CN107640739A - Drop method self-driven over long distances on wetting gradient surface - Google Patents
Drop method self-driven over long distances on wetting gradient surface Download PDFInfo
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Abstract
The present invention discloses drop method self-driven over long distances on wetting gradient surface, gradient surface is soaked by uniform silica striped and silicon nanoneedle structure composition, wetting gradient surface of solids hydrophilic area uses static contact angle as 15.5 ° of silica, wetting gradient solid bottom is the silicon nanometer needle construction using deep reaction ion etching, the static contact angle of silicon nanoneedle is 166.0 °, angle of lag is 3.0 °, greatly widen the surface of solids and soak gradient scope up to more than 150 °, optimize the hysteresis of contact line before and after drop, the long range that fine droplet 38mm can be achieved is self-driven, and devise drop and orient self-driven a variety of mobile routes, it is novel in design, it is a kind of good innovation scheme.
Description
Technical field
The present invention relates to microfluidic control system, more particularly to drop on wetting gradient surface side self-driven over long distances
Method.
Background technology
In microfluidic system, the orientation under drop acts on without external force is self-driven, particularly in chemical analysis, biomedicine
Etc. application study enjoy domestic and international extensive concern.Drop orientation is self-driven usually require it is extraneous provide energy (active
Or passive), to overcome the intrinsic contact line of solid liquid interface to lag.The common method for breaking surface of solids wetting symmetry has：
Chemical gradient, topological structure gradient, topological structure gradient, thermograde, electromagnetic force, mechanical oscillation, pH value induction and a variety of sides
The mixing of method.In these methods, the surface of solids prepared by topological structure and chemical material inhomogeneities soaks gradient, because
It reduces extraneous function and the advantage such as easy to operation and is enjoyed extensive concern.Although chemical material wetting Gradient methods obtain
Significant progress, but the functional group on functionally gradient material (FGM) surface and wetability can be in long-term operation, because surface organic molecule moves
Move or degrade and be destroyed.So surface of solids topological structure realizes wetting gradient, chemical material wetting ladder can be preferably made up
The deficiency of degree.
Self-driven for long range drop, the surface of solids needs larger static contact angle gradient and less angle of lag.
For increase wetting gradient scope and reduce angle of lag, that has reported is achieved in that：Water delivery coating is coated by surface, realizes table
The superhydrophobic characteristic in face, the wetting gradient surface in the region from super hydrophilic to super-hydrophobic can not be but realized in the same surface of solids, because
The gradient scope of this existing wetting gradient surface of solids is no more than 120 °.And this less wetting gradient scope reduces liquid
The driving force of wetting gradient surface movement is dropped in, limits displacement, it is impossible to meet the higher demand of industry development.
In summary, for prior art the defects of, it is accordingly required in particular to which drop is self-driven over long distances on wetting gradient surface
Method, to solve the deficiencies in the prior art.
The content of the invention
For above-mentioned technological deficiency, the purpose of the present invention is：Propose drop wetting gradient surface on grow away from
From self-driven method, the wetting gradient scope (being more than 150 °) of the surface of solids is greatly broadened, reduces the angle of lag on surface.
To achieve these goals, technical scheme is as follows：
Drop self-driven method over long distances on wetting gradient surface, wetting gradient surface by uniform silica striped and
Silicon nanoneedle structure composition, static contact angle is used at the top of wetting gradient surface of solids striped as 15.5 ° of silica；Wetting ladder
Degree solid bottom is silicon nanoneedle body structure surface prepared by micromachined, and it is 166.0 ° super-hydrophobic that static contact angle, which can be achieved,
Surface, its angle of lag are not more than 3.0 °, greatly reduce the angle of lag of the surface of solids, can be real by adjusting close and distant water area ratio
Existing wetting gradient surface of the surface of solids from super hydrophilic to super-hydrophobic, moistened surface gradient scope are up to more than 150 °.
Further, the wetting gradient surface from super hydrophilic to super-hydrophobic, by adjusting hydrophobe region area ratio, in solid
The different isometric wetting zones of several wetting zones are designed on surface, and the order successively decreased according to contact angle arranges, realize from
Dissipate the wetting gradient surface of solids of formula gradual change.
