CN103007859A - Glass spherical surface ultrasound focused cavitation reinforcement microreactor and preparation method thereof - Google Patents
Glass spherical surface ultrasound focused cavitation reinforcement microreactor and preparation method thereof Download PDFInfo
- Publication number
- CN103007859A CN103007859A CN2012105890636A CN201210589063A CN103007859A CN 103007859 A CN103007859 A CN 103007859A CN 2012105890636 A CN2012105890636 A CN 2012105890636A CN 201210589063 A CN201210589063 A CN 201210589063A CN 103007859 A CN103007859 A CN 103007859A
- Authority
- CN
- China
- Prior art keywords
- glass
- enhanced
- micro
- microreactor
- cavitation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Micromachines (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a glass spherical surface ultrasound focused cavitation reinforcement microreactor which comprises a substrate with a micro flow channel groove, a shallow groove and micro concave points and a system formed by the combination of glass wafers forming structures of glass micro flow channel cavities and spherical glass micro cavities corresponding to the micro flow channel groove and the shallow groove, wherein the system comprises a micro reaction cavity, a micro air chamber, a micro flow channel, an ultrasound excitation source, a fluid inlet and a fluid outlet; and in the structure, ultrasonic wave is utilized to be focused on the micro air chamber, and the cavitation reinforcement effect is realized. The invention also discloses a preparation method of the glass spherical surface ultrasound focused cavitation reinforcement microreactor. The preparation method of the glass spherical surface ultrasound focused cavitation reinforcement microreactor comprises the following steps of: firstly etching the micro flow channel groove and the micro concave points on a silicon substrate; adding a calcium bicarbonate solution in the grooves, then evaporating and heating, thereby obtaining a calcium carbonate high-temperature out-gassing agent finally; then carrying out anodic bonding on the silicon substrate with etched grooves and micro concave points and borosilicate glass wafers so as to form a sealed cavity body; and heating, releasing positive pressure generated by gases released by the high-temperature out-gassing agent so as to form small micro cavities. The glass spherical surface ultrasound focused cavitation reinforcement microreactor and the preparation method of the glass spherical surface ultrasound focused cavitation reinforcement microreactor provided by the invention have the advantages of good controllability and good cavitation effect.
Description
Technical field
The present invention relates to a kind of microreactor and preparation method, relate in particular to a kind of glass sphere focus ultrasonic cavitation-enhanced microreactor and preparation method.
Background technology
Microreactor or all becomes more and more important no matter in laboratory scale biological or chemical reaction in industrial production.The micro-structural of microreactor has many advantages: increase biological or chemical repercussion study efficient, reduce the reactant consumption to save cost.And the phonochemistry technology mainly refers to utilize ultrasonic wave to accelerate chemical reaction, improves the process of chemical yield.The essence of phonochemistry technology is ultrasonic cavitation, comprise cavitation nucleus appearance, cavitation bubble grow up the explosion of cavitation bubble.Ultrasonic microreactor has fabulous heat transfer and mass transfer ability, can realize that the moment of material evenly mixes and efficiently heat transfer, and therefore many reactions that can't realize in the popular response device can realize in the microreactor.Ultrasonic microreactor can also utilize ultrasonic cavitation to reduce the contamination in the reaction chamber and effectively reduce the harmful effects such as obstruction that the sediment in the runner causes.The design of the ultrasonic microreactor of at present, phonochemistry being combined with microorganism or chemical reaction and preparation have become the focus of domestic and international research.
Cavitation refers to bubble in liquid under sound intensity effect, a series of dynamic processes of generation.Usually under the effect of the ultrasonic pressure wave that causes, the average distance of molecule changes along with the vibration of molecule in the liquid.When liquid was applied enough negative pressure, intermolecular distance surpassed the scf molecule spacing that keeps liquid effects, will form the hole, i.e. cavitation bubble.The generation type of this cavitation bubble causes cavitation bubble time of occurrence, position uncertainty or randomness to occur, thereby causes repeatability and the reaction efficiency of testing lower.And cause that the required energy comparison of cavitation phenomenon is high, so cause the waste of energy.Therefore, improve location positioning, generation intensive and the repeatability of ultrasonic cavitation in microreactor, the loss that reduces ultrasonic energy is a difficult problem and the key in the present ultrasonic microreactor.
Kinetics is one of important research content in the chemical analysis, need to realize fast as far as possible reaction with the least possible sample reagent consumption, and the rapid mixing between the differential responses thing is the key that realizes above-mentioned requirements.How to realize the mixing in the microreactor, with mixing-reaction-detecting integrated is the problem that the microreactor system must consider.
Summary of the invention
It is simple to the purpose of this invention is to provide a kind of technique, with low cost, glass sphere focus ultrasonic cavitation-enhanced microreactor and preparation method that integrated level is higher.
