CN1773274A - Method for producing miniflow control chip - Google Patents

Method for producing miniflow control chip Download PDF

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Publication number
CN1773274A
CN1773274A CN 200510019720 CN200510019720A CN1773274A CN 1773274 A CN1773274 A CN 1773274A CN 200510019720 CN200510019720 CN 200510019720 CN 200510019720 A CN200510019720 A CN 200510019720A CN 1773274 A CN1773274 A CN 1773274A
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electrode
glass
chip
micron
hole
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CN100425984C (en
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王升高
汪建华
杨茂荣
李艳琼
王涛
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Wuhan Chemistry College
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Wuhan Chemistry College
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Abstract

The present invention relates to a microflow control chip and its preparation method. Said method includes the following steps: selecting glass component, adding proper quantity of photosensitizer and crystal nucleus agent, high-temperature melting, drawing or pouring to obtain sheet material, grinding and polishing to obtain glass sheet, making the glass sheet successively undergo the processes of optical irradiation, high temperature and acid corrosion treatment so as to obtain the glass chip with microflow channel, liquid cell, high-pressure isolation structure and hole array for integrating electrodes; utilizing plasma chemical gas-phase deposition method, hot wire chemical gas-phase deposition method or high-temperature cracking method to respectively integrate nano carbon tube working electrode, reference electrode and electrophoretic separation electrode in the correspondent holes and packaging so as to obtain the invented microflow control chip.

Description

The preparation method of micro-fluidic chip
Technical field
The present invention relates to physics, chemistry, electronics and material field, the preparation method of the micro-fluidic chip that particularly a kind of height is integrated.The main core technology of this micro-fluidic chip is the integrated of the preparation of photosensitive glass-ceramics chip material and CNT electrode.Have multiple functions such as reaction, separation, detection, be applicable to whole analysis fields, comprise biological medicine, environmental monitoring, food hygiene, criminal science and national defence etc.
Background technology
Micro-fluidic chip is the core of micro-full analytical system, representing analytical instrument to move towards microminiaturized, integrated developing direction, be intended to the intersection by analytical chemistry, micro electronmechanical processing, material science, electronics and biology, medical science, the realization analytic system is handled whole microminiaturization, robotization, the integrated and portability that detects from sample.Its advantage is by automatic micro-fluidic operation in the chip channel, significantly reduces consuming, and makes that analysis speed improves greatly, expense significantly descends.It is support based on analytical chemistry with micro electronmechanical process technology, is architectural feature with the microchannel network, is applicable to whole analysis fields, comprises biological medicine, environmental monitoring, food hygiene, criminal science and national defence etc.
The final state of development of micro-fluidic chip depends on the degree of integration of microminiaturized chemical reaction, separation and detection system.Aspect the detection collection of signal, have the main means that height sensitivity and compatible electrochemical method have become chip detection simultaneously.Its detection volume is little, dimensionally with the concept matching of chip lab, can directly electrode be integrated on the chip, very high to substance responds that electrochemical reaction is arranged, can be widely used for the detection of amino acid, peptide, carbohydrates, neurotransmitter, medicine, inorganic ions etc., equipment is simple, cheap, is convenient to promote the use of.
The report of at present relevant micro-fluidic chip based on Electrochemical Detection is a lot, and its chip material mainly contains glass, quartz or superpolymer.Advantages such as for the said chip material, glass or quartz glass chip have structural stability, the electric osmose performance is good, and the life-span is long, but its processing difficulties.The superpolymer chip material is easy to process, but structural stability is relatively poor, can not satisfy the needs of long-term test.With regard to electrochemical detection electrode, electrode and sample to be tested contact area are more little, and signal to noise ratio (S/N ratio) is high more.Electrode size reduces to help improving mass transfer velocity, respond electrochemical properties such as rapid and signal to noise ratio (S/N ratio) height.When the size of electrode further is reduced to nanoscale, not only be suitable for microcell and trace analysis and sweep volt-ampere soon and kinetics of electrode process research, have higher steady-state current density and shorter response time, and have high mass transfer velocity and high resolution.Can in the presence of a large amount of non-reversible reaction materials, measure the electroactive substance of trace good reversibility in view of the above.But the detecting electrode material is mainly metal membrane material at present, and bigger with the testing liquid contact area, signal to noise ratio (S/N ratio) is just low like this.
