CN1194800C - Chip micro flow electroosmosis pump - Google Patents

Chip micro flow electroosmosis pump Download PDF

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Publication number
CN1194800C
CN1194800C CNB011349360A CN01134936A CN1194800C CN 1194800 C CN1194800 C CN 1194800C CN B011349360 A CNB011349360 A CN B011349360A CN 01134936 A CN01134936 A CN 01134936A CN 1194800 C CN1194800 C CN 1194800C
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pump
micro flow
electroosmosis
chip micro
chip
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CN1419954A (en
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关亚风
陈令新
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a low pressure micro flow quantity infusion pump designed and made on a chip, which is an electroosmosis flow driving infusion pump capable of directly driving a fluid by electricity and regulating the output pressure intensity and the flow quantity of the fluid by controlling voltage and the length or the combination of filled channels (connected in series and/or in parallel). The output end of the electroosmosis flow driving infusion pump is connected with a gas eliminating device in series. The infusion pump is characterized in that rigid insulating materials or semiconductor materials with equivalent inner diameters of 1 mu m to 1000 mu m are used for filling microchannels, and the equivalent grain diameters of the filling materials are from 50 nm to 3 mu m; used electrodes are planar or unfolding electrodes; used guide pipes are capillary channels with the equivalent inner diameters of 0.1 to 100 mum; driving voltage is supplied by a direct-current power supply of 5 to 200V. The infusion pump can generate output pressure of 0.01 to 700KPa, has precise and adjustable flow quantity, and can output fluids from an muL/min grade and an nL/min grade to an fL/min grade.

Description

Chip micro flow electroosmosis pump
Technical field
The present invention relates to a kind of EOF that designs and produces on chip and drive infusion pump, is a kind of low pressure Microfluidic Pump of utilizing the controllable flow amount of the direct drive fluid of electric energy.Mainly be applicable to the liquid driven of micrometeor system, particularly in micro-full analytical system (the trace transfusion in fields such as μ-TAS), clinical medicine.
Background technology
Peucc in 1803 just did the experiment of electroosmosis, and he manages clay is fixed in " U " shape pipe, and medium during energising (water) moves to the negative pole direction.Reuss also noticed electroosmosis in 1809, i.e. the phenomenon that moves with respect to charged tube wall under the effect of DC electric field of liquid.Under the effect of extra electric field, decentralized medium moves by perforated membrane or superfine capillary (radius 1-10nm), and promptly solid phase is motionless and liquid phase moves, and this phenomenon is called electric osmose (electroosmosis).Experiment shows that the direction that liquid moves is different because of the character of perforated membrane.When used perforated membrane is filter paper, glass or cotton when constituting perforated membrane, then decentralized medium moves to negative electrode, expression liquid phase positively charged this moment; When used perforated membrane was aluminium oxide, brium carbonate formation perforated membrane, then the decentralized medium anode moved, and expression liquid phase this moment is electronegative.The same with electrophoresis, it is very remarkable to the influence of electric osmose speed to add electrolyte, and with the increase of electrolyte concentration, electric osmose speed reduces, even can change the direction of liquid flow.
Utilized electric osmosis principle development electroosmotic pump to obtain some progress with practical value in recent years.The porous stem stem electroosmotic pump that is used for the FIA system of inventions such as He Youzhao (He Youzhao, Gan five or two, Chinese patent application ZL97,212,126; 1997), count microlitre to milliliter (μ L-mL/min) level, can't be applied to micro-system but its range of flow is a per minute.Owing to need regular exhaust, pump can not continuous operation, following (the Sub-μ L/min) flow of microlitre still is difficult to control.The electronic high pressure pump (February 1,2000 for Paul, et al United States Patent 6,019,882) of invention such as Paul is declared to access 2, the pressure of 500Psi, but application example only reaches hundreds of Psi pressure.Patent that the more important thing is Paul does not solve the eliminating air bubble problem: when electricity drove, electrode surface always will produce gas, the time long slightly bubble that just forms in that electrochemical process takes place.In direct driving system, bubble enters in the capillary column inevitably, and electric-force gradient becomes at the bubble place greatly, and the part produces higher Joule heat and makes bubble volume expansion, causes liquid stream to open circuit and the electric osmose interruption; In indirect driving system, the gathering of gas can cause that bubble is counter goes into the electric osmose post, and the electric osmose process is interrupted.So this pump can not continuous operation, can not practicability.The open pipe capillary electroosmotic pump output pressure that relates in other document is too low again, is difficult to satisfy some transfusion requirements.