The present invention adopts following technical scheme: a kind of preparation method of glass sphere focus ultrasonic cavitation-enhanced microreactor comprises the steps:
The first step, etching fluid channel groove on silicon substrate, little shallow slot, large shallow slot and nick point, large palpulus are shaped as circular or square according to certain ratio.Little shallow slot links to each other by the fluid channel groove with large shallow slot, and the nick point is positioned at large shallow slot, if single nick point, then it is positioned at the center of large shallow slot, if the array that is comprised of a plurality of nick points, then this array is symmetrical centered by the central point of large shallow slot;
Second step adds calcium bicarbonate solution in little shallow slot, evaporate, heat, and obtains at last calcium carbonate high temperature bubble release agent;
The 3rd step, with above-mentioned silicon substrate and Pyrex7740 (a kind of brand of Pyrex that is etched with fluid channel groove, shallow slot and nick point, U.S. CORNING-corning company is produced, and its size is identical with the Si disk) glass wafer carries out anode linkage, the formation seal chamber.Bonding temperature is 400 ℃, and voltage is 600V;
The 4th step, at good Pyrex7740 glass wafer one side surface of above-mentioned bonding, splash-proofing sputtering metal bar figure on the corresponding position of the figure of large shallow slot;
The 5th step, the disk that above-mentioned bonding is good is heated to 850 ℃ ~ 900 ℃, keep 10-15min, the high temperature bubble release agent is emitted the normal pressure of γ-ray emission so that form little glass micro-cavity corresponding to the glass of little shallow slot, gas forms the glass micro-channel chamber by the fluid channel groove, and under the gas effect, formed the spherical glass micro-cavity of surface with the bonding jumper figure corresponding to the glass of large shallow slot, then annealing, cooling;
The 6th step in the punching of little glass micro-cavity place, formed fluid intake and outlet, passed into inside the product that cleaning fluid stays to remove the high temperature releasing agent;
In the 7th step, the upset disk makes substrate upper, and glass wafer one faces down, and is filled with liquid until the exit has liquid to flow out at entrance, closes entrance and exit, the disk that overturns again, and nick point position forms gas-liquid interface on the substrate, thereby has formed little air chamber;
The 8th step placed magnetic field with system, added the alternating current of CF to bonding jumper, and the Lorentz force on the bonding jumper drives whole spherical microcavity generation resonance, and the ultrasonic wave of the 20KHz-1MHz of generation is by the fluid transport in the spherical glass reaction chamber and focus on.
The present invention obtains following technique effect:
The present invention can solve cavitation phenomenon in the general ultrasonic microreactor occur uncontrollable, weak effect, the repeatable problem such as low.Cavitation refers to bubble in liquid under sound intensity effect, a series of dynamic processes of generation.Usually under the effect of the ultrasonic pressure wave that causes, the average distance of molecule changes along with the vibration of molecule in the liquid.When liquid was applied enough negative pressure, intermolecular distance surpassed the scf molecule spacing that keeps liquid effects, will form the hole, i.e. cavitation bubble.The generation type of this cavitation bubble causes the generation position of cavitation bubble uncertainty or randomness to occur, thereby causes the problems such as the repeatability of testing and cavitation effect are lower, and causes that the required energy comparison of cavitation phenomenon is high, so cause the waste of energy.The present invention is owing to introduce little air chamber as source of the gas, hyperacoustic focal zone is also above little air chamber, can realize in the microreactor the accurate control to the cavitation effect position, thereby control is exposed to the amount of liquid under the phonochemistry effect, also can improve generation intensive and the repeatability of cavitation.
2. the present invention is based on MEMS glass sphere ultrasonic transducer, the source of serving as cavitation nucleus at the little air chamber of the central configuration of spherical glass micro-cavity is its most significant feature.When concentration ultrasonic acts on little air chamber, can make little air chamber volumetric expansion, form the bubble ball, be referred to as " female bubble ".Its principle is the process of the dynamic equilibrium of pressure sum that extraneous hydraulic pressure and surface tension cause and the air pressure in little air chamber.And when ultrasonic wave caused that hydraulic pressure is negative pressure less than certain value, the gas in little air chamber will outwards expand." female bubble " constantly expands under the ultrasonic pressure effect, and to a certain moment explosion, the minimum gas that radiates during explosion is wrapped up by extraneous liquid, form many microbubbles, be cavitation nucleus, cavitation nucleus is constantly grown up by the impact of positive and negative acoustic pressure period effects, forms cavitation bubble.Form with Non-Linear Ocsillation in the cavitation bubble growth process is vibrated several cycle in liquid, and the miniflow around the bubble of oscillatory process hollow produces shear action to other particulate.The cavitation bubble thermal insulation is contracted to collapses moment, can produce high temperature and pneumatics in the bubble, causes free radical formation and produces powerful shock wave and jet, thereby destroy eucaryotic cell structure or make enzyme deactivation, and this can be used for smudge cells.