Summary of the invention
The present invention is in order to overcome the defect problem that above-mentioned prior art exists, a kind of preparation method who is integrated with the micro-fluidic chip of Electrochemical Detection function is provided, and this micro-fluidic chip has good photochemistry processing characteristics, good electrophoretic separation performance and good Electrochemical Detection performance.
A kind of preparation method of micro-fluidic chip comprises the steps:
(1), the preparation of glass-chip: choose Li 2O-Al 2O 3-SiO 2Glass ingredient, add an amount of photosensitizer and nucleus agent, high temperature melting, draw or pour into sheet, it is the glass sheet of 0.2mm-2.0mm that grinding and polishing becomes thickness, handle through photoirradiation, thermal treatment and acid corrosion successively, on glass-chip, obtain to be used for electrophoretic separation microchannel, liquid pool that storaging liquid is used, eliminate the high pressure isolation structure of affected by high and through the opening structure that is used for Integrated electrode of glass-chip material; The microchannel width is that 10-100 micron, the degree of depth are the 10-40 micron;
(2), the CNT working electrode, contrast electrode and integrated to electrode: with above-mentioned glass substrate with component on the lead-in wire that prints electrode, the glass substrate bonding on glass-chip that the first step is made and charged road again, bonding temperature is 400-600 ℃, in electrochemical working electrode micron hole, utilize the electrochemical plating supported catalyst, the employed electroplate liquid of preparation catalyzer is for containing iron, the salt solusion of cobalt and/or nickel, or with the mixed solution of rare earth metal salt, utilize plasma chemical vapor deposition, hot filament CVD or high-temperature cracking method synthesis of carbon nanotube electrode, in the contrast electrode hole, behind the deposition filamentary silver, prepare the Ag/AgCl contrast electrode by anodic oxidation; Utilize electrochemical production electrophoretic separation metal platinum electrode in position, separate mesh electrode hole;
(3), encapsulation: get quartz glass plate, the position of liquid pool punching in respect to glass-chip as the passage of sample, damping fluid injection and discharging of waste liquid, again with the chip material bonding behind this slide and the Integrated electrode, gets micro-fluidic chip.
Described nucleus agent is silver, copper, gold, silver oxide, Cu oxide, silver salt, mantoquita and/or golden salt.
Described photosensitizer is tin-oxide, pink salt, cerium oxide and/or cerium salt.
Described light irradiation processing is fixed on the glass sheet for the mask that will be carved with microchannel, liquid pool, micron hole pattern, utilize the 100W-500W ultraviolet source to glass radiation treatment 1-5 hour, the photoirradiation time at place, micron hole is microchannel, liquid pool exposure time 2 times.
Described glass heat is treated to and places 400-800 ℃ high temperature insulation after 1.0-5.0 hour the glass sheet behind the ultraviolet light irradiation, slowly cooling annealing.
Described acid corrosion is that the glass after the thermal treatment is invaded in the mixed solution of hydrofluorite and hydrochloric acid, etching time 3.0-10.0 hour, acquisition contains the chip material of required microchannel structure, liquid pool and micron Confucianism, wherein HF content is 0.1mol/L in the mixed solution, and HCl content is 0.12mol/L.
Electroplate liquid is the mixed solution that contains nickelous sulfate, cobaltous sulphate and/or iron sulfate and boric acid in the preparation of described CNT electrode, the concentration of each sulfate is 0.01-0.1mol/L, boric acid content is 0.03mol/L, electroplating voltage 10V, electroplating time 30 seconds, the catalyzer nickel film, cobalt film and/or the iron film thickness that are obtained are 10-200nm; Utilize microwave electron cyclotron resonance plasma chemical vapour deposition technique integrated nanometer carbon pipe electrode in the micron hole: microwave power 100-500W, coil magnetization electric current 5-30A, plasma chamber internal pressure 200-1000Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity, synthesising reacting time 10-30min; Or utilize hot filament CVD integrated nanometer carbon pipe electrode in the micron hole: heater power 100-2000W, synthetic cavity internal pressure 1000-4000Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity, generated time 10-30min; Or utilize high-temperature cracking method integrated nanometer carbon pipe electrode in the micron hole: synthesis temperature 400-600 ℃, cavity internal pressure 1000-4000Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity, generated time 10-30min.Gas flow is the amount under the standard state.