Usually relate to the problem of liquid with precise control tiny flow quantity aspect microminiaturized at Flow Injection Analysis (FIA), Capillary Electrophoresis (CE), gas phase and liquid phase chromatogram (GC/LC) and mass spectrum (MS) etc.The micrometeor of liquid drives and control technology, and particularly (fields such as μ-TAS), the transfusion of clinical medicine trace are a challenging key issue all the time at micro-full analytical system.Traditional reciprocating machine infusion pump is owing to little seepage of valve and dynamic seal (packing), and its leakage is 10 -1-1 μ L/min level, thereby be difficult to accurately carry less than μ L/min level flow, can't satisfy the harsh requirement of micro-system.Having occurred with sound, electricity, light, magnetic, heat etc. in recent years is the Micropump miscellaneous of basic excitation form, for example piezoelectric type, thermal type, sound wave type, electrohydrodynamic formula, magneto hydrodynamic formula, electric osmose formula or the like.
Summary of the invention
The object of the present invention is to provide a kind of EOF that designs and produces on chip to drive Microfluidic Pump, this pump can accurately be controlled output flow, can provide per minute to ascend to heaven, receive the liquid output flow that rises to microlitre (fL, nL, μ L/min) level and the output pressure of 0.01-700KPa.
To achieve these goals, chip micro flow electroosmosis pump of the present invention is in series with the air scavenge device to the packed column microchannel, drain conduit, electrode and the electric osmose delivery side of pump that constitute electroosmotic pump, all is arranged on the chip piece.Described chip air scavenge device has liquid input channel, liquid output channel, reservoir compartment and has hydrophobic microcapillary array and the gas of porous damping layer or liquid-gas mixed liquor discharge channel.
The principle of electroosmotic pump of the present invention is as follows.
Small solid particle is owing to there is big specific surface usually to produce the unsaturation of key, cause its surface to lose electroneutral and charged, the ion that has an opposite charges with particle surface in polar solvent or electrolyte solution is attracted on its surface with its electric charge of balance, and this effect realizes by the coulomb reciprocation.In general, belong to strong physical absorption, be called close bed near one deck of particle surface, its effect is balance particulate surface electrically; From the more weak adsorption layer of particulate then formation far away slightly, be called dispersion layer.Because anxious poly-decline of strong adsorption layer inner potential slowly reduces in weak adsorption layer, the result produces the current potential downward gradient in whole adsorption layer.Above-mentioned two-layer formation electric double layer.The present invention utilizes the electric osmose drive principle of current-carrying, and promptly under the situation of filler particles (or bonded stationary phase) surface charging in filling the microchannel, the current-carrying of band heterocharge is made the electric osmose travel motion in the diffusion layer of solid-liquid interface electric double layer under External Electrical Field.In filler particles (or bonded stationary phase) particle size range that the present invention adopts, the electric double layer superposition phenomenon can not appear, and can adopt the Smoluchowski equation to provide the EOF expression formula
Ueo=ε 0ε rζE/η (1)
In the formula: Ueo is an electric osmose speed, ε 0Be permittivity of vacuum, ε rBe the current-carrying dielectric constant, ζ is that Zeta potential is an eletrokinetic potential, and η is the fluid viscosity coefficient, and E is an electric-field intensity;
Electric osmose flow Q can be expressed as:
Q=UeoA=ε 0ε rζEA/η (2)
Wherein A is a net sectional area.By selecting for use different electric osmose media and connected mode to change range of flow, regulate field intensity and change the current-carrying flow like this, conversion field intensity direction changes current-carrying and flows to.