3. the ultrasonic wave among the present invention can be produced by the glass resonator, because its good spherical symmetric structure, make the burnt territory of radiated sound field of ball intracavity ultrasonic controlled, thereby can control the hyperacoustic power density that produces, and need not to utilize other ultrasonic focusing systems to carry out the focus supersonic field distribution that focus ultrasonic just can obtain the required sound intensity.In addition, in spherical glass resonator focus supersonic, can form ultrasonic reflection on the substrate surface, improved to greatest extent the ultrasonic energy density in the spherical glass resonator, reduced energy loss, greatly promote the capacity usage ratio of this focusing generation system, avoided the design of power amplification circuit.Simultaneously, the spherical symmetric structure guarantees that ultrasonic wave focuses on the central area of this structure, passes through control ball chamber height during design, the large shallow slot degree of depth, and nick point position can guarantee that the position of focal zone and little air chamber is crossing, thereby obtains the effect of the little air chamber of focus ultrasonic.And focus supersonic can reduce little air chamber and expand into and produce the required ultrasonic energy of cavitation nucleus, reduces power consumption and the unification that strengthens the cavitation effect to reach.
4. the present invention can realize the integrated of glass resonator and little hybrid chamber, reaction microchamber, mixes-reaction-detect experimental system on the microreactor sheet that is integrated thereby form.This moment, the spherical glass resonator was that little hybrid chamber also is reaction microchamber, and when substrate forms the nick lattice array, the better effects if of mixing, scope can expand to whole reaction chamber.Ultrasonic energy during little the mixing will be lower than reaction microchamber, can not destroy reactant composition or cell.Little mixing cardinal principle is based on the sound wave blender that bubbles, the a certain degree that reaches bubble in liquid no longer continues to expand, stable cavitation namely, and ul-trasonic irradiation is in bubble surface, cause the vibration of bubble, thereby produce large-scale miniflow, destroy original laminar flow interface, form convection current, promoted the mixing between the different phase reaction things.Premixed can add speed and the productive rate of fast response, reduces the use amount of sample reagent.Realize the rapid mixing of microsecond yardstick, be conducive to strengthen reaction microchamber internal reaction effect.
5. device portions of the present invention the present invention is based on the traditional MEMS processing technology based on traditional MEMS processing technology, at first big or small shallow slot and the fluid channel groove structure of a kind of processing for molding in silicon or quartz or invar alloy or Kovar alloy, in specific little shallow slot, inject the high temperature bubble release agent, utilize with the substrate wafer bonding of anode linkage technique with Pyrex7740 glass and etching shallow slot, then be heated to temperature and be higher than the glass softening point temperature, the gas that discharges is transferred in each big or small shallow slot by fluid channel, and normal pressure in the chamber is so that melten glass forms the glass spherical microcavity or glass micro-channel chamber.According to the requirement in preparation microcavity and fluid channel chamber, adjust the size ratio in microcavity and fluid channel chamber.Integrated fluid channel grid is because its material is the Pyrex7740 glass that Corning company produces, its to wave-length coverage in the visible light transmittance rate of 300nm-2000nm up to 90%, and the spherical structure in ball chamber is convenient to light focusing, therefore whole SOC(system on a chip) extremely is easy to observe or to the micrology research of little reaction etc., and glassy phase is more high temperature resistant for macromolecular material, and many chemical reagent or solvent are all kept good chemical inertness, so be the quality material of preparation microreactor.
6. the present invention adopts the high temperature bubble release agent to be interpreted as the glass spherical microcavity and the glass micro-channel thermoforming provides source of the gas, and it is simple to have technique, with low cost, and forming degree is high, the characteristics of good sphericity.The high temperature bubble release agent has residue usually, because gas motion, a small amount of residue can stick on the glass tube walls, pollutes.The present invention can adopt local filled high-temperature bubble release agent, after the high-temperature molding, the zone of polluting can be removed by scribing process, also can after punching, repeatedly clean with cleaning fluid.Advantage of the present invention just is to produce high pressure by the high temperature bubble release agent, avoids again residue to the pollution of MEMS fluid channel simultaneously.The radius size of the spherical glass reaction chamber by this technological forming is 1-20mm, and the thickness of reaction chamber is 0.005mm-0. 2mm.
7. the microreactor system is connected with glass micro-channel between each cavity take each glass ball cavity as main body among the present invention, and the medium in the integrated system is water or other fluid media (medium)s.Design various shapes such as reactant solution or the reaction gas inlet of the shapes such as " T ", " Y ", " W " according to research or need of production, so that the passive mixing such as the focusing of the water conservancy before reacting or chaotic advection, the biological or chemical of being convenient to simultaneously carry out under the multiple phase hybird environments such as liquid phase one liquid phase or liquid phase one gas phase reacts, and in reaction, can carry out ultrasonic processing to sample as required, the active of bubbling such as sound wave mixes.
8. be carved with the silicon chip of microflute and the anode linkage of glass among the present invention and have very high intensity, the characteristics of good leak tightness are difficult for the generation leakage and cause the moulding failure in heating process.400 ℃ of temperature, under the bonding conditions of voltage direct current 600V, anode linkage can reach better sealing effectiveness.