The present invention has following major advantage:
1 selected glass-chip material has good photochemistry processing characteristics, is convenient to the integrated of CNT electrode, and chemical stability is good, and liquid pool and microchannel have advantages such as good reproducibility, easily processing, difficult generation dead volume;
2 CNT working electrodes are integrated in the hole of glass-chip material, Stability Analysis of Structures, and the Electrochemical Detection excellent performance, mass transfer velocity is fast, easily sets up the stable state mass transfer, and signal to noise ratio (S/N ratio) is extremely low;
3 can be distributed in the CNT electrode on the chip with array format, and number of electrodes is numerous, and the chip life-span is long;
4 chips have microminiaturization, integrated characteristics, have separation, reaction and measuring ability, and the detection sensitivity height can be used for trace analysis, and scope is wide, is applicable to whole analysis fields of electrochemical response.
Embodiment
Embodiment 1:
A glass-chip material is made:
(1) glass smelting and glass sheet are made: according to following each percentage by weight: 64.32%SiO 2, 4.60%Al 2O 3, 25.65%Li 2O, 3.69%K 2O, 0.71%Na 2O, 1.26%ZnO, 0.025%CeO 2, 0.017%SnO 2, 0.061%Ag 2O, 0.25%Sb 2O 3, get above-mentioned substance and be made into compound, under 1500 ℃ temperature conditions, found into glass metal, melting time varies with temperature, glass metal is drawn into sheet after, grinding and polishing becomes the glass sheet of thick 0.8mm;
(2) light irradiation processing: the mask that will be carved with microchannel, liquid pool, micron hole figures is fixed on the glass sheet, utilizes the 300W ultraviolet source to glass radiation treatment 3 hours, processing time and the ultraviolet source power relation of being inversely proportional to.The photoirradiation time at place, micron hole is 2 times of exposure times such as microchannel, liquid pool;
(3) glass heat is handled: after placing 520 ℃ high temperature to be incubated 2.5 hours the glass sheet behind the ultraviolet light irradiation, and slowly cooling annealing.
(4) acid corrosion: the glass after the thermal treatment is invaded in the mixed solution of hydrofluorite and hydrochloric acid, etching time 5 hours, acquisition contains the chip material in required microchannel structure, liquid pool and micron hole.HF content is 0.1mol/L in the mixed solution, and HCl content is 0.12mol/L.
The B electrode is integrated:
(1) after printing contact conductor on the sheet glass, with the prepared glass-chip bonding that contains microchannel, liquid pool, micron hole of itself and process A, bonding temperature is 560 ℃.
(2) utilize electrochemical plating used catalyzer of load synthesis of carbon nanotube in the micron hole, employed electroplate liquid is the mixed solution of nickelous sulfate and boric acid, wherein nickel sulfate content is 0.02mol/L, boric acid content is 0.03mol/L, electroplating voltage 10V, electroplating time 30 seconds, the catalyzer nickel film thickness that is obtained is 50nm.
(3) utilize microwave electron cyclotron resonance plasma chemical vapour deposition technique integrated nanometer carbon pipe electrode in the micron hole: microwave power 200W, coil magnetization electric current 20A, plasma chamber internal pressure 800Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity, synthesising reacting time 15min.The tolerance flow is the amount under the standard state.
(4) utilizing electrochemical method to prepare respectively in the relevant hole of chip separates with platinum electrode and Ag/AgCl contrast electrode.
The C encapsulation
Getting a thickness is the thick flat glass film of 1.0mm, utilizes laser punching with the corresponding position of chip material upper liquid pool, and the diameter in hole is 0.5mm.Chip material bonding under 560 ℃ of conditions of itself and integrated electrode is got final product.
Embodiment 2:
The materials processing of A glass-chip is with embodiment 1A.
The B electrode is integrated
(1) after printing contact conductor on the sheet glass, with the prepared glass-chip bonding that contains microchannel, liquid pool, micron hole of itself and process A, bonding temperature is 560 ℃.
(2) utilize electrochemical plating used catalyzer of load synthesis of carbon nanotube in the micron hole.Employed electroplate liquid is the mixed solution of cobaltous sulphate and boric acid, and wherein cobaltous sulphate content is 0.02mol/L, and boric acid content is 0.03mol/L, electroplating voltage 10V, and electroplating time 30 seconds, the catalyst cobalt film thickness that is obtained is 50nm.
(3) utilize microwave electron cyclotron resonance plasma chemical vapour deposition technique integrated nanometer carbon pipe electrode in the micron hole: microwave power 200W, coil magnetization electric current 20A, plasma chamber internal pressure 800Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity.Generated time 20min.The tolerance flow is the amount under the standard state.
(4) utilizing electrochemical method to prepare respectively in the relevant hole of chip separates with platinum electrode and Ag/AgCl contrast electrode.
The C encapsulation is with embodiment 1C.
Embodiment 3:
The materials processing of A glass-chip is with embodiment 1A.
The B electrode is integrated
(1) after printing contact conductor on the sheet glass, with the prepared glass-chip bonding that contains microchannel, liquid pool, micron hole of itself and process A, bonding temperature is 560 ℃.
(2) utilize electrochemical plating used catalyzer of load synthesis of carbon nanotube in the micron hole.Employed electroplate liquid is the mixed solution of iron sulfate and boric acid, and wherein iron sulfate content is 0.01/L, and boric acid content is 0.03mol/L, electroplating voltage 10V, and electroplating time 30 seconds, the catalyzer iron film thickness that is obtained is 40nm.
(3) utilize microwave electron cyclotron resonance plasma chemical vapour deposition technique integrated nanometer carbon pipe electrode in the micron hole: microwave power 200W, coil magnetization electric current 20A, plasma chamber internal pressure 800Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity.Generated time 25min.The tolerance flow is the amount under the standard state.
(4) utilizing electrochemical method to prepare respectively in the relevant hole of chip separates with platinum electrode and Ag/AgCl contrast electrode.
The C encapsulation is with embodiment 1C.
Embodiment 4:
The materials processing of A glass-chip is with embodiment 1A.
The B electrode is integrated
(1) after printing contact conductor on the sheet glass, with the prepared glass-chip bonding that contains microchannel, liquid pool, micron hole of itself and process A, bonding temperature is 560 ℃.
(2) utilize electrochemical plating used catalyzer of load synthesis of carbon nanotube in the micron hole, employed electroplate liquid is the mixed solution of cobaltous sulphate, nickelous sulfate and boric acid, wherein cobaltous sulphate content is 0.01mol/L, nickel sulfate content is 0.01mol/L, boric acid content is 0.03mol/L, electroplating voltage 10V, electroplating time 30 seconds, the catalyst cobalt that is obtained, nickel film thickness are 50nm.
(3) utilize microwave electron cyclotron resonance plasma chemical vapour deposition technique integrated nanometer carbon pipe electrode in the micron hole: microwave power 200W, coil magnetization electric current 20A, plasma chamber internal pressure 800Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity.Generated time 30min; The tolerance flow is the amount under the standard state.
(4) utilizing electrochemical method to prepare respectively in the relevant hole of chip separates with platinum electrode and Ag/AgCl contrast electrode.
The C encapsulation is with embodiment 1C.
Embodiment 5:
The materials processing of A glass-chip is with embodiment 1A.
The B electrode is integrated
(1) after printing contact conductor on the sheet glass, with the prepared glass-chip bonding that contains microchannel, liquid pool, micron hole of itself and process A, bonding temperature is 560 ℃.
(2) utilize electrochemical plating used catalyzer of load synthesis of carbon nanotube in the micron hole.Employed electroplate liquid is the mixed solution of cobaltous sulphate, nickelous sulfate and boric acid, and wherein cobaltous sulphate content is 0.02mol/L, and nickel sulfate content is 0.03mol/L, boric acid content is 0.03mol/L, electroplating voltage 10V, electroplating time 30 seconds, the catalyst cobalt that is obtained, nickel film thickness are 70nm.
(3) utilize microwave electron plasma chemical vapor deposition integrated nanometer carbon pipe electrode in the micron hole: microwave power 300W, plasma chamber internal pressure 1500Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity, generated time 10min.The tolerance flow is the amount under the standard state.
(4) utilizing electrochemical method to prepare respectively in the relevant hole of chip separates with platinum electrode and Ag/AgCl contrast electrode.
The C encapsulation is with embodiment 1C.
Embodiment 6:
The materials processing of A glass-chip is with embodiment 1A.
The B electrode is integrated
(1) after printing contact conductor on the sheet glass, with the prepared glass-chip bonding that contains microchannel, liquid pool, micron hole of itself and process A, bonding temperature is 560 ℃.
(2) utilize electrochemical plating used catalyzer of load synthesis of carbon nanotube in the micron hole.Employed electroplate liquid is the mixed solution of cobaltous sulphate, nickelous sulfate and boric acid, and wherein cobaltous sulphate content is 0.02mol/L, and nickel sulfate content is 0.03mol/L, boric acid content is 0.03mol/L, electroplating voltage 10V, electroplating time 30 seconds, the catalyst cobalt that is obtained, nickel film thickness are 70nm.
(3) utilize hot filament CVD integrated nanometer carbon pipe electrode in the micron hole: heater power 200W, synthetic cavity internal pressure 2100Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity.Generated time 10-30min.The tolerance flow is the amount under the standard state.
(4) utilizing electrochemical method to prepare respectively in the relevant hole of chip separates with platinum electrode and Ag/AgCl contrast electrode.
The C encapsulation is with embodiment 1C.
Embodiment 7
The materials processing of A glass-chip is with embodiment 1A.
The B electrode is integrated
Its step (1) and step (2) be step (1) and the step (2) in integrated with the electrode of embodiment 6.After in the micron hole, preparing catalyzer, utilize high-temperature cracking method integrated nanometer carbon pipe electrode in the micron hole: 520 ℃ of synthesis temperatures, cavity internal pressure 3000Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity, generated time 20min.The tolerance flow is the amount under the standard state.
Embodiment 8
Utilize the Ag in gold replacement embodiment 1 glass ingredient 2O, consumption are 0.061%, with embodiment 1 identical condition under carry out that glass-chip material preparation, light irradiation processing, glass heat processing, acid corrosion and CNT electrode are integrated, Chip Packaging etc., can prepare micro-fluidic chip.

Claims (9)

1, a kind of preparation method of micro-fluidic chip comprises the steps:
(1), the preparation of glass-chip: choose Li 2O-Al 2O 3-SiO 2Glass ingredient, add an amount of photosensitizer and nucleus agent, high temperature melting, draw or pour into sheet, it is the glass sheet of 0.2mm-2.0mm that grinding and polishing becomes thickness, handle through photoirradiation, high temperature and acid corrosion successively, on glass sheet, etch microchannel, liquid pool, high pressure isolation structure and be used for the hole of Integrated electrode;
(2), the CNT working electrode, contrast electrode and integrated to electrode: with above-mentioned glass substrate with component on the lead-in wire that prints electrode, the glass substrate bonding on glass-chip that the first step is made and charged road again, bonding temperature is 400-600 ℃, supported catalyst in electrochemical working electrode micron hole, catalyzer is that employed electroplate liquid contains iron, the salt solusion of cobalt and/or nickel, or with the mixed solution of rare earth metal salt, utilize plasma chemical vapor deposition, hot filament CVD or high-temperature cracking method synthesis of carbon nanotube electrode, in the contrast electrode hole, behind the deposition filamentary silver, prepare the Ag/AgCl contrast electrode by anodic oxidation; Utilize electrochemical production electrophoretic separation metal platinum electrode in position, separate mesh electrode hole;
(3), encapsulation: get quartz glass plate, the position of liquid pool punching in respect to glass-chip again with the chip material bonding behind this slide and the Integrated electrode, gets micro-fluidic chip.
2, method according to claim 1 is characterized in that: described nucleus agent is silver, copper, gold, silver oxide, Cu oxide, silver salt, mantoquita and/or golden salt.
3, method according to claim 1 is characterized in that: described photosensitizer is tin-oxide, pink salt, cerium oxide and/or cