CN104107734A - Micro-fluidic chip and self-assembling method - Google Patents
Micro-fluidic chip and self-assembling method Download PDFInfo
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Abstract
The invention discloses a micro-fluidic chip and a self-assembling method. The micro-fluidic chip comprises a first channel, a second channel, a third channel, a fourth channel and a plurality of branched chain channels, wherein liquid enters from the first channel and the second channel respectively and then is gathered at an intersection of the first channel, the second channel and the third channel; monodispersed micro-droplet particles are formed after the liquid is gathered by adjusting the flowing speed of fluid; the particles and the liquid are separated through the fourth channel by a branched chain structure, so that self-assembling of the particles in the fourth channel is realized. Due to adjustment of the flowing speed of the liquid and change of the sizes of the channels, the particles with different particle sizes can be obtained, and a single-layer/double-layer/multi-layer three-dimensional ordered compound self-assembled structure is realized. The self-assembling method can be used for self-assembling of the particles.
Description
Technical field
The present invention relates to microflow control technique, relate to specifically a kind of micro-fluidic chip for self assembly and utilize this chip to realize the technology of monodisperse particles self assembly.
Background technology
Microflow control technique comes across the beginning of the eighties in last century, is an emerging field of having gathered engineering science, physics, chemistry, biotechnology, micro-fabrication technique.Microflow control technique, by the chip of several centimeter square, is effectively precisely controlled and handles minute yardstick fluid, especially refers in particular to micron to submicrometer structure, so micro-fluidic chip is the main platform of its realization.Utilize that microflow control technique is can be within even shorter time a few minutes online to be produced a large amount of micro-liquid pearls (speed can reach 1Hz ~ 10
4hz), the liquid pearl of generation can carry out the controlled adjustment of original position in the position of specifying, and reaches the object that is self-assembled into ordered structure.Therefore, can be by the method binding function material (polymer macromolecule, solid particle, liquid particles, bubble etc.) for three-dimensional self-assembling method and technology, make corresponding device, be applied to photonic bandgap material (photonic crystal), colored demonstration, catalysis, sensing, chemical/biological separation and energy storage etc.
Self assembly SAM (Self-assembled monolayers) refers to that a disordered system is not having under outside intervention, by the interaction between indivedual parts, and an organized configuration process of composition.As a kind of new technique, self-assembling technique can design the structure of molecule on molecular level, obtains excellent properties and specific function, because of its have advantages of highly sensitive, selective good.Particle self assembly, general process can experience: prepare particle, screening particle, discrete particles is in solvent, and external force drives the lower several processes of particle self assembly.The fluid mixture that contains particle carries out self assembly and generally removes decentralized photo medium by means such as evaporation, microwave catalysis volatilization or dialysis, thereby by tightly packed particle and form periodic regular texture; Or the solution-air that adopts chemistry to drive and to cause, the variation of liquid-liquid interface energy, makes particle in interface self assembly.
But there is following shortcoming in these existing self-assembling methods: first, need preparation separately for the particle of self assembly, be difficult to control because preparation method's difference can cause the dispersiveness of particle and size; Secondly, because particle is dispersed in solvent (being continuous phase), need a large amount of decentralized photos to disperse, need to consume a large amount of decentralized photos, variation, the change of pH etc. by molecular separating force, chemical potential make the particle in decentralized photo carry out self assembly, this process need consumes long time, and needs special experiment condition and equipment support, has therefore limited the wide model application of self-assembled material in fields such as photonic crystal, acoustics, micro-manufacturing system, medicine release, sensings.
Summary of the invention
The technical problem to be solved in the present invention is: for solving the problem of above-mentioned prior art in particle self assembly, the invention provides a kind of micro-fluidic chip, and utilize this chip to realize the method for monodisperse particles self assembly.
The solution that the present invention solves its technical problem is: a kind of micro-fluidic chip is provided, comprises first passage, second channel, third channel, four-way and some side chain passages; Liquid enters from first passage and second channel respectively, converge in the crosspoint of first passage, second channel and third channel and flow in four-way, side chain passage through third channel, wherein four-way is connected with some side chain passages respectively, and described third channel width is less than the width of described first passage, second channel and four-way.
