would form
above the plotted design and eventually, with increasing pres-
sure and inflation, bend the underlying substrate. We used this
concept to fabricate a variety of soft robotic actuators (Figure 2
and Figure S5 in the Supporting Information). These actuators
function following a mechanism that is essentially the same
as the widely investigated “pnue-net” actuators—a strain-lim-
iting interface between an elastic layer and a support layer that
together with the channel geometry determines the motion of
actuation—but our approach does not require molding, liquid
prepolymers, or the associated tools/materials, which consider-
ably simplify the process of making soft actuators. Instead the
described method relied on the strong adhesion between the
oxidized silicone and the treated transparency sheet.
This method also allows channels with dimensions < 1 mm
in size to be readily produced, reducing the footprint of these
devices down to the millimeter to centimeter scale enabling
applications that require the manipulation of small objects and
allowing many actuators to be fabricated in one bonding step.
The smallest channel widths made using this approach are
500 µm, on par with the smallest reported soft actuators, made
through photolithography and replica molding,[20] but featuring
the convenience of the simplified workflow described here. We
mainly focused on designs that mimicked those common to
previously characterized soft actuators in order to demonstrate
the general applicability of the reported method, while also
exploring unique designs (Figure 2D–F; Figure S5D–S5L in the
Supporting Information). As an example, a 2 mm thick 2D ser-
pentine channel, when pressurized, folded up on itself creating
a 3D enclosure (Figure 2D–F; analogous designs of less thick-
ness did not, Figure S5K in the Supporting Information).
We could also control movement of these soft actuators by
creasing the underlying thermoplastic to create favorable “bend”
sites (i.e., articulation sites), which is unique to this method of
fabrication (Figure 2G–N). These bend sites weaken the under-
lying polymer, allowing further control over the direction and
the degree of curvature of the actuation (Figure 2G–L; Video S1
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in the Supporting Information). For example, by creasing a
linear actuator orthogonal to the channel axis, we decreased
the radius of curvature possible in the pressurized state relative
to that of the unmodified actuator (Figure 2G,H). Further, by
creasing the actuator at a +45° or −45° angle, we could cause
it to bend to the right or to the left (Figure 2I,J). We could also
compound this angled creasing to obtain actuation that looped
around to the left or to the right, depending on which direction
was creased first (Figure 2K,L). To further elaborate the capabil-
ities of articulation provided by creasing, we fabricated pop-up
enclosures and polyhedral cells (which through combination
could yield extended structures)[21] (Figure 2M,N). The ability to
transform planar polymer sheets to 3D structures has attracted
recent attention for its potential applications in assembly, pack-
aging, and bioanalytical devices.[22]
We leveraged the articulation of creasing in the develop-
ment of milliscale soft grippers (Figure 3A–E; Figure S6 in the
Supporting Information). When pressurized, the three arms
Figure 3. Milliscale soft grippers. A) Grippers designs were printed,
B) bonded to an Ecoflex film, C) cut out, D) equipped with pneumatic
lines, and E) creased to introduce articulation. F,G) Photos of the actua-
tion of noncreased grippers (left column, edge-on views; right column,
bottom views; 5 mm scale bars). H,I) Photos of the actuation of the
creased grippers (left column, edge-on views; right column, bottom
views; 5 mm scale bar). J) Manipulation of a flower, and K) manipulation
of a 5 mm diameter nut using the creased soft gripper from panel H
(10 mm scale bar).
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of the gripper would bend but not close (Figure 3F,G); when
we creased the “fingers” of the gripper, it closed completely
(Figure 3H,I; Video S2, Supporting Information), imbibing it
with functionality ideal for the manipulation of small and deli-
cate objects (Figure 3J,K; Videos S3 and S4 in the Supporting
Information). We demonstrated the versatility of these gripers
by manipulating a small flower (Figure 3J; Video S3, Sup-
porting Information) and by picking up and placing a 5 mm
nut in a vial (Figure 3K; Video S4 in the Supporting Informa-
tion). These demonstrations illustrate some of the unique
advantages of articulated soft robotic grippers which are easily
accessible following the reported fabrication scheme.
