The following relates to the fluid flow processing arts, mass transport arts, electro-osmotic, electrophoresis, and electrokinetic device arts, and related arts.
Electrokinetics relates to electrically driven mass transport, and is of technological importance in various forms. One electrokinetic process is the electrically driven flow of a fluid with respect to a solid surface, referred to as electro-osmosis. Another electrokinetic process is the electrically driven transport of particles in fluids, referred to as electrophoresis. A necessary condition of electrokinetics is separation of electric charges in space. Once separated, these charges can be carried by an applied electric field, thus producing electro-osmosis or electrophoresis.
A known approach for achieving charge separation at a solid-fluid interface is through dissociation of molecular groups and the formation of electric double layers. Another approach is to separate charges by the applied electric field, but this is applicable only to highly polarizable solid components. In an isotropic electrolyte fluid, the solid component mediates separation of charges, and the fluid supplies counterions to complete the double layer buildup.
These approaches have substantial disadvantages. For example, to achieve electrophoresis by these mechanisms the transported particles must be polarizable, e.g. an ionic compound such as a salt that can be separated into cation and anion components. This limits the range of particles that can be subjected to electrophoresis by these mechanisms in terms of surface charge magnitude, polarizability, shape asymmetry, and other properties.
In some illustrative embodiments, a transport device comprises: a fluid cell comprising parallel substrates; an anisotropic electrolyte disposed in the fluid cell; and electrodes configured to apply an AC electric field to the anisotropic electrolyte disposed in the fluid cell. A substrate of the fluid cell includes a pattern that induces a director distortion pattern in the anisotropic electrolyte disposed in the fluid cell. The director distortion pattern has a gradient configured to induce electrokinetic flow of the anisotropic electrolyte in the fluid cell in response to the AC electric field applied by the electrodes. Cargo, such as particles, gas bubbles, or fluid, is dispersed in the anisotropic electrolyte and transported in the fluid cell by the induced electrokinetic flow of the anisotropic electrolyte. The induced electrokinetic flow may be linear, curvilinear, or circular so as to induce mixing, depending on the director pattern. The director pattern might be non-singular (defect-free) or may contain defects such as disclinations that produce pumping effects and can trap cargo at a core of the disclination.
In some illustrative embodiments, a transport method is disclosed. A director distortion pattern is induced in an anisotropic electrolyte disposed in a fluid cell. The induced director distortion pattern has a gradient configured to induce electrokinetic flow of the anisotropic electrolyte. An AC electric field is applied to the anisotropic electrolyte disposed in the fluid cell whereby electrokinetic flow of the anisotropic electrolyte is induced. The director distortion pattern may be induced by forming a pattern on a substrate of the fluid cell, the pattern inducing the director distortion pattern. In some illustrative embodiments, the pattern on the substrate is formed by performing patterned photoalignment of a photosensitive layer disposed on the substrate using a plasmonic mask with nanoslits.
Disclosed herein are versatile approaches to generating electrokinetic effects by using a liquid crystal (LC) with surface-patterned molecular orientation as an electrolyte. The patterned molecular orientation may be described by spatial variations of the director {circumflex over (n)}(r). By producing a desired pattern of {circumflex over (n)}(r), for example by photo-alignment of substrates bounding a LC cell, a desired electrokinetic flow path can be defined. The substrate-imposed pattern imposes director distortions extending a substantial distance into the LC bulk and possibly extending through the entire LC bulk, because of the elastic nature of the LC orientational order. As disclosed herein, in the presence of a uniform alternating current (ac) electric field, the spatially varying molecular orientation produces space charge that triggers streaming flows of the LC. The ensuing electrokinetics can transport solid, fluid, and even gaseous inclusions along a predesigned trajectory. The patterned LC electrolyte represents an active form of matter in which the energy input that drives the system out of equilibrium is localized at the gradients of the orientation order of the LC medium rather than at the particles embedded in the LC medium. Since the source of activity is rooted in the properties of the LC medium, the approach removes many limitations imposed by isotropic electrolytes on the properties of electrokinetically active interfaces and particles in them (such as the magnitude of surface charge, polarizability, shape asymmetry, etc.).