Preferably, described micro-fluidic chip also comprises the wing passage with some side chain channel connections, and the liquid flowing out from side chain passage like this can be unified to collect after approaching side passage, needn't be respectively at each side chain channel setting fluid collection device.
Preferably, described first passage and second channel have respectively inlet; Described four-way and wing passage have respectively liquid outlet, are convenient to like this liquid and inject and self assembly sample collection.
Preferably, described first passage is arranged taking second channel as axial symmetry; Described side chain passage and wing passage are arranged taking four-way as axial symmetry, and side chain channel vertical is in four-way.Can better eliminate like this interference of other factor convection cells, be more conducive to accurately control self assembling process.Described first passage is arranged as axial symmetry taking second channel, refers to that first passage has many, the symmetrical second channel both sides that are distributed in, and these first passages can have same inlet, also can have separately independent inlet.
Further preferably, the width of described third channel is 10 ~ 100 μ m, and the width of described four-way is 100 ~ 400 μ m, and the width of described side chain passage is 10 ~ 100 μ m.
The present invention also provides a kind of method of utilizing this micro-fluidic chip to carry out self assembly, and the method comprises the following steps:
(1) select immiscible two liquid A phases and B phase;
(2) under room temperature, A is injected to first passage mutually, B injects second channel mutually;
(3) regulate two-phase fluid speed, make to converge while entering third channel when two-phase, B phase liquid forms uniform and stable monodisperse particles and is scattered in A phase liquid;
(4) mixed liquor of A phase liquid and B phase liquid particles enters four-way, and A phase liquid flows out after entering the side chain passage of micro-fluidic chip, and B phase liquid particles is self-assembled into close-packed structure in the four-way of micro-fluidic chip;
(5) in-situ solidifying self-assembled structures collection.
The invention has the beneficial effects as follows: the present invention is by providing a kind of micro-fluidic chip, comprise first passage, second channel, third channel, four-way and some side chain passages, liquid enters from first passage and second channel respectively, crosspoint at first passage, second channel and third channel is converged, by adjusting the flow velocity of fluid, make liquid after converging, form monodispersed micro-drop particle, then enter four-way, utilize its branched structure, realize separating of particle and liquid, particle carries out self assembly in four-way.Described micro-fluidic chip has advantages of integrated height, it is easy to manipulate, be easy to control; Use its method of carrying out self assembly to there is accurately controlled, granule-morphology homogeneous of condition; By regulation and control flow rate of liquid, the size that changes passage can obtain the particle of different-grain diameter, realizes the self-assembled structures of the ordered composite of individual layer/bilayer/multi-layer three-dimension solid.The present invention can be used for the self assembly of particle.
Brief description of the drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing of required use during embodiment is described is briefly described.Obviously, described accompanying drawing is a part of embodiment of the present invention, instead of whole embodiment, and those skilled in the art is not paying under the prerequisite of creative work, can also obtain other designs and accompanying drawing according to these accompanying drawings.
Fig. 1 is the structural representation of the micro-fluidic chip of the embodiment of the present invention 1;
Fig. 2 is the structural representation of the micro-fluidic chip of the embodiment of the present invention 2;
Fig. 3 is the structural representation of the micro-fluidic chip of the embodiment of the present invention 3.
Detailed description of the invention
Below with reference to embodiment and accompanying drawing, the technique effect of design of the present invention, concrete structure and generation is carried out to clear, complete description, to understand fully object of the present invention, feature and effect.Obviously; described embodiment is a part of embodiment of the present invention, instead of whole embodiment, based on embodiments of the invention; other embodiment that those skilled in the art obtains under the prerequisite of not paying creative work, all belong to the scope of protection of the invention.Each technical characterictic in the invention, can combination of interactions under the prerequisite of not conflicting conflict.