To demonstrate liquid handling and fabrication capabili-
ties beyond that previously reported in laminants of this type
(again because of inadequate bonding strengths), we explored
a variety of microfluidic mixers (Figure 4D) and droplet gen-
erators (Figure 4E–G,I,J; Figure S7 and Videos S5 and S6, Sup-
porting Information), which were readily operated using con-
ventional syringe pumps. To fabricate these devices, we printed
our microfluidic design onto a transparency sheet (Figure 4A),
treated it using UVO, followed by APTES (Figure 4B), and then
placed the treated sheet into conformal contact with an oxidized
silicone film (Figure 4C). There are two unique characteristics
of these devices: (i) the channel height increases as a func-
tion of the width of the channel and pressure applied, where
pressure was proportional to flow rate (Figure S8, Supporting
Information), and (ii) the bottom surface of the channels can
be created using colored ink on the transparent PET substrates,
and this feature was easily integrated into the device design
(Figure S9 in the Supporting Information). Using the geom-
etry–pressure relationship of the channels, we demonstrated
“confinement-based” droplet generation in devices that gradu-
ally increased in height, where this characteristic was easily
achieved following the reported fabrication strategy relative to
traditional methods (Figure 4E; Video S5 in the Supporting
Information).[23] We used coloration to fabricate channels with
“built-in” optical filtering functionality useful to the analysis of
colored droplets (Figure 4F–H). Specifically, we tracked a pair of
droplets (one blue, one red) through the device, observing that
the optical signature of a droplet significantly decreased when it
passed through the channel segment of matching color, while it
remained high when it passed through segments of the oppo-
site color (Figure 4G,H; Figure S7 and Video S6 in the Sup-
porting Information). Simple image analysis of these segments
shows the functionality of in-channel optical filtering and could
simplify the application of droplet-based analytics when only
basic imaging systems are available. We further demonstrated
this capability by printing channel with a series of segments
of increasing red intensity, which acted to filter the optical
signal from droplets of varying red dye concentrations, essen-
tially allowing one to print microfluidic devices with “built-in”
calibration filters, directly (Figure 4I–K). The ability to use laser
printing to fabricate these devices allows for rapid prototyping
of new and modified geometries in a time frame of about an
hour, which is much faster than traditional photolithography-
based microfluidic fabrication, which could take upward of two
weeks to fabricate a new geometry (i.e., time to design and plot
a new mask and to fabricate the device using standard photo-
lithography and molding procedures). Furthermore, the use
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Figure 4.  Laser printing of microfluidic devices. A) The trace of a fluidic
channel was printed on a transparency film, B) bonded to silicone using
the method described herein, C) and liquid was flowed within the device,
where toner masked bonding along the channel. D) Perspective image
of a microfluidic mixer with a bulging reservoir near the outlet at right.
E) Top down view of a droplet generator, where droplets were formed as the
liquid expanded into an oil reservoir at right. F) A double T-junction droplet
generator device created alternating red and blue droplets. H) Expansions
of the area indicated in panel F where two droplets were tracked as they
moved through the device. I) Gray scale image analysis of the droplets
performed in the regions indicated for each time point in panel H.
J) Optical image of a T-junction droplet generator device with a “built-in”
calibration filter. K) Expanded images of the calibration zone showing drop-
lets of increasing concentration of Red Dye 40 pass through the device.
L) Gray scale image analysis of the droplets was performed, and a threshold
of 0.4 was set to distinguish droplets in each region. The 5 × 10−3 m
droplet exceeded the threshold in regions I and II, the 10 × 10−3 m droplet
exceeded the threshold in regions I, II, and III, and the 25 × 10−3 m droplet
exceeded the threshold in all four regions. All scale bars are 5 mm.
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of transparencies as backing coupled with the ability to pro-
cess many devices at one time made them mechanically flex-
ible, durable (the devices are not made of brittle materials and
can thus withstand blunt forces and bend without failure), and
disposable (the commodity substrates are inexpensive). The
narrowest channel width that we printed was 150 µm trans-
lating to a feature density of 60 features per square centimeter,
illustrating a limitation of the laser printing process; however,
we believe the technique reported could be applied to much
smaller channels when implemented using high-resolution
printing technologies (e.g., precision laser photoplotting).