9. the annealing process that adopts among the present invention can effectively be eliminated Pyrex7740 glass and bear the stress that forms in the high temperature positive pressure forming process, thereby makes its strength and toughness higher.Annealing temperature is that temperature retention time is 30min in 550 ℃～570 ℃ scopes, and then Slow cooling is to room temperature.Under this condition, anneal, the stress of can effectively decorporating, can also so that the shape of microcavity substantially without changing, and the too high microcavity shape that easily causes of annealing temperature changes, excessively low annealing temperature then can't effectively be removed inside glass stress.
10. the Pyrex7740 glass that the thermal coefficient of expansion of the present invention's preparation and Si is suitable is as fluid channel chamber and spherical glass micro-cavity structure, because the coupling of the heat between silicon and the glass is fine, the impact of stress is very little when therefore preparing microcavity.
11. the present invention selects calcium bicarbonate solution as the method for adding calcium carbonate high temperature bubble release agent, by evaporative removal moisture, generates high temperature bubble release agent calcium carbonate crystal by heating so that calcium bicarbonate decomposes.Adopt this solwution method to add calcium bicarbonate, finally in groove, obtain calcium carbonate crystal, have the following advantages: one, calcium bicarbonate is soluble in water, its concentration can accurately be controlled, according to the volume that injects, can accurately control the quality of calcium bicarbonate, thereby can accurately control the quality of the calcium carbonate that generates, the final accurately size of control glass micro-cavity that realizes; Two, the aqueous solution is with respect to simple calcium carbonate or titanium hydride powders, easier being introduced in the microflute, and can not cause powder residual at bonding face; Three, the activity in production of microelectronic industry is all carried out under based on the ultra-clean chamber condition, has strict requirement for airborne dust Control, therefore in the volume production process, directly control high temperature bubble release agent (such as the calcium carbonate in this patent) powder and can pollute ultra-clean chamber easily, thereby cause potential risks, and adopt calcium bicarbonate solution can be easy to can not exert an influence to ultra-clean chamber in the calcium carbonate lead-ingroove with accurate quantification (calcium carbonate crystal that the heating calcium bicarbonate generates after decomposing can be adsorbed on the silicon rooved face).
Description of drawings
Fig. 1 is glass sphere focus ultrasonic cavitation-enhanced microreactor system on chip structure schematic diagram.
Fig. 2 is the transverse sectional view that is etched with the substrate of shallow slot and nick point before the bonding.
Fig. 3 be populated liquid and form little air chamber after the transverse sectional view of microreactor.
The specific embodiment
Embodiment 1
The preparation method of experimental system on the fluid channel mesh flake of a kind of integrated ball surface glass chamber focus ultrasonic transmitter may further comprise the steps:
The first step adopts the oxide layer of method oxidation 5000 on the silicon wafer of single-sided polishing of dried wet oxygen combination, burnishing surface spin coating AZ P4620 photoresist, and exposure imaging is removed the photoresist that needs etching microcavity surface.Utilize Si micro fabrication etching fluid channel groove and big or small shallow slot on 4 inches Si disks, the fluid channel groove couples together big or small shallow slot, used silicon chip can be the silicon chip of standard thickness, thickness is 500 microns, and the degree of depth of described big or small shallow slot is the 50-150 micron, and little shallow slot width is the 100-1000 micron, large shallow slot width is the 1000-10000 micron, being shaped as of they is square or circular, and the fluid channel groove is that bore is 50 microns bar shaped chamber, 5 millimeters of length.The micro fabrication of described Si pattern on wafer structure is wet corrosion technique, and used corrosive liquid is TMAH solution, and concentration is 25%, and temperature is 90 degrees centigrade, and etch period is 1. 5-2 hours.Then in large shallow slot center, etching a bore with focused particle beam is the 0.5-20 micron, and the degree of depth is the column type nick point of 1-50 micron.
Second step adopts dispensing technology that miniature silicon groove is quantitatively injected solution in several little shallow slots, evaporates, heats, and obtains at last calcium carbonate.Repeat the described step of second step 2-50 time, until the amount of calcium carbonate meets the requirement of moulding.There is the microchannel to link to each other between the described miniature silicon groove array.Heating-up temperature is 40 in the second step, for example temperature can for ℃,,,, ℃,,,, ℃,,;
The 3rd step, the anode linkage under 0.5Pa with above-mentioned Si disk and Pyrex7740 glass wafer, make Pyrex7740 above-mentioned shallow chamber on glass form seal chamber, bonding surface should keep highly cleaning and minimum surface roughness before bonding, to satisfy the requirement of conventional bonding, technological requirement according to anode linkage or other bondings is carried out conventional Cleaning and polishing, and described anode linkage process conditions are: 400 ℃ of temperature, voltage: 600V.The reaction microchamber chamber air-tightness is good, is convenient to carry out biochemical test.Simultaneously, preparation fluid channel integrated reaction system transparent good up to 90%, is convenient to carry out the quantitative determination and analysis of reacted product to the light transmittance of visible light.