The manufacture craft of micro-fluidic chip is the technology of current comparative maturity, the professional knowledge that those skilled in the art can have according to it selects suitable technique to realize, and can use glass, silicon materials or macromolecular material to be used as the material of micro-fluidic chip as dimethyl silicone polymer, epoxy resin, polyurethane etc.Preferably, use and there is the material of waterproof or grease proofness as the material of micro-fluidic chip.While adopting glass material to do chip, first make mask plate, the methods such as recycling photoetching, etching are etched in its model on solid substrate, then carry out device package.Use macromolecular material during as chip material, manufacturing process is: mask blank, photoetching, copies template, finally by the macromolecule chip attach obtaining to slide, obtain particle self assembly micro-fluidic chip of the present invention.Passage on described micro-fluidic chip can pass through plastic tube, glass tube etc. and be connected with fluid pump, and flow rate of liquid is by fluid pump control.
Embodiment 1
With reference to Fig. 1, the structural representation of the micro-fluidic chip of the preferred embodiment of the present invention, liquid enters respectively after first passage 1 and second channel 2 and converges and enter third channel 3, the some side chain passages 5 that enter four-way 4 and be communicated with four-way after third channel of flowing through, chip also comprises the wing passage 6 with side chain channel connection, the width of third channel 3 is less than first passage 1, the width of second channel 2 and four-way 4, first passage 1 distributes taking second channel 2 as axial symmetry, side chain passage 5 and wing passage 6 distribute taking four-way 4 as axial symmetry, and side chain passage 5 vertical connections are in four-way 4, first passage 1 and second channel 2 have respectively inlet a, b, four-way 4 and wing passage 6 have respectively liquid outlet c, d.
In practice, should prepare as required the various factors such as particle diameter and fluid properties of particle, select suitable channel width, according to test, the width that can make described third channel 3 is 10 ~ 100 μ m, the width of described four-way 4 is 100 ~ 400 μ m, and the width of described side chain passage 5 is that the above number range of 10 ~ 100 μ m is comparatively suitable.
The micro-fluidic chip of the present embodiment can carry out self assembly by following steps:
(1) select immiscible two-phase liquid, be denoted as respectively A phase and B phase; Preferably, described immiscible two-phase liquid, wherein one is oil-soluble organic solvent mutually, another is mutually for the aqueous solution comprises: the aqueous solution of distilled water, running water, deionized water or other materials.Described oil-soluble organic solvent is the one or more kinds of mixing in dodecane, hexadecane, dimethicone, kerosene, mineral oil, vegetable oil; The described aqueous solution is the one in the polyethyleneglycol diacrylate aqueous solution, acrylonitrile compolymer acrylamide aqueous solution, the NIPA aqueous solution, inorganic salt solution etc., described inorganic salts can be any in common inorganic salts, as villaumite, carbonate, nitrate, sulfate, sulfonate, carbonate, bicarbonate, disulfate, phosphate, hydrophosphate, dihydrogen sulfate salt etc.Particularly, as sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ferric nitrate, ferrous nitrate, sodium sulphate, sodium sulfonate, potassium sulfate, calcium sulfate, sodium carbonate, potash, magnesium carbonate etc.
Further, in order to regulate the interfacial tension of two-phase liquid, make stable generation particle stable existence carry out self assembly, in described two-phase liquid, can add surfactant.Preferably, described surfactant is the one or more kinds of mixing in lauryl sodium sulfate, tween (Tween), Qu Latong (Triton), sapn (Span), polyvinyl alcohol (PVA), cetyl polyethylene/polypropylene glycol-10/1 dimethyl siloxane (EM90).Wherein tween refers to tween series, comprises polysorbas20 (Tween-20), tween 21(Tween-21), polysorbate40 (Tween-40), polysorbate60 (Tween-60), Tween61 (Tween-61), Tween 80 (Tween-80), sorbimacrogol oleate100 (Tween-81), polysorbate85 (Tween-85) etc.; Equally, Qu Latong, sapn also refer to respectively Qu Latong series and sapn series, comprise respectively triton x-100 (TritonX-100), Qu Latong X-114(TritonX-114) etc. and span 20 (Span20), span 40 (Span40), sorbester p18 (Span60), sorbester p38 (Span65), sorbester p17 (Span80), sorbester p37 (Span85) etc.