The diffusion layer Potential Distributing that produces electroosmosis meets the Gouy-Chapman theory, promptly can be expressed as when ζ is little:
Ψ=F(ζ)e -κx
In the formula: F (ζ) is the function of ζ, x be in the diffusion region somewhere to the distance of adsorption layer.κ decision diffusion layer electromotive force increases the speed that descends, κ with distance x -1Claim electric double layer thickness again;
κ -1=(∑n iz i 2e 20ε rkT) -1/2 (3)
In the formula: k is the Boltzmann constant, and T is an absolute temperature, and e is an electron charge.By (2) (3) as seen, diffusion layer sphere of action and solution ion strength n iWith electricity price z iRelevant.When water is made current-carrying, κ -1Maximum, electric osmose flow and adjustable range are bigger.
Under the direct current External Electrical Field, there is frictional resistance in small filler particles (or bonded stationary phase) surface in migration liquid in the diffusion layer and the filling channel, balance between them has determined the motion of liquid in the diffusion layer, and electric osmose power then depends on the electric field force that acts on diffusion layer and " excessive charge " in the diffusion layer; Polar solvent or electrolyte solution will flow to negative pole end from positive terminal capillaceous under the effect of electric osmose power, form EOF (EOF) thus, if the output at EOF adds a resistance, liquid stream will accumulate in output and form the electric osmose pressure electric osmose power of contending with, till the two reaches balance.When EOF is output as zero, can obtain maximum pressure output, as a same reason, when output electric osmose pressure is zero, can obtain the highest EOF output.
The low pressure microflow electroosmosis pump is by etched one or several fillings microchannel at insulating materials or semi-conducting material manufacturing, amounting to internal diameter is 1 μ m-1000 μ m, in fill out the filler (silica gel of equivalent grain size 50nm-3 μ m, finishing silica gel, ion exchange resin, polymer microsphere, inorganic ball-type or unformed filler, interior moulding filler) or the formed in situ filler, (adopt inert metal by plane or expansion electrode, alloy, conducing composite material and conductive plastic material are made) connect with non-filling channel (conduit) and/or parallel connection is combined into the pump housing, and providing electric power by single dc source, driving voltage is 5-200V.Get rid of the bubble that electrode produces by depassing unit, regulate output flow and pressure, to satisfy various micrometeor transfusion requirement by control voltage or EOF; The uninterruptedly continuous operation for a long time of this pump, the flow adjustable extent is big, and does not have the minimum flow restriction.
Concrete technical scheme of the present invention is as follows:
From formula (1), (2) as seen, electric osmose speed Ueo and current-carrying DIELECTRIC CONSTANTS r, the zeta current potential is that eletrokinetic potential ζ, electric field strength E are directly proportional, and is inversely proportional to fluid viscosity coefficient η; And electric osmose flow Q is except that having identical relation therewith, also and the net sectional area A of " perforated membrane " be directly proportional.In fact owing to the complexity of solution, these parameters influence each other, and have very complicated relation.For certain fluid, output flow is only relevant with electric osmose voltage (field intensity), and output pressure also is directly proportional with filling channel resistance coefficient and mobile phase viscosity coefficient, as shown in Figure 1.Experiment of the present invention (condition: electric osmose passage 2.6cm * 320 μ m i.d.100nm silica gel, the 2.0mmol/L phosphate buffer, PH8.0) result shows, output pressure is directly proportional with the length of packed column, is directly proportional with resistance in fact exactly.But use very long filling channel can make driving voltage too high.Solved this problem by the filling channel pumping system that constitutes of connecting with non-filling channel (connecting duct), can reduce driving voltage by shortening filling channel length.As shown in Figure 2, its output pressure is the multiple relation.Therefore it is strong to produce higher pump pressure with lower voltage, extremely is fit to microchip and uses.