The disclosed electrokinetic approach is referred to herein as substrate-controlled liquid-crystal-enabled electrokinetics (LCEK), and is explained in greater detail as follows. LCs are anisotropic electrolytes, in that the electric conductivity σ∥ measured along the average molecular orientation {circumflex over (n)} is usually higher than the conductivity σ⊥ measured along the direction perpendicular to {circumflex over (n)}. This anisotropy gives rise to the Carr-Helfrich effect of destabilization of a uniformly aligned LC cell, {circumflex over (n)}(r)=const. In the disclosed approach for achieving an electrokinetic effect, the starting point is a LC with a predistorted director pattern {circumflex over (n)}(r)≠const imposed by designed LC cell substrates. The applied electric field E moves charges of opposite signs along the curved director lines defined by the imposed pattern {circumflex over (n)}(r)≠const, accumulating the charges of different charge polarities in different regions of the LC bulk. The gradients of the director thus lead to the electric field E creating a nonvanishing volume density of charges ρ(r). This volume density of charges depends on the conductivity, and on the dielectric permittivity of the LC and its anisotropy. The electric field acts on the space charge ρ(r), creating flows of the LC. These flows carry particles dispersed in the LC, since the separation of charges occurs in the bulk of the LC medium rather than at (or near) the particle's surface, as in the case of existing electrokinetic approaches that employ electric double layers around particles in isotropic electrolytes and charges separated by director distortions near the colloidal particles placed in an otherwise uniform LC.
In illustrative embodiments, the bulk director distortions operating to provide substrate-controlled LCEK are achieved through patterned photoalignment. To define the flow pattern for LCEK, the molecular orientation should change from point to point in pattern. To precisely implement the desired {circumflex over (n)}(r) pattern defining the flow, methods of surface alignment such as buffing or rubbing of the substrates with the tip of a cantilever in an atomic force microscopy setup are not practical for large-scale manufacturing. In the illustrative embodiments, a modified version of photoalignment is used, in which the cell substrates are irradiated through plasmonic masks with nanoslits. When such a mask is illuminated with nonpolarized light, the slits transmit a polarized optical field that is projected onto a photoaligning layer. The polarized optical field projected onto the photoaligning layer imposes the desired director field {circumflex over (n)}(r) at the substrate and in the adjacent LC.
With reference to
Experiments employing the microfluidic chamber 10 of
To form the patterned alignment layers, the photosensitive material Brilliant Yellow (BY) (from Sigma-Aldrich) was used without further purification. BY was mixed with N,N-dimethylformamide (DMF) solvent at 1 wt % concentration. In order to improve the stability of BY, the reactive mesogen RM257 was mixed with DMF at the concentration 0.2 wt % and then mixed with the solution of BY in DMF (1 wt %) in the ratio 1:1. After vortexing for 1 min, the solution was spin coated onto two cleaned glass plates, including both the bare glass plate 12 and the glass plate 14 with the two patterned ITO electrodes 16, 18 separated by the gap L of 10 mm. The glass plates 12, 14 were baked at 95° C. for 30 min. The two glass plates 12, 14 were assembled in a parallel fashion with a gap of 50 μm between them, set by spherical silica spacers (not shown in
With reference to
Various experiments were performed on microfluidic chambers 10 assembled as just described. The testing apparatuses are described next.
The velocities of the electro-osmotic flows were measured by videomicroscopy using a Nikon Eclipse E600 microscope with a motorized stage (Prior Scientific) equipped with a CARV confocal imager (BD Biosciences) and Photometrics Cascade 650 video camera. The fluorescent illumination system X-Cite 120 was used with the excitation wavelength of 480 nm and emission wavelength of 535 nm. The LC is doped with a small amount (˜0.01 wt %) of tracers, representing fluorescent polystyrene spheres (Bangs Laboratories) of diameter 2R=0.2 μm. The small size of the tracers allows for elimination of the potential influence of dielectrophoretic effects. The microscope was focused at the middle plane of the cell. The tracers caused no visible distortions of the director and are practically nonpolarizable. The fluorescent signal of tracers was recorded as a TIFF image with a typical exposure time Δτ=325 ms. The flow trajectories were established using the software package MetaMorph (Molecular Devices) to superimpose over 1500 images to render a single composite picture. The experimental flow velocity fields were obtained using the microparticle imaging velocimetry (μPIV) software PIVLAB operated in MATLAB version R2010b which correlates the position of tracers in consecutive images.
The director fields produced by photopatterning were established using a polarizing microscope (Nikon E600) equipped with the Cambridge Research Abrio LC-PolScope package. This system uses monochromatic illumination at 546 nm and maps the optical retardance and orientation of the optical axis.