(2) under room temperature, A is injected to first passage 1 by inlet a mutually, B injects second channel 2 by inlet b mutually, can adopt the introducings such as fluid pump.
(3) regulate two-phase fluid speed, make to converge while entering third channel 3 when two-phase, B phase liquid forms uniform and stable monodisperse particles and is scattered in A phase liquid; General A phase flow rate of liquid is at 40 ~ 1500 μ L/h, B phase flow rate of liquid is at 15 ~ 600 μ L/h, according to the speed size of two-phase fluid, and the width of third channel can observe like several patterns such as stopper, bead, injection thread or linear flows at meet, the mechanism (extruding, drip, line spray, linear flow) of these four kinds of patterns based on different and forming accordingly.
(4) mixed liquor enters four-way 4, due to impact and the passage geometry designs of flow velocity, four-way 4 and side chain passage 5 have pressure differential, A phase liquid is taken away by the side chain passage 5 of micro-fluidic chip like this, flowed out by liquid outlet d through wing passage 6, it is large that B phase liquid particles concentration becomes, because minimum energy principle is self-assembled into close-packed structure in the four-way 4 of micro-fluidic chip, A phase liquid can be taken away by wing passage within several seconds even shorter time, the spontaneous ordered arrangement of only remaining B phase liquid particles forms individual layer, double-deck, the regular close-packed structure of multilayer, it is self-assembled into one dimension, two dimension, three-dimensional closs packing stereochemical structure depends on the character of two-phase fluid, the grain diameter size producing, the flow rate of fluid, the factor of the each side such as the geometry designs of passage.
(5) in-situ solidifying, obtains self-assembly equipments, and collects at four-way exit c.Curing method comprises that UV solidifies, chemosetting, heat cure etc.
In above-mentioned steps, in order to control the speed of fluid, can add therein tackifier, so that regulate fluid rate, realize the self assembly effect needing.In addition, also can add light trigger, crosslinking agent etc., so that self-assembled structures is curing.
Utilize the micro-fluidic chip of embodiment 1, the specific embodiment that carries out particle self assembly is as follows:
Embodiment A
A is hexadecane mutually, wherein add 2.5wt% Span80 as surfactant, B is deionized water mutually, adopt fluid pump, A, B two-phase are introduced to first passage 1 and second channel 2 by inlet a, b respectively, and when A phase flow velocity is 40 ~ 100 μ L/h, B phase flow velocity is 15 ~ 50 μ L/h, the mutually micro-liquid pearl of B obtaining is of a size of 30 ~ 48 μ m, the one dimension close-packed structure that self assembly forms.When A phase flow velocity is 100 ~ 400 μ L/h, B phase flow velocity is 50 ~ 100 μ L/h, and the mutually micro-liquid pearl of B obtaining is of a size of 25 ~ 30 μ m, the two-dimentional close-packed structure that self assembly forms.
When A phase flow velocity is 400 ~ 600 μ L/h, B phase flow velocity is 100 ~ 200 μ L/h, and the mutually micro-liquid pearl of B obtaining is of a size of 20 ~ 30 μ m, the three-dimensional close-packed structure that self assembly forms.
Embodiment B
A is hexadecane mutually, add 2.5wt% Span80 as surfactant, B is the 6wt% NIPA aqueous solution mutually, adopt fluid pump, A, B two-phase are introduced to first passage 1 and second channel 2 by inlet a, b respectively, and regulating A phase flow velocity is 900 ~ 1200 μ L/h, and B phase flow velocity is 400 ~ 600 μ L/h, the mutually micro-liquid pearl of B size 18 ~ 30 μ m that obtain, the one dimension close-packed structure that self assembly forms.
Embodiment C
A is mineral oil mutually, add 10wt% EM90 as surfactant, B is the 18wt% NIPA aqueous solution mutually, adopt fluid pump, A, B two-phase are introduced to first passage 1 and second channel 2 by inlet a, b respectively, and regulating A phase flow velocity is 40 ~ 250 μ L/h, and B phase flow velocity is 15 ~ 60 μ L/h, the mutually micro-liquid pearl of B size 8 ~ 30 μ m that obtain, the one dimension close-packed structure that self assembly forms.