In addition to laser printing, we could fabricate channels
using ink from a marker as a mask. Though printed channels
can be more precise and include intricate geometries that cannot
be easily written by hand, writing channels manually is very
simple and can complement printed designs (Figure 5A–D),
and it can be used for plastics that are too thick or otherwise
not compatible with standard printers. Here, we demonstrated
“on-the-fly” editing using a single microfluidic template and a
marker, fabricating devices with four distinct channel layouts
(many other layouts are possible with this template). Specifically,
we connected different microfluidic modules to make a standard
serpentine design (Figure 5E), another that weaved through
three different colored channels to take advantage of optical
filtering (Figure 5F), and a third and fourth to generate drop-
lets that ran through designated paths (Figure 5G,H; Video S7
in the Supporting Information). This templating approach to
microfluidic designs could be an option for teaching/research
labs who require a simple way to explore/instruct on microflu-
idics in a low-cost environment, without heavily investing in
photolithographic equipment (e.g., flood lamps, photoresists,
spin coaters, mask aligners, etc.). We could also fabricate devices
entirely from hand-drawn channels (Figure 5I), and we could
leverage the ability of duplex printing to fabricate multilayered
microfluidic devices of interwoven channels (Figure 5J–L).
We have demonstrated an approach to the fabrication of
pneumatic and liquid-based microfluidic technologies that have
several advantages over traditional fabrication methods: the
procedure is (i) low cost and scalable to reel-to-reel processing,
(ii) iterative and amicable to rapid prototyping, (iii) and intui-
tive and readily applicable to the fabrication of new variants of
soft robotic and fluidic technologies. This method takes advan-
tage of UVO oxidation and laser printing using commodity
“off-the-shelf” plastics and silicones, which are affordable and
available in large quantities. The use of laser printing allows
a new channel to be designed, printed, and bonded in a time
frame of about an hour. We have shown the unique ability to
print the channel in any color, which can mask droplets con-
taining dyes (or by extension fluorophores) for sorting appli-
cations and be used to determine the concentration of these
dyes. Further, the ability to crease the substrates provided a
simple method to control the motion of soft actuators enabling,
in this work, the manipulation of delicate, small objects. This
strategy represents a new approach to soft actuator/robot fab-
rication that includes a diverse set of commodity polymers and
that circumvents the molding procedures typical to traditional
modes of fabrication. A critical component of this success was
the use of UVO instead of O2 plasma, offering several advan-
tages, including technical simplicity, process scalability, design
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.

Acknowledgements
The authors thank the Department of Chemistry and the Nebraska
Center for Materials and Nano Science (NCMN), at the University of
Nebraska–Lincoln, and the University of Nebraska–Lincoln for start-up
funds. S.A.M. thanks 3M for support through a Non-Tenured Faculty
Award. This work was supported by the National Science Foundation
under Grant No. 1555356. This research was performed in part at the
Nebraska Nanoscale Facility: National Nanotechnology Coordinated
Infrastructure and the Nebraska Center for Materials and Nanoscience,
which are supported by the National Science Foundation under Award
ECCS: 1542182, and the Nebraska Research Initiative.

Conflict of Interest
The authors declare no conflict of interest.

Keywords
actuation, laminates, microfluidics, silicone bonding, soft robotics

Received: September 15, 2017

Revised: November 3, 2017
Published online:

[1] a) G. M. Whitesides, Nature 2006, 442, 368; b) D. C. Duffy,

Figure 5.  “On-the-fly” microfluidics via manual editing. A) Microfluidic
template was printed, B) treated, C) a marker was used to customize
the flow path of the template, and D) then bonded to a silicone film.
E–H) Representative microfluidic devices fabricated using this approach.