Some microfluidic devices (i.e. microfluidic chambers) were fabricated for micromixing. In these devices, a photoresist, SU-8 2025 (MicroChem) was spin coated onto the cleaned glass substrates at 500 rpm for 30 s and 1500 rpm for 30 sec to create a film with the thickness 50 μm that will be the depth of the channels. After photoresist coating, the substrates were prebaked at 65° C. for 2 min and then at 95° C. for 8 min. The inlets of the devices have a width of 500 μm and the main channel has a width of 1 mm. The angle between the inlets is 40°. This microchannel design is patterned in the SU-8 films by using a maskless photopatterning system with the digital micromirror devices as dynamic masks. After UV exposure for 30 sec, the substrates were postbaked at 65° C. for 1 min and at 95° C. for 5 min. After development in SU-8 developer (MicroChem) for 5 min, the substrates were rinsed with isopropanol for 1 min to form microchannels. The substrate with the microfluidic channel was spin coated with BY-RM257 mixture at 1500 rpm for 30 sec and baked at 95° C. for 30 min. Two holes were drilled in the substrate with a microabrasive sand blaster (Problast by Vaniman Manufacturing), in order to provide the inlets for the fluids. This substrate was then covered by another glass substrate with patterned ITO electrodes and also coated with the same photoalignment material. The mixing microfluidic chamber was photoaligned as described with reference to
To characterize the micromixing efficiency, an approach was used that is based on the standard deviation in the intensity of optical microscopy images of the mixing chamber. The comparison was made for two different modes of mixing, by passive diffusion and by LCEK flows. The time development of mixing was tracked by taking 3000 images by videomicroscopy. Each image contains N=653×492=321,276 pixels of variable intensity Ii, as determined by fluorescent particles. The value of Ii is dimensionless, being normalized by the maximum possible intensity Imax. In addition to the intensity of each pixel Ii, the average intensity of each image,
was also calculated. The standard deviation is defined as
In the unmixed state, the mixing pad was divided into two parts of equal area, one with the maximum fluorescent intensity Imax=1 and the other with the minimum intensity Imin=0; the average intensity is Iav=0.5, so that:
In the completely mixed state, the fluorescent intensity Ii=Iave, so that
Numerical simulations of the electro-osmotic flows were also performed as follows. A transport model was developed to simulate electro-osmotic flows for different photopatterned arrays, using the Leslie-Ericksen hydrodynamics. The model includes anisotropic mobilities μij=μ⊥δij+Δμninj where the anisotropic contribution is Δμ=μ∥−μ⊥. We consider positive and negative ions of equal concentration, n0≈1019 ions·m−3. The model was solved numerically using the finite-element software package COMSOL in two dimensions, with the parameters of the nematic cell, applied field amplitude, and frequency being the same as those used in laboratory experiments, namely, E=40 mV/μm and 5 Hz.
A condition for electrokinetic motion of the LC is spatial separation of charges. In the following, the spatial charge created by a non-uniform director field in the presence of an electric field is derived using Maxwell's equations.
In the disclosed substrate-controlled LCEK, the space charge is induced by the electric field because of the preimposed director deformations. The space charge density ρ is derived in the following for the director field distorted in the xy plane, {circumflex over (n)}={cos α(x,y), sin α(x,y), 0}, where α is the angle between the director {circumflex over (n)} and the x axis. The starting point is Maxwell's equation for the magnetic field H:
Consider a low-frequency harmonic field E(t)=Ee−iωt that creates the current density J(t)=Je−iωt=σEe−iωt and the electric displacement D(t)=De−iωt=ε0εEe−iωt; here σ=σ⊥I+Δσ{circumflex over (n)}⊗{circumflex over (n)} and ε=ε⊥I+Δε{circumflex over (n)}⊗{circumflex over (n)} are, respectively, the conductivity and dielectric tensors in the laboratory frame, Δε=ε∥−ε⊥ is the dielectric anisotropy, and ⊗ is the external product of two vectors. The operation's result is a tensor with components [{circumflex over (n)}⊗{circumflex over (n)}]ij=ninj. It is assumed here that the diagonal components σ∥ and σ⊥ of the conductivity tensor and the diagonal components ε∥ and ε⊥ of the dielectric tensor are frequency independent. Equation (1) can be rewritten as
where {tilde over (σ)}=σ−iωε0ε is the effective conductivity tensor.