EOF drives infusion pump systems, can by control voltage, filling channel length or or combination of channels (series connection and/or in parallel) regulate the output pressure and the output flow of fluid; The adjusting of flow can by or the size of filling channel change and obtain, the number in parallel of the filling channel of same size is many more or single size is big more, flow is big more.Delivery side of pump is in series with the air scavenge device, whether need can select exhaust as required; And satisfy following condition:
A. rigid insulation material or the semi-conducting material of equivalent internal diameter 1 μ m-1000 μ m adopted in used filling microchannel, and packing material size is 50nm-3 μ m;
B. electrode used therein adopts the expansion electrode of planar shaped or other shape; Electrode is with plated film mode, original position synthesis mode or be coated with the stain mode and make, and realizes with thin-film technique or original position synthesis mode;
C. used conduit adopts the etching capillary channel of equivalent internal diameter 0.1-100 μ m;
D. driving voltage is the 5-200V DC power supplier;
E. pressure limit is 0.01-700KPa, and flow is adjustable, can export μ L/min, nL/min until fL/min level fluid;
Air scavenge device (Fig. 3) has utilized thin pore principle of hydrophobic microtriche and porous damping layer afterwards on the chip, and a microcapillary array is arranged in the device, and sectional dimension is compared very little with fluid channel dimensions.The microcapillary inwall has the character of hydrophobicity, gas in the liquid is induced when running into the hydrophobic wall to be disengaged, higher and when surpassing surface tension capillaceous when liquid pressure, liquid-gas mixed liquor is known from experience by microcapillary and porous damping layer and is flowed out, and the gas in the liquid is discharged from.
Described filler is selected a kind of in silica gel, finishing silica gel, ion exchange resin, polymer microsphere, inorganic ball-type or unformed filler, the interior moulding filler for use.
Description of drawings
Fig. 1 is the influence of electric osmose voltage to pump output pressure and output flow
Fig. 2 is low pressure microflow electroosmosis pump on the chip (totally eight sections filling microchannels are in series by the etching microchannel) schematic diagram
Fig. 3 is air scavenge schematic representation of apparatus on the chip (last figure is a vertical view, and figure below is a side view).
Wherein: 1-connects dc source; 2-fills microchannel, electric osmose source; 3-etching microchannel, transfusion catheter; The 4-electrode when directly making chip with the filling microchannel, is made; 5-chip air scavenge device; The 6-liquid storage tank; 7-chip fluid control device; The thin passage of 15-microtriche (on cover porous damping layer 16); 16-porous damping layer; The 17-gas passage; 18-chip air scavenge device side view; 100-liquid.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is described in detail.
Embodiment 1: single hop filling channel pump, the copper plate electrode, adopt the long 2.0cm of filling channel, equivalence internal diameter 75 μ m, in fill out the silica filler of particle diameter 1 μ m, etching microchannel equivalence internal diameter 10 μ m, aqueous ph value is 7.0, driving voltage 130-200V, range of flow 0.1-0.4nL/min, output pressure 0.3-3kPa;
2: two sections filling channel pumps of embodiment, the stainless steel flat plate electrode, adopt the long 2.0cm of filling channel, equivalence internal diameter 200 μ m, in fill out the silica filler of particle diameter 1 μ m, etching microchannel equivalence internal diameter 5 μ m, all the other conditions are with embodiment 1, driving voltage 80-150V, range of flow 0.3-2.5nL/min, output pressure 0.1-1.5KPa;
3: eight sections filling channel pumps of embodiment cross golden plate electrode, adopt in the long 0.5cm of filling channel and fill out equivalent internal diameter 100 μ m, the interior moulding filler of particle diameter 1 μ m, etching microchannel equivalence internal diameter 10 μ m, driving voltage 30-50V, range of flow 0.2-0.5nL/min, output pressure 0.1-5KPa.