The 4th step, the metal band of specific region sputter Cr-Cu-Au three-decker above the bonding disk, their thickness: Cr is about 0.06 micron, and Cu is about 0. 7 microns, and Au is about 0. 5 microns.Wherein Cr is as the metal adhesion layer, and Cu is main conductive metal layer, and Au has increased the ductility of this metal structure.The metal of Cr-Cu-Au three-decker, when having guaranteed metal band electric conductivity, metal may produce the situation of fracture because stretch when also having overcome because of the thermoplasticity stretching.
The 5th step, the disk that above-mentioned bonding is good is heated to 850 ℃ ~ 900 ℃ under an atmospheric pressure, under this temperature, be incubated 5 ~ 10min, the high temperature bubble release agent is fully thermal decomposition fast, gas diffuses to whole sealing system, each microcavity internal pressure balance presses the glass after chamber external and internal pressure official post is softened to form the structure corresponding with above-mentioned shallow slot patterning.Be cooled to 25 ℃ of normal temperature, obtain the wafer level spherical microcavity, again disk is inserted annealing furnace, be heated to 550 ℃～570 ℃, insulation 30min, then slowly air-cooled to normal temperature (for example 25 ℃), the lower stress relieving by annealing of normal pressure (atmospheric pressure).
In the 6th step, in the punching of specific little microcavity place, form fluid intake and outlet.Then, the upset disk makes substrate upper, and glass wafer one faces down, and is filled with liquid until the exit has liquid to flow out at entrance, closes entrance and exit, the upset disk, and nick point position forms gas-liquid interface on the substrate, thereby has formed little air chamber.
The 7th step, in sputter the glass ball cavity place of metal band in addition perpendicular to the stationary magnetic field of metal band, and metal band passed to the alternating current of certain frequency, make the Lorentz force that produces opposite direction in the different cycles on the metal band, thereby drive the resonance of glass ball cavity.The resonant frequency of spherical glass chamber focus ultrasonic transmitter can be regulated according to the size of glass micro-cavity, and adjustable range is 20kHz-1MHz.
The 8th goes on foot, and utilizes the resonance in spherical glass chamber, and the resonant frequency of spherical glass chamber focus ultrasonic transmitter can be regulated according to the size of glass micro-cavity, and adjustable range is 20kHz-1MHz.Utilize the ultrasonic wave of different frequency, the hydraulic pressure scope-0.6MPa of generation ~ 0.2MPa when suction function during in little air chamber, expands and explosion little air chamber, forms cavitation nucleus, has just become cavitation bubble after growing up.The burnt territory energy density of spherical glass chamber focus ultrasonic transmitter is 0.35W/cm2 ~ 0.5W/cm2, be enough to make cavitation bubble vibration or explosion, thereby realize breaking liquid phase-liquid phase or liquid phase-gas phase interface, increase the reactant contact area, perhaps produce free radical, accelerate reaction rate etc.
Embodiment 2
The preparation method of experimental system on the fluid channel mesh flake of a kind of integrated ball surface glass chamber focus ultrasonic transmitter may further comprise the steps:
The first step adopts the oxide layer of method oxidation 5000 on the silicon wafer of single-sided polishing of dried wet oxygen combination, burnishing surface spin coating AZ P4620 photoresist, and exposure imaging is removed the photoresist that needs etching microcavity surface.Utilize Si micro fabrication etching fluid channel groove and big or small shallow slot on 4 inches Si disks, the fluid channel groove couples together big or small shallow slot, used silicon chip can be the silicon chip of standard thickness, thickness is 500 microns, and the degree of depth of described big or small shallow slot is the 50-150 micron, and little shallow slot width is the 100-1000 micron, large shallow slot width is the 1000-10000 micron, being shaped as of they is square or circular, and the fluid channel groove is that bore is 50 microns bar shaped chamber, 5 millimeters of length.The micro fabrication of described Si pattern on wafer structure is wet corrosion technique, and used corrosive liquid is TMAH solution, and concentration is 25%, and temperature is 90 degrees centigrade, and etch period is 1. 5-2 hours.Then in large shallow slot center, etching a bore with focused particle beam is the 0.5-20 micron, and the degree of depth is the column type nick point of 1-50 micron.
Second step adopts dispensing technology that miniature silicon groove is quantitatively injected calcium bicarbonate solution in several little shallow slots, evaporates, heats, and obtains at last calcium carbonate.Repeat the described step 10 of second step time, until the amount of calcium carbonate meets the requirement of moulding.There is the microchannel to link to each other between the described miniature silicon groove array.Heating-up temperature is 150 ℃ in the second step;
In the 3rd step, deposited polycrystalline silicon thin film or piezoceramics film in specific shallow chamber, film thickness are 2 microns ~ 10 microns.Utilization is carried in the alternating voltage on the film, can make film produce exciting, thereby drives the resonance in spherical glass chamber, produces frequency at the ultrasonic wave of 20kHz-1MHz.