For low frequency
(where c is the speed of light and L is the distance between the electrodes), {tilde over (σ)}≈σ and E=−∇V, where the potential V obeys the equation div(σ∇V)=0, or:
σ⊥∇2V+Δσdiv[({circumflex over (n)}·∇V){circumflex over (n)}]=0 (3)
and thus the charge density ρ=divD reads:
Consider the external field E0 applied along the x axis and assume a weak anisotropy of conductivity, Δσ<<σ⊥. The electric field acting on the LC can be represented as E={E0+{tilde over (E)}x(x,y),{tilde over (E)}y(x,y)}, where {tilde over (E)}x(x,y) and {tilde over (E)}y(x,y) are small corrections caused by the director inhomogeneity that satisfy Equation (4). In the first perturbation order:
The electric field E creates the spatially varying charge density:
The field-induced charge density ρ is being acted upon by the applied electric field, thus creating a force density f=ρE0∝E02 that causes the flow of the LC controlled by the surface-imposed director pattern. Note that Equation (6) shows the space charge being dependent on both the conductivity anisotropy Δσ and the dielectric anisotropy Δε; either one of them or both can lead to charge separation. In the experimentally studied material, there is no dielectric anisotropy; thus in what follows, Equation (6) is used with Δε=0. This choice simplifies the analysis by eliminating the dielectric torques on the director. However, nonzero dielectric anisotropy can be used to create, enhance, or control the space charge, depending on the sign of Δε, as evident from Equation (6).
In the following, experimental results obtained using the foregoing experimental tests presented.
With reference to
in
is the triangle wave of the amplitude π/2 and period l.
In the absence of an electric field, the ions are distributed homogeneously in the sample. When the electric field is applied along the x axis, E=(E0, 0), it separates the positively and negatively charged ions along the y axis, by moving them along the “guiding rail” of the director. For example, in
The space charge is steady, as long as there are predesigned director distortions, i.e., the spatial derivatives ∂α/∂x and ∂α/∂y are nonzero.
Once the charges are separated, the periodic bulk force fx(y)=ρE0∝E02 acting on the ionic clouds causes spatially periodic LC electrokinetic flow.
The predesigned director pattern in
A principal difference between the classic electroconvection phenomena described by the Carr-Helfrich model and the electrokinetics of the disclosed LCEK is here noted. In the Carr-Helfrich effect, the LC is aligned uniformly and the director distortions appear as a result of charge separation at director fluctuations. The director distortions usually adapt a form of “anomalous” reorientation, linear rolls, and a two-dimensional array of vortices, determined by the balance of electrohydrodynamic and elastic forces. By contrast, in the LCEK approach the principal director distortions are predesigned by surface alignment even before the electric field is applied. The concrete shape of these distortions determines the patterns of charge separation and controls the electrokinetic flows when the electric field is applied.
Furthermore, the patterns in
on the distance measured along the y axis, where n=200 and ux(xi, y) is the local velocity component along the x axis, known from the experiment in
where y0=200 μm and h=50 μm is the cell thickness, is practically zero: its deviation from the total volumetric flow defineu as
is less than 1%. It can be concluded that the patterns in
In contrast, the asymmetric pattern shown in
Results for electrokinetic flows in patterned LC electrolytes with topological defects are next described. In classic linear electrokinetics, the fluid velocity u is proportional to the electric field and the resulting flows are irrotational, ∇×u=0. For practical applications such as mixing, it is desirable to trigger flows with vortices. Vortices are readily produced in the patterned LC cells, by using localized surface patterns, for example, with topological defects. The topological defects offer another degree of freedom in manipulating colloids as they can be used for entrapment and release.
Director patterns with pairs of disclinations of strength (m=½,−½) and triplets such as (m=−½,1,½) and (m=½,−1,½) are created following the general form nx=cos α(x,y), ny=sin α(x,y), where:
Here d is the distance between the cores of two neighboring defects. In all cases, the total topological charge Σi mi is zero, which allows one to smoothly embed the distorted pattern into an otherwise uniform director field. The charge (strength) m is determined by how many times the director rotates by the angle 2π when one circumnavigates the defect once. In the case of pairs, m1=−m2=½ and m3=0. In the case of triplets, m1=m3=−½ and m2=1. Equation (9) follows the principle of superposition valid for a director field in a one-constant approximation. These patterns are used to produce the pattern of slits in the photomask 34 and then are reproduced as the true director field in the assembled and photoaligned LC chambers.
The director and flow patterns are further analyzed in
Once the electric field is applied, the distorted director,
Pumping efficiency is quantified by the volumetric flow
measured in the vertical xz cross-sections of the cell for each point along the x-axis in the range |x|≤x0,
is an antisymmetric function close to zero, as seen in
The maximum velocity measured in the center of the disclination pair grows linearly with the separation d between the defects,
With reference now to
In
In terms of the produced electro-osmotic flows, the main feature of triplets is that they produce four vortices, as seen in
The (−½, 1, −½) triplet produces a flow of the “pusher” type, with the fluid moving from the central +1 defect (split into two closely located ½ disclinations) towards the two −½ disclinations at the periphery, as seen in
To verify the disclosed mechanism of patterned LCEK, numerical simulations were performed of the flows for the three-defects set shown in
Surface patterning offers broad freedom in the design of flows. For example, a two-dimensional array of topological defects is designed in the form nx=cos α(x,y), ny=sin α(x,y) where:
where dm=√{square root over (3)}md, m=0, ±1, ±2, . . . , dn=3nd, n=0, ±1, ±2, . . . ,
p=0, ±1, ±2, . . . ,
q=0, ±1, ±2, . . . , and d is the distance between the defects of strength 1 and −½. Typical values of m, n, p, and q in the photomasks were 4-5.