Claims (8)

1. chip micro flow electroosmosis pump, the packed column microchannel, drain conduit, electrode and the electric osmose delivery side of pump that it is characterized in that constituting electroosmotic pump are in series with the air scavenge device and all are arranged on the chip piece, described chip air scavenge device has liquid input channel, liquid output channel, reservoir compartment and has hydrophobic microcapillary array and the gas of porous damping layer or liquid-gas mixed liquor discharge channel.
2. the chip micro flow electroosmosis pump of claim 1 is characterized in that:
A. it is 1 μ m-1000 μ m that equivalent internal diameter is adopted in used packed column microchannel, and the filler equivalent grain size is 50nm-3 μ m;
B. electrode used therein adopts planar shaped or launches electrode;
C. used conduit adopts the capillary channel of equivalent internal diameter 0.1-100 μ m;
3. the chip micro flow electroosmosis pump of claim 2 is characterized in that, described filler is selected a kind of in silica gel, finishing silica gel, ion exchange resin, polymer microsphere, inorganic ball-type or unformed filler, the interior moulding filler for use.
4. the chip micro flow electroosmosis pump of claim 2 is characterized in that, described electrode adopts inert metal, alloy, conducing composite material or conductive plastic material.
5. claim 1 or 2 chip micro flow electroosmosis pump is characterized in that used filling microchannel uses material to be insulating materials or semi-conducting material.
6. the chip micro flow electroosmosis pump of claim 2 is characterized in that, driving voltage is the 5-200V dc source.
7. claim 1 or 2 chip micro flow electroosmosis pump is characterized in that, can connect and/or combination in parallel in the electroosmotic pump unit that packed column microchannel, drain conduit and electrode are constituted.
8. the chip micro flow electroosmosis pump of claim 7 is characterized in that, the shared one group of power supply of the electroosmotic pump that combines.
CNB011349360A 2001-11-15 2001-11-15 Chip micro flow electroosmosis pump Expired - Fee Related CN1194800C (en)

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CN101059526B (en) * 2007-05-24 2011-04-20 上海交通大学 Method for driving fluid movement in micropassage using electric heat flow
CN102872531B (en) * 2011-09-28 2014-11-19 上海交通大学 Preparation method of electric osmosis driving unit of electric osmosis current controllable medicine conveying chip
CN102335479B (en) * 2011-09-28 2013-03-13 上海交通大学 Implanted miniature electroosmotic controllable medicine delivery chip and manufacturing method thereof
CN103816805B (en) * 2012-11-16 2015-12-02 中国科学院理化技术研究所 Electroosmosis micropump device
CN103316722A (en) * 2013-05-27 2013-09-25 苏州扬清芯片科技有限公司 Micro fluidic electrophoresis chip integrated with electroosmosis pump
CN103285947A (en) * 2013-05-27 2013-09-11 苏州扬清芯片科技有限公司 Droplet micro-fluidic chip and operation method thereof
CN103285946A (en) * 2013-05-27 2013-09-11 苏州扬清芯片科技有限公司 Biochip and control method thereof
CN104767354A (en) * 2015-03-19 2015-07-08 华南理工大学 Electrofluid power micropump based on double-pole-piece composite electric field
CN109529962A (en) * 2019-01-18 2019-03-29 江苏医联生物科技有限公司 The method of film electroosmotic pump and its detection pressure and flow velocity based on microchannel plate
CN110339878B (en) * 2019-07-08 2021-01-19 西安交通大学 Device and method for controlling volume flow of power law fluid in microchannel
CN110755699A (en) * 2019-09-18 2020-02-07 浙江省北大信息技术高等研究院 Implantable electroosmotic micropump device
CN110787851B (en) * 2019-10-25 2020-12-04 浙江大学 Multi-channel liquid drop quantitative measuring device and method based on pressure driving

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