In panel E, the location of the manual edit was indicated using black
arrows. I) A device fabricated entirely from a manually drawn channel
path. J–L) Duplex printing enabled multilayered device fabrication:
J) schematic, M) side view of the device as dye was flowed through it,
and L) a top down image of the same device as in panel M (black arrows
indicate direction of fluid flow). All scale bars are 5 mm.
versatility, and material diversity. We believe this fabrication
strategy and the demonstrated applications will be of interest to
not only those studying soft robotics and microfluidics, but also
to those interested in manufacturing/fabrication techniques
involving the combination of hard material components with
soft elastic polymers (e.g., additive manufacturing, rubber/
plastic hybrid structures, and pop-up assembly).[14,24]
Experimental Section
See the Supporting Information for further details.
J. C. McDonald, O. J. A. Schueller, G. M. Whitesides, Anal. Chem.
1998, 70, 4974.
[2] a) H. Q. Jiang, D. Y. Khang, J. Z. Song, Y. G. Sun, Y. G. Huang,
J. A. Rogers, Proc. Natl. Acad. Sci. USA 2007, 104, 15607;
b) J. A. Rogers, T. Someya, Y. G. Huang, Science 2010, 327, 1603;
c) S. Xu, Z. Yan, K. I. Jang, W. Huang, H. R. Fu, J. Kim, Z. Wei,
M. Flavin, J. McCracken, R. Wang, A. Badea, Y. Liu, D. Q. Xiao,
G. Y. Zhou, J. Lee, H. U. Chung, H. Y. Cheng, W. Ren, A. Banks,
X. L. Li, U. Paik, R. G. Nuzzo, Y. G. Huang, Y. H. Zhang, J. A. Rogers,
Science 2015, 347, 154.
[3] a) R. F. Shepherd, F. Ilievski, W. Choi, S. A. Morin, A. A. Stokes,
A. D. Mazzeo, X. Chen, M. Wang, G. M. Whitesides, Proc. Natl.
Acad. Sci. USA 2011, 108, 20400; b) P. Polygerinos, N. Correll,
S. A. Morin, B. Mosadegh, C. D. Onal, K. Petersen, M. Cianchetti,
M. T. Tolley, R. F. Shepherd, Adv. Eng. Mater. 2017, 1700016,
https://doi.org/10.1002/adem.201700016.
[4] R. V. Martinez, C. R. Fish, X. Chen, G. M. Whitesides, Adv. Funct.
Mater. 2012, 22, 1376.
[5] a) J. W. C. Dunlop, P. Fratzl, Annu. Rev. Mater. Res. 2010, 40, 1;
b) A. Miserez, T. Schneberk, C. J. Sun, F. W. Zok, J. H. Waite, Sci-
ence 2008, 319, 1816; c) J. D. Fox, J. R. Capadona, P. D. Marasco,
S. J. Rowan, J. Am. Chem. Soc. 2013, 135, 5167.
[6] L. Tang, N. Y. Lee, Lab Chip 2010, 10, 1274.
[7] K. Liu, P. Gu, K. Hamaker, Z. H. Fan, J. Colloid Interface Sci. 2012,
365, 289.
[8] a) V. Sunkara, D. K. Park, H. Hwang, R. Chantiwas, S. A. Soper,
Y. K. Cho, Lab Chip 2011, 11, 962; b) V. Sunkara, D. K. Park,
Y. K. Cho, RSC Adv. 2012, 2, 9066.
[9] V. Sunkara, Y. K. Cho, ACS Appl. Mater. Interfaces 2012, 4, 6537.

Adv. Mater. 2018, 1705333 1705333  (7 of 8) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
[10] W. Wu, J. Wu, J. H. Kim, N. Y. Lee, Lab Chip 2015, 15, 2819.
[11] a) L. N. Bui, M. Thompson, N. B. Mckeown, A. D. Romaschin,
P. G. Kalman, Analyst 1993, 118, 463; b) J. A. Howarter,
J. P. Youngblood, Macromolecules 2007, 40, 1128.
[12] S. Felton, M. Tolley, E. Demaine, D. Rus, R. Wood, Science 2014,
345, 644.
[13] J. P. Deng, L. F. Wang, L. Y. Liu, W. T. Yang, Prog. Polym. Sci. 2009,
34, 156.