With reference to
In the example of
In the following, transport of solid, fluid, and gaseous “cargo” in patterned LCEK flows is considered.
With reference to
The LCEK directed by surface patterning does not impose any limitations on the properties of the “cargo”, such as separation of surface charges, polarizability or ability to distort the LC. The latter feature is especially important as compared to the effects of colloidal transport in an otherwise uniform LC cell caused by asymmetric director distortions at the surface of the particle. In particular, the polystyrene sphere transport (
The trajectory of the cargo transport by LCEK is determined by the pattern of molecular orientation. For example, in the conveyor's configurations, the solid sphere (
Micro-mixing by patterned LC-enabled electrokinetic flows is next considered. Surface-imprinted director patterns can be used to facilitate mixing. The circular director distortion is designed as:
With reference to
In the experiments of
An intriguing question about the experimental setup is how far the director distortions produced by photoalignment at the bounding substrates can propagate into the bulk of the LC. Generally, in absence of any other external aligning factors, the surface-induced alignment is replicated into the LC bulk over macroscopic distances. This is certainly true for the cells used in the here-described experiments, of thickness 50 μm. In these (and thinner) cells, the disclination lines are joining the top and bottom plates 12, 14 (see
As disclosed herein, the spatially varying director field of an LC electrolyte achieved through photo-imprinted surface alignment allows for the creation of electrokinetic flows of practically any complexity and vorticity. The flows are persistent, as their velocities are proportional to the square of the applied field, so that the driving field can be of an AC type. The transport of LC and particles dispersed in it is easily controlled by the predesigned director gradients; no mechanical parts and no external pressure gradients are needed. The flow polarity can be changed either by changing the director patterns or the electric field direction. Since the charges are separated in the bulk of electrolytic LC medium rather than at the solid-liquid interfaces, the disclosed approach eliminates the need for polarizable/charged interfaces. For example, experiments reported herein demonstrate that LCEK created by surface patterns can carry inclusions such as solid colloids, droplets of water and air bubbles even if these inclusions have no electrophoretic activity (zero charge or zero polarizability) on their own. The cross-sections of the patterned LC microfluidic chambers are not obstructed by any barriers (such as ridges, electrode posts or colloidal particles, needed in other electrokinetic devices), thus combining efficiency of flows with simplicity of design.
The disclosed approach is suitable for lab-on-the-chip and microfluidic devices. From the fundamental point of view, the described patterned LC electrolyte represents a new type of active matter in which the energy input that drives the system out of equilibrium occurs locally through orientation distortions of the medium rather than at the particles dispersed in it. This is a significant practical difference as compared to active materials with artificial or biological swimmers embedded in an otherwise inert surrounding medium such as water. The patterned LC electrolytes add a new dimension to active systems, as both the medium and the dispersed particles can be used for energy input and departure from equilibrium.
It will be appreciated that various of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. It will be further appreciated that various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims.
This application claims the benefit of U.S. Provisional Application No. 62/259,190 filed Nov. 24, 2015 and titled “LIQUID CRYSTALS WITH PATTERNED MOLECULAR ORIENTATION AS AN ELECTROLYTIC ACTIVE MEDIUM” and claims the benefit of U.S. Provisional Application No. 62/403,918 filed Oct. 4, 2016 and titled “LIQUID CRYSTALS WITH PATTERNED MOLECULAR ORIENTATION AS AN ELECTROLYTIC ACTIVE MEDIUM”. U.S. Provisional Application No. 62/259,190 filed Nov. 24, 2015 and U.S. Provisional Application No. 62/403,918 filed Oct. 4, 2016 are both hereby incorporated by reference in its entirety into the specification of this application. This invention was made with Government support under grant/contract no. DMR-1507637 and DMS-1434185 awarded by the National Science Foundation (NSF). The Government has certain rights in this invention.
Number | Name | Date | Kind |
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6897915 | Lavrentovich | May 2005 | B1 |
9146415 | Baek | Sep 2015 | B2 |
20150261023 | Lavrentovich | Sep 2015 | A1 |
20170144148 | Lavrentovich | May 2017 | A1 |
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20170144148 A1 | May 2017 | US |
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62403918 | Oct 2016 | US |