Embodiment D
A is hexadecane mutually, add 2.6wt% Span80 as surfactant, B is the 15wt% NIPA aqueous solution mutually, wherein contains light trigger 1.5wt%, crosslinking agent 3wt%, adopt fluid pump, A, B two-phase are introduced to first passage 1 and second channel 2 by inlet a, b respectively, and regulating A phase flow velocity is 80 ~ 180 μ L/h, and fixing B phase flow velocity is 20 μ L/h, the mutually micro-liquid pearl of B size 8 ~ 15 μ m that obtain, the three-dimensional close-packed structure of a peacekeeping that self assembly forms.Less than or equal to 120 μ L/h, obtain one dimension close-packed structure in A phase speed, when A phase speed is higher than 120 μ L/h, obtain 3 D stereo close-packed structure, liquid bead footpath is little of 8 μ m.
Embodiment E
A is mineral oil mutually, add 10wt% EM90 as surfactant, B is the 40wt% NIPA aqueous solution mutually, wherein contains light trigger 0.5wt%, crosslinking agent 2wt%, adopt fluid pump, A, B two-phase are introduced to first passage 1 and second channel 2 by inlet a, b respectively, and regulating A phase flow velocity is 20 ~ 80 μ L/h, and B phase flow velocity is 20 ~ 30 μ L/h, the mutually micro-liquid pearl of B size 23 ~ 47 μ m that obtain, the one dimension close-packed structure that self assembly forms.
Embodiment F
A is 0.3% sodium dodecyl sulfate aqueous solution mutually, and B is dodecane mutually, adopts fluid pump, and A, B two-phase are introduced to first passage 1 and second channel 2 by inlet a, b respectively,
When A phase flow velocity is 10 ~ 50 μ L/h, B phase flow velocity is 10 ~ 15 μ L/h, and the mutually micro-liquid pearl of B obtaining is of a size of 40 ~ 50 μ m, the one dimension close-packed structure that self assembly forms.
When A phase flow velocity is 50 ~ 80 μ L/h, B phase flow velocity is 15 ~ 25 μ L/h, and the mutually micro-liquid pearl of B obtaining is of a size of 20 ~ 40 μ m, the two-dimentional close-packed structure that self assembly forms.
When A phase flow velocity is 80 ~ 100 μ L/h, B phase flow velocity is 25 ~ 30 μ L/h, and the mutually micro-liquid pearl of B obtaining is of a size of 5 ~ 25 μ m, the three-dimensional close-packed structure that self assembly forms.
Embodiment G
A is the olive oil of 60v% and the mixed liquor of 40v% sunflower oil mutually, adding 1.5wt% Tween60 is the 18wt% NIPA aqueous solution with 1wt% Span40 as surfactant B mutually, adopt fluid pump, A, B two-phase are introduced to first passage 1 and second channel 2 by inlet a, b respectively, regulating A phase flow velocity is 300 ~ 500 μ L/h, B phase flow velocity is 50 ~ 150 μ L/h, and the mutually micro-liquid pearl of B obtaining is of a size of 15-50 μ m, the two-dimentional close-packed structure that self assembly forms.
Embodiment H
A is the mixed liquor of dodecane, 20v% hexadecane and the 50v% mineral oil of 30v% mutually, add 1.5wt %PVA as surfactant, B is the polyethyleneglycol diacrylate aqueous solution mutually, adopt fluid pump, A, B two-phase are introduced to first passage 1 and second channel 2 by inlet a, b respectively, and regulating A phase flow velocity is 800 ~ 1200 μ L/h, B phase flow velocity 300 ~ 600 μ L/h, the mutually micro-liquid pearl of B obtaining is of a size of 5-15 μ m, the three-dimensional close-packed structure that self assembly forms.
Embodiment 2
As Fig. 2, provide the structural representation of the embodiment 2 of micro-fluidic chip of the present invention, the difference of the chip of itself and embodiment 1 is only: two first passages 1 have respectively independently inlet a.