[14] G. A. Castillo, L. Wilson, K. Efimenko, M. D. Dickey, C. B. Gorman,
J. Genzer, ACS Appl. Mater. Interfaces 2016, 8, 35641.
[15] G. T. Hermanson, Bioconjugate Techniques (Ed: J. Audet), Elsevier/
AP, Waltham, MA, USA 2013, pp. 259–264.
[16] a) J. J. Bowen, J. M. Taylor, C. P. Jurich, S. A. Morin, Adv. Funct.
Mater. 2015, 25, 5520; b) M. A. Rose, J. M. Taylor, S. A. Morin,
Chem. Mater. 2016, 28, 8513; c) T. P. Vinod, J. M. Taylor, A. Konda,
S. A. Morin, Small 2017, 13.
[17] a) A. Konda, J. M. Taylor, M. A. Stoller, S. A. Morin, Lab Chip 2015,
15, 2009; b) M. A. Stoller, A. Konda, M. A. Kottwitz, S. A. Morin,
RSC Adv. 2015, 5, 97934.
[18] a) R. O. Kadara, N. Jenkinson, C. E. Banks, Electrochem. Commun.
2009, 11, 1377; b) T. Kaufmann, B. J. Ravoo, Polym. Chem. 2010,
1, 371; c) D. M. Tsai, K. W. Lin, J. M. Zen, H. Y. Chen, R. H. Hong,
Electrophoresis 2005, 26, 3007; d) Y. N. Xia, G. M. Whitesides,
Angew. Chem., Int. Ed. 1998, 37, 550; e) J. A. Rogers, Z. Bao,
K. Baldwin, A. Dodabalapur, B. Crone, V. R. Raju, V. Kuck, H. Katz,
Adv. Mater. 2018, 1705333 1705333  (8 of 8)
www.advmat.de
K. Amundson, J. Ewing, P. Drzaic, Proc. Natl. Acad. Sci. USA 2001,
98, 4835.
[19] a) L. F. Macmanus, M. J. Walzak, N. S. McIntyre, J. Polym. Sci., Part
A: Polym. Chem. 1999, 37, 2489; b) D. O. H. Teare, C. Ton-That,
R. H. Bradley, Surf. Interface Anal. 2000, 29, 276; c) I. Mathieson,
R. H. Bradley, Int. J. Adhes. Adhes. 1996, 16, 29; d) C. Ton-That,
D. O. H. Teare, P. A. Campbell, R. H. Bradley, Surf. Sci. 1999, 433, 278.
[20] a) S. Konishi, S. Shimomura, S. Tajima, Y. Tabata, Microsyst.
Nanoeng. 2016, 2, 15048; b) L. Hines, K. Petersen, G. Z. Lum,
M. Sitti, Adv. Mater. 2017, 29, 1603483.
[21] J. T. B. Overvelde, T. A. de Jong, Y. Shevchenko, S. A. Becerra,
G. M. Whitesides, J. C. Weaver, C. Hoberman, K. Bertoldi, Nat.
Commun. 2016, 7, 10929.
[22] a) X. Y. Guo, H. Li, B. Y. Ahn, E. B. Duoss, K. J. Hsia, J. A. Lewis,
R. G. Nuzzo, Proc. Natl. Acad. Sci. USA 2009, 106, 20149;
b) E. Hawkes, B. An, N. M. Benbernou, H. Tanaka, S. Kim,
E. D. Demaine, D. Rus, R. J. Wood, Proc. Natl. Acad. Sci. USA 2010,
107, 12441; c) Y. Liu, J. K. Boyles, J. Genzer, M. D. Dickey, Soft
Matter 2012, 8, 1764; d) Y. Liu, J. Genzer, M. D. Dickey, Prog. Polym.
Sci. 2016, 52, 79.
[23] R. Dangla, S. C. Kayi, C. N. Baroud, Proc. Natl. Acad. Sci. USA 2013,
110, 853.
[24] a) J. A. Lewis, G. M. Gratson, Mater. Today 2004, 7, 32;
b) A. S. Gladman, E. A. Matsumoto, R. G. Nuzzo, L. Mahadevan,
J. A. Lewis, Nat. Mater. 2016, 15, 413.
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