The 4th step, the anode linkage under 0.5Pa with above-mentioned Si disk and Pyrex7740 glass wafer, make Pyrex7740 above-mentioned shallow chamber on glass form seal chamber, bonding surface should keep highly cleaning and minimum surface roughness before bonding, to satisfy the requirement of conventional bonding, technological requirement according to anode linkage or other bondings is carried out conventional Cleaning and polishing, and described anode linkage process conditions are: 400 ℃ of temperature, voltage: 600V.The reaction microchamber chamber air-tightness is good, is convenient to carry out biochemical test.Simultaneously, preparation fluid channel integrated reaction system transparent good up to 90%, is convenient to carry out the quantitative determination and analysis of reacted product to the light transmittance of visible light.
The 5th step, the disk that above-mentioned bonding is good is heated to 850 ℃ ~ 900 ℃ under an atmospheric pressure, under this temperature, be incubated 5 ~ 10min, the high temperature bubble release agent is fully thermal decomposition fast, gas diffuses to whole sealing system, each microcavity internal pressure balance presses the glass after chamber external and internal pressure official post is softened to form the structure corresponding with above-mentioned shallow slot patterning.Be cooled to 25 ℃ of normal temperature, obtain the wafer level spherical microcavity, again disk is inserted annealing furnace, be heated to 550 ℃～570 ℃, insulation 30min, then slowly air-cooled to normal temperature (for example 25 ℃), the lower stress relieving by annealing of normal pressure (atmospheric pressure).
In the 6th step, in the punching of specific little microcavity place, form fluid intake and outlet.Then, the upset disk makes substrate upper, and glass wafer one faces down, and is filled with liquid until the exit has liquid to flow out at entrance, closes entrance and exit, the upset disk, and nick point position forms gas-liquid interface on the substrate, thereby has formed little air chamber.
The 7th step in having deposited the spherical glass chamber of piezoelectric film material, passed to the alternating voltage of certain frequency to piezoelectric film material, made piezoelectric produce exciting, thereby drove the resonance of glass ball cavity.The resonant frequency of spherical glass chamber focus ultrasonic transmitter can be regulated according to the size of glass micro-cavity, and adjustable range is 20kHz-1MHz.
The 8th goes on foot, and utilizes the resonance in spherical glass chamber, and the resonant frequency of spherical glass chamber focus ultrasonic transmitter can be regulated according to the size of glass micro-cavity, and adjustable range is 20kHz-1MHz.Utilize the ultrasonic wave of different frequency, the hydraulic pressure scope-0.6MPa of generation ~ 0.2MPa when suction function during in little air chamber, expands and explosion little air chamber, forms cavitation nucleus, has just become cavitation bubble after growing up.The burnt territory energy density of spherical glass chamber focus ultrasonic transmitter is 0.35W/cm2 ~ 0.5W/cm2, be enough to make cavitation bubble vibration or explosion, thereby realize breaking liquid phase-liquid phase or liquid phase-gas phase interface, increase the reactant contact area, perhaps produce free radical, accelerate reaction rate etc.
Claims (16)
1. glass sphere focus ultrasonic cavitation-enhanced microreactor, it is characterized in that forming the system that the glass wafer (2) of glass micro-channel chamber (21) and spherical glass micro-cavity (22) structure is combined into the substrate (1) of fluid channel groove (11), shallow slot and nick point (12) with corresponding to fluid channel groove and shallow slot, this system comprises reaction microchamber (3), little air chamber (4), fluid channel (5), ultrasonic action source (6), fluid intake and outlet (7), utilize ultrasonic wave to focus on little air chamber in the structure, realize the cavitation-enhanced effect.
2. glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 1 is characterized in that described glass is Pyrex, and substrate is a kind of in silicon or quartz or invar alloy or the Kovar alloy.
3. glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 1 is characterized in that described little air chamber is formed by nick point inwall and the sealing of air-liquid interface, and the center at this interface overlaps substantially with the centre of sphere of spherical glass reaction chamber
Glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 1 is characterized in that described nick point can be the nick lattice array that single nick point or a plurality of nick point form.
4. glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 1, it is characterized in that described ultrasonic action source can be coupling in for the ultrasonic transducer that the flexible piezoelectric material is made surface, ball chamber, also can be the circuitous type bonding jumper that is integrated in ball-type glass micro-cavity surface.
5. glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 1, the geometry that it is characterized in that described nick point is cylinder or cone or cuboid, its Breadth Maximum and depth bounds are 0.1-100 μ m.
6. glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 1, the radius size that it is characterized in that spherical glass micro-cavity is 1mm-20mm.