Further, the wetting gradient surface of solids of discrete type gradual change, the silica width of each wetting zones can be 30
Between~100 μm, length can be between 1~5mm, the wetting characteristics on wetting zones, can be according to Cassie-Baxter contact angles
Formula calculates, and sets the wetting characteristics of each wetting zones.
The wetting gradient surface of solids of discrete type gradual change, according to driving force FdExpression formula, drop titrate the pure of initial position
Between nano-silicon pin region and adjacent wetting zones, sufficiently large contact angle gradient should be left, is provided for drop movement larger
Initial drive force, driving force FdExpression formula is：
Wherein γLV、Rb、θdThe dynamic of respectively liquid-gas surface tension coefficient, solid-liquid contact radius and drop movement connects
Feeler.
Further, wetting gradient surface of solids preparation technology flow includes：
(a) aoxidize；
(b) pattern transfer is carried out by ultraviolet photolithographic；
(c) dry etching surface oxide layer；
(d) dry etching silicon nanoneedle；
(e) degumming process.
Further, with reference to miromaching, devise drop and orient self-driven a variety of mobile routes, can be according to need
Design the drop movement surface of solids of free routing.
The beneficial effects of the invention are as follows：The present invention prepares a kind of nanometer grain surface topology knot using miromaching
Structure, the 3D silicon nanometer needle constructions of etching are as super-hydrophobic region.And for super hydrophilic region, static contact angle is used as 15.5 °
Silica.So, prepared nanometer grain surface wetting gradient scope can be extended to 150 ° (from 15.5 ° to 166.0 °).
The surface of solids by increasing the area ratio in hydrophilic silicas region, be miniflow drop one contact angle of continuous self-driven offer from
Dissipate the wetting gradient mobile route that formula reduces.Generally, the contact angle hysteresis of the surface of solids provides extra energy for liquid drop movement
Potential barrier.The present invention is 3.1 ° with the silicon nanoneedle body structure surface angle of lag with superhydrophobic characteristic, before greatly optimizing drop
The hysteresis of contact line afterwards, further demonstrate miniflow drop and orient self-driven required critical wetting ladder at room temperature
Degree, and devise drop and orient self-driven a variety of mobile routes, it is novel in design, it is a kind of good innovation scheme.
Brief description of the drawings
Describe the present invention in detail with reference to the accompanying drawings and detailed description：
Fig. 1 is the patterned structures figure of present invention wetting gradient；
Fig. 2 is surface graphics structure of the present invention and its wetting characteristics figure；
Fig. 3 is wetting gradient surface self-driven video interception of the drop of the present invention in two kinds of sizes；
Fig. 4 is that drop of the present invention soaks the video interception moved on gradient paths in three species diversities；
Embodiment
In order that the technical means, the inventive features, the objects and the advantages of the present invention are easy to understand, tie below
Conjunction is specifically illustrating, and the present invention is expanded on further.
Referring to Fig. 1, drop method self-driven over long distances on wetting gradient surface, wetting gradient surface is by uniformly aoxidizing
Silicon strip line and silicon nanoneedle structure composition, static contact angle is used at the top of wetting gradient surface of solids striped as 15.5 ° of oxidation
Silicon, wetting gradient solid bottom are the silicon nanometer needle constructions using deep reaction ion etching, and the static contact angle of silicon nanoneedle is
166.0 °, to realize that the surface of solids of discrete type gradual change soaks gradient, using Cassie-Baxter as theoretical direction, by close, thin
The interleaved structure of aqua region striped, the area ratio of hydrophobe material is adjusted, designs the different wetting with wettability contrast
Region surface, these wetting zones are connected by the order that contact angle successively decreases without interval, form the discrete type wetting of the surface of solids
Gradient.The influence of surface of solids wetting gradient is compared for quantitatively characterizing hydrophobe material area, introduces dimensionless group f
Wherein：And ASNPIt is the area of silica and silicon nanometer needle construction respectively, so, wetting gradient surface hydrophilic area
Area gradually increases from left to right than f, and forms a wetting gradient surface from super-hydrophobic to super hydrophilic, designed difference
The area of the hydrophilic fringe area of wetting zones is 0,1/7,1/6,1/5,1/4,1/3,1/2.5,1/2,1/1.7,1/ than respectively
1.4th, 1/1.1 and 1, wherein, the wetting zones that area is 0 and 1 represent pure nano-silicon needle construction region and silica zone respectively
Domain.