Embodiment 3
Fig. 3 has provided the structural representation of the embodiment 3 of micro-fluidic chip of the present invention, and the difference of the chip of itself and embodiment 1 is: first passage 1, second channel 2 form y-type structure with third channel 3, and side chain passage 5 tilts to be communicated in four-way 4.
The method of carrying out self assembly about the chip that utilizes embodiment 2 and enforcement 3 is succinct for composing a piece of writing, and does not repeat them here.
Above preferred embodiments of the present invention is illustrated, but the invention is not limited to described embodiment, those of ordinary skill in the art also can make all equivalent modifications or replacement under the prerequisite without prejudice to spirit of the present invention, and the modification that these are equal to or replacement are all included in the application's claim limited range.
Claims (10)
1. a micro-fluidic chip, is characterized in that: comprise first passage, second channel, third channel, four-way and some side chain passages; Liquid enters from first passage and second channel respectively, converges and flow in four-way, side chain passage through third channel in the crosspoint of first passage, second channel and third channel, and wherein four-way is connected with some side chain passages respectively; Described third channel width is less than the width of described first passage, second channel and four-way.
2. micro-fluidic chip according to claim 1, is characterized in that: also comprise the wing passage with some side chain channel connections.
3. according to the micro-fluidic chip described in claim 1 ~ 2 any one, it is characterized in that: described first passage and second channel have respectively inlet; Described four-way and wing passage have respectively liquid outlet.
4. micro-fluidic chip according to claim 1, is characterized in that: described first passage is arranged taking second channel as axial symmetry; Described side chain passage and wing passage are arranged taking four-way as axial symmetry.
5. micro-fluidic chip according to claim 1, is characterized in that: the width of described third channel is 10 ~ 100 μ m, and the width of described four-way is 100 ~ 400 μ m, and the width of described side chain passage is 10 ~ 100 μ m.
6. a method for self assembly, the method comprises the steps:
(1) select immiscible two liquid A phases and B phase;
(2) under room temperature, A is injected to first passage mutually, B injects second channel mutually;
(3) regulate two-phase fluid speed, make to converge while entering third channel when two-phase, B phase liquid forms uniform and stable particle and is scattered in A phase liquid;
(4) mixed liquor of A phase liquid and B phase liquid particles enters four-way, and A phase liquid flows out after entering the side chain passage of micro-fluidic chip, and B phase liquid particles is self-assembled into close-packed structure in the four-way of micro-fluidic chip;
(5) in-situ solidifying self-assembled structures collection.
7. the method for self assembly according to claim 6, is characterized in that: described A phase and B phase liquid, and wherein one is oil-soluble organic solvent mutually, another is distilled water, running water, deionized water or the aqueous solution mutually.
8. the method for self assembly according to claim 7, is characterized in that: described oil-soluble organic solvent is the one or more kinds of mixtures in dodecane, hexadecane, dimethicone, kerosene, mineral oil, vegetable oil; The described aqueous solution is the one in the polyethyleneglycol diacrylate aqueous solution, acrylonitrile compolymer acrylamide aqueous solution, the NIPA aqueous solution, inorganic salt solution.
9. the method for self assembly according to claim 6, is characterized in that: in described A phase or B phase liquid, be added with surfactant.
10. self-assembling method according to claim 6, wherein the flow velocity of A phase liquid is 40 ~ 1500 μ L/h, the flow velocity of B phase liquid is 15 ~ 600 μ L/h.
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Address after: 510631 Guangdong Institute of technology, South China Normal University, Guangzhou City, the Institute of color dynamic electronic paper display technology research institute Patentee after: South China Normal University Patentee after: Shenzhen Guohua Optoelectronics Tech. Co.,Ltd. Patentee after: SHENZHEN GUOHUA OPTOELECTRONIC Research Institute Address before: 510631 Guangdong Institute of technology, South China Normal University, Guangzhou City, the Institute of color dynamic electronic paper display technology research institute Patentee before: South China Normal University Patentee before: Shenzhen Guohua Optoelectronics Tech. Co.,Ltd. Patentee before: SHENZHEN GUOHUA PHOTOELECTRIC RESEACH INSTITUTE |