7. the preparation method of a glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 1, it is characterized in that comprising the steps: at first, etching fluid channel groove on silicon substrate, little shallow slot (131), large shallow slot (132) and nick point; In little shallow slot, add calcium bicarbonate solution, evaporate again, heat, obtain at last calcium carbonate high temperature bubble release agent (8); Then above-mentioned silicon substrate and the Pyrex disk that is etched with fluid channel groove, shallow slot and nick point carried out anode linkage, form seal chamber; Then splash-proofing sputtering metal bar figure on the good Pyrex disk one side surface relevant position of above-mentioned bonding; At this moment, the disk that above-mentioned bonding is good is heated to the Pyrex softening point temperature, the high temperature bubble release agent is emitted the normal pressure of γ-ray emission so that form little microcavity (221) corresponding to the glass of little shallow slot, gas forms the glass micro-channel chamber by the fluid channel groove simultaneously, and has formed the spherical glass micro-cavity of surface with the bonding jumper figure corresponding to the glass of large shallow slot under the gas effect; In the punching of little microcavity place, form fluid intake and outlet after the cooling,
8.Then, the upset disk makes substrate upper, and glass wafer one faces down, and is filled with liquid until the exit has liquid to flow out at entrance, closes entrance and exit, the upset disk, and nick point position forms gas-liquid interface on the substrate, thereby has formed little air chamber.
8. system is placed magnetic field, the alternating current that adds CF to bonding jumper, Lorentz force on the bonding jumper drives whole spherical microcavity generation resonance, and the ultrasonic wave of generation is by the fluid transport in the spherical glass reaction chamber and focusing, and ultrasonic wave focuses on little air chamber.
9. glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 8 is characterized in that the described step of repetition second step 2-50 time, until the amount of calcium carbonate meets the requirement of moulding.
10. glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 1 is characterized in that adopting dispensing technology that little shallow slot is quantitatively injected solution.
11. the preparation method of glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 8 is characterized in that described etching fluid channel groove, the lithographic method of little shallow slot, large shallow slot is wet etching, and the method for etching nick point is dry etching.
12. the preparation method of glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 8 is characterized in that described nick point can be the nick lattice array that single nick point or a plurality of nick point form.
13. the preparation method of glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 8, the drilling method that it is characterized in that fluid intake and outlet is laser boring, and the diameter that forms the hole is 0.1mm-3mm.
14. the preparation method of glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 8, the geometry that it is characterized in that described nick point is cylinder or cone or cuboid, and its size range is 0.1-100 μ m.
15. the preparation method of glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 8, the radius size that it is characterized in that the spherical glass reaction chamber is 1-20mm.
16. the preparation method of glass sphere focus ultrasonic cavitation-enhanced microreactor according to claim 8, it is characterized in that the gas of filling in little air chamber is air, filling liquid in spherical glass reaction chamber and the fluid channel is water, can add enzyme or cell in the liquid, polymeric particles, perhaps chemical reagent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105890636A CN103007859A (en) | 2012-12-31 | 2012-12-31 | Glass spherical surface ultrasound focused cavitation reinforcement microreactor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105890636A CN103007859A (en) | 2012-12-31 | 2012-12-31 | Glass spherical surface ultrasound focused cavitation reinforcement microreactor and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103007859A true CN103007859A (en) | 2013-04-03 |
Family
ID=47957292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105890636A Pending CN103007859A (en) | 2012-12-31 | 2012-12-31 | Glass spherical surface ultrasound focused cavitation reinforcement microreactor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103007859A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104162395A (en) * | 2014-03-21 | 2014-11-26 | 中国科学院大连化学物理研究所 | Method for enhancing gas-liquid process in micro-reactor |
| CN104437686A (en) * | 2013-09-18 | 2015-03-25 | 中国科学院理化技术研究所 | Micro heater |
| CN104923137A (en) * | 2014-03-19 | 2015-09-23 | 中国科学院大连化学物理研究所 | Method for enhancing fluid mixing in micro-reactor |
| CN105755730A (en) * | 2016-04-11 | 2016-07-13 | 李鸿 | Ultrasonic washing ball |
| CN113198403A (en) * | 2021-05-10 | 2021-08-03 | 南京科技职业学院 | Micro-channel reactor |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218521A (en) * | 1996-04-10 | 1999-06-02 | 动力有限公司 | Method for removal of film from metal surfaces using electrolysis and cavitation action |
| CN2581058Y (en) * | 2002-08-29 | 2003-10-22 | 程树群 | Emulsifying device for iodipin and medicinal preparation |
| CN1546219A (en) * | 2003-11-28 | 2004-11-17 | 戴露雯 | Ultrasonic focusing processing unit |
| WO2008011759A1 (en) * | 2006-07-21 | 2008-01-31 | Beijing Yuande Bio-Medical Engineering Co., Ltd. | An ultrasound phase-control focusing transducer based on spherical lens |
| CN101905859A (en) * | 2010-04-16 | 2010-12-08 | 东南大学 | Method for preparing wafer-level uniform-dimension glass microcavity by positive pressure thermal forming |
| CN102341162A (en) * | 2009-04-14 | 2012-02-01 | 比奥卡尔齐什股份有限公司 | Hifu induced cavitation with reduced power threshold |
| CN102430512A (en) * | 2011-09-30 | 2012-05-02 | 东南大学 | Integrated system on ultrasonic transducer sheet with MEMS (Micro-Electromechanical Systems) glass sphere and preparation method thereof |
-
2012
- 2012-12-31 CN CN2012105890636A patent/CN103007859A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218521A (en) * | 1996-04-10 | 1999-06-02 | 动力有限公司 | Method for removal of film from metal surfaces using electrolysis and cavitation action |
| CN2581058Y (en) * | 2002-08-29 | 2003-10-22 | 程树群 | Emulsifying device for iodipin and medicinal preparation |
| CN1546219A (en) * | 2003-11-28 | 2004-11-17 | 戴露雯 | Ultrasonic focusing processing unit |
| WO2008011759A1 (en) * | 2006-07-21 | 2008-01-31 | Beijing Yuande Bio-Medical Engineering Co., Ltd. | An ultrasound phase-control focusing transducer based on spherical lens |
| CN102341162A (en) * | 2009-04-14 | 2012-02-01 | 比奥卡尔齐什股份有限公司 | Hifu induced cavitation with reduced power threshold |
| CN101905859A (en) * | 2010-04-16 | 2010-12-08 | 东南大学 | Method for preparing wafer-level uniform-dimension glass microcavity by positive pressure thermal forming |
| CN102430512A (en) * | 2011-09-30 | 2012-05-02 | 东南大学 | Integrated system on ultrasonic transducer sheet with MEMS (Micro-Electromechanical Systems) glass sphere and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437686A (en) * | 2013-09-18 | 2015-03-25 | 中国科学院理化技术研究所 | Micro heater |
| CN104437686B (en) * | 2013-09-18 | 2016-01-13 | 中国科学院理化技术研究所 | micro-heater |
| CN104923137A (en) * | 2014-03-19 | 2015-09-23 | 中国科学院大连化学物理研究所 | Method for enhancing fluid mixing in micro-reactor |
| CN104162395A (en) * | 2014-03-21 | 2014-11-26 | 中国科学院大连化学物理研究所 | Method for enhancing gas-liquid process in micro-reactor |
| CN105755730A (en) * | 2016-04-11 | 2016-07-13 | 李鸿 | Ultrasonic washing ball |
| CN105755730B (en) * | 2016-04-11 | 2018-06-08 | 李鸿 | Ultrasonic wave washing ball |
| CN113198403A (en) * | 2021-05-10 | 2021-08-03 | 南京科技职业学院 | Micro-channel reactor |
| CN113198403B (en) * | 2021-05-10 | 2022-04-15 | 南京科技职业学院 | Micro-channel reactor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103007859A (en) | Glass spherical surface ultrasound focused cavitation reinforcement microreactor and preparation method thereof | |
| Le Gac et al. | Sonoporation of suspension cells with a single cavitation bubble in a microfluidic confinement | |
| JP6367717B2 (en) | Fast on-demand droplet generation and single-cell encapsulation driven by induced cavitation | |
| Rivas et al. | Efficient sonochemistry through microbubbles generated with micromachined surfaces | |
| Quinto-Su et al. | Examination of laser microbeam cell lysis in a PDMS microfluidic channel using time-resolved imaging | |
| Gao et al. | Trapping and control of bubbles in various microfluidic applications | |
| Jiao et al. | In situ tunable bubble wettability with fast response induced by solution surface tension | |
| AU2020104434A4 (en) | Array type paper chip for 2019-nCoV virus high-throughput detection and manufacturing method of array type paper chip | |
| Gallego-Juárez et al. | Ultrasonic defoaming and debubbling in food processing and other applications | |
| CN103981090A (en) | Gene introduction chip and gene introduction method | |
| CN101503817B (en) | Photo-assisted electro chemical etching apparatus | |
| CN110171812A (en) | Multi-layer porous hollow bowl-type carbon material of one kind and preparation method thereof | |
| CN102430512B (en) | Integrated system on ultrasonic transducer sheet with MEMS (Micro-Electromechanical Systems) glass sphere and preparation method thereof | |
| WO2002058847A9 (en) | Cell transformation using a single chip silicon microfabricated array incorporating integrated micro-piercing injectors | |
| CN103691384A (en) | Micro-bubble generator as well as manufacturing method and application thereof | |
| Yong et al. | Self‐Driving Underwater “Aerofluidics” | |
| JP2008290027A (en) | Reaction apparatus and reaction method | |
| CN107824105B (en) | Micro mixer capable of adjusting solution concentration gradient based on moving bubbles | |
| US20160068798A1 (en) | Systems and methods for single cell isolation and analysis | |
| CN107876112A (en) | A kind of method of glass Direct Bonding artistic glass base microfluidic channel sealing-in | |
| Tsvetkov et al. | On the role of supercritical water in laser-induced backside wet etching of glass | |
| CN114621857A (en) | High-flux cracking system based on resonance microbubble array | |
| CN115569675B (en) | Micro-droplet generation method and generation device thereof | |
| CN114308151A (en) | Acoustic microfluidic system for cell fusion and preparation method and application thereof | |
| US20240150748A1 (en) | Acoustic microfluidic system for cell fusion, preparation method therefor and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130403 |