Preferably, wetting gradient surface of solids preparation technology flow includes：
(a) aoxidize；
(b) pattern transfer is carried out by ultraviolet photolithographic；
(c) dry etching surface oxide layer；
(d) dry etching silicon nanoneedle；
(e) degumming process；
The length of each silica striped of wetting gradient surface of preparation is 1mm, width is 90 μm, is highly 2 μm.It is adjoint
The area ratio for hydrophilic area progressively increases to 1 from 0, and the spacing of two adiacent silica stripeds is reduced to 0 from 180 μm of discrete types, Gu
Body surface wettability also gradually increases.In order to obtain the maximum moving distance of miniflow drop, two kinds of wetting zones length are devised
The wetting gradient surface droplet travel paths of (1mm and 3mm).
We use OCA15EC Drop Shape Analysis (Dataphysics, Germany) contact angle measurement,
The static contact angle and angle of lag in specific measurement different wetting region.Fig. 2 represents surface of solids static contact angle and angle of lag edge
Soak the change of gradient direction, it is seen that, as patterned surface hydrophilic area area ratio from 0 increases to 1, static contact angle with
15.5 ° that super hydrophilic region is reduced to from 166.0 ° of discrete types in super-hydrophobic region, while with the reduction of static contact angle,
Solid-liquid contact area gradually increases, drop different wetting gradient region shape also from the gradual moisture film shape of segment shape.The present invention
The wetting gradient surface being previously mentioned, the wetting gradient surface of the solid more than 150 ° from super-hydrophobic to super hydrophilic can be achieved.
Referring to Fig. 2 surface graphics structures and its wetting characteristics.Silica Stripe Size is：Long 1mm, wide 90 μm, high 2 μ
M. soak gradient surface top view, the direction reduced along wetting gradient, hydrophilic area area than be 0 respectively, 0.33,0.40,
0.50th, 0.59,0.71,0.91,1, both silica fringe spacing be respectively：180μm、135μm、90μm、63μm、36μm、9μm、0
μm.The sectional drawing at solid-liquid contact interface.Static contact angle and the angle of lag change of different wetting gradient region.
Referring to Fig. 3, wetting gradient surface self-driven video interception of the 7 μ L drops in two kinds of sizes：Fig. 3 a wetting zones
Length is 1mm, the displacement of drop is 5.2mm, and Fig. 3 b wetting zones length is 3mm, the displacement of drop is
3.2mm。
For, this bright a variety of shiftings for devising wetting gradient surface self-driven deeper into the long range orientation for exploring drop
Dynamic path, such as：Annular movement path, long linear travel paths and serpentine path.Fig. 4 represents miniflow drop in wetting gradient
The scope drop mobile video sectional drawing self-driven more than 150 ° of diverse paths surface, drop is during self-driven, its shape
Shape gradually becomes flat moisture film from segment shape.As shown in figure 4, soak gradient surface, the inner and outer diameter point in its path for annular
It is not 3mm and 20mm, and is made up of the sector of 12 different wetting gradients.For larger volume drop (such as 60uL), can have
Effect increase solid-liquid contact interface, so as to the contact angle gradient for increasing inlet wire before drop, retreating line, this big drop is in annular wetting ladder
When being moved on degree mobile route, 210 ° of angular displacements from super-hydrophobic region to super hydrophilic region can be realized.Designed long straight line
Type path is by the Grad region of 10 equal lengths, total length 47mm.60uL drops on this long linear pattern path from
During driving, achievable maximum moving distance is 37.5mm.In addition, the total length of designed " S " type mobile route is 34mm,
When this path is self-driven, to do deflecting self-driven according to the direction of wetting gradient for drop.The realization of these diversity mobile routes, it is
Drop long range non-rectilinear orientation is self-driven to provide possibility, and will be widely applied to microfluidic system.
It should be understood by those skilled in the art that the present invention is not limited to the above embodiments, above-described embodiment and explanation
Merely illustrating the principles of the invention described in book, it is of the invention without departing from the spirit and scope of the present invention also to have respectively
Kind changes and improvements, these changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by
Appended claims and its equivalent define.
Claims (6)
1. drop method self-driven over long distances on wetting gradient surface, it is characterised in that：Gradient surface is soaked by uniform oxygen
SiClx striped and silicon nanoneedle structure composition, static contact angle is used at the top of wetting gradient surface of solids striped as 15.5 ° of oxygen
SiClx；Wetting gradient solid bottom is silicon nanoneedle body structure surface prepared by micromachined, and achievable static contact angle is
166.0 ° of super hydrophobic surface, its angle of lag is not more than 3.0 °, greatly reduces the angle of lag of the surface of solids, close and distant by adjusting
Water area ratio, can be achieved wetting gradient surface of the surface of solids from super hydrophilic to super-hydrophobic, and moistened surface gradient scope is up to
More than 150 °.
2. drop method self-driven over long distances on wetting gradient surface according to claim 1, it is characterised in that：From super parent
Water, by adjusting hydrophobe region area ratio, several wetted areas is designed in the surface of solids to super-hydrophobic wetting gradient surface
The different isometric wetting zones in domain, and the order successively decreased according to contact angle arranges, and realizes that the wetting gradient of discrete type gradual change is consolidated
Body surface face.
3. drop method self-driven over long distances on wetting gradient surface according to claim 1, it is characterised in that：Discrete type
The wetting gradient surface of solids of gradual change, the silica width of each wetting zones can be between 30~100 μm, and length can be 1
Between~5mm, the wetting characteristics on wetting zones, angle formula can be contacted according to Cassie-Baxter and calculated, set each wetting
The wetting characteristics in region.
4. according to 1 and 2 drop of claim on wetting gradient surface self-driven method over long distances, it is characterised in that：From
The wetting gradient surface of solids of formula gradual change is dissipated, according to driving force FdExpression formula, drop titrate the pure nano-silicon pin area of initial position
Between domain and adjacent wetting zones, sufficiently large contact angle gradient should be left, larger initial driving is provided for drop movement
Power, driving force FdExpression formula is：
<mrow>
<msub>
<mi>F</mi>
<mi>d</mi>
</msub>
<mo>&cong;</mo>
<msub>
<mi>&gamma;</mi>
<mrow>
<mi>L</mi>
<mi>V</mi>
</mrow>
</msub>
<msubsup>
<mi>R</mi>
<mi>b</mi>
<mn>2</mn>
</msubsup>
<mi>&pi;</mi>
<mfrac>
<mrow>
<mi>d</mi>
<mi> </mi>
<msub>
<mi>cos&theta;</mi>
<mi>d</mi>
</msub>
</mrow>
<mrow>
<mi>d</mi>
<mi>x</mi>
</mrow>
</mfrac>
</mrow>
Wherein γLV、Rb、θdThe respectively dynamic contact angle of liquid-gas surface tension coefficient, solid-liquid contact radius and drop movement.
5. drop method self-driven over long distances on wetting gradient surface according to claim 1, it is characterised in that：Wetting ladder
Degree surface of solids preparation technology flow includes：
(a) aoxidize；
(b) pattern transfer is carried out by ultraviolet photolithographic；
(c) dry etching surface oxide layer；
(d) dry etching silicon nanoneedle；
(e) degumming process.
6. drop method self-driven over long distances on wetting gradient surface according to claim 1, it is characterised in that：With reference to micro-
Mechanical processing technique, devise drop and orient self-driven a variety of mobile routes, the drop of free routing can be designed as needed
The mobile surface of solids.
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| CN108823569A (en) * | 2018-07-03 | 2018-11-16 | 哈尔滨工业大学 | The preparation method on the special wellability surface of drop directed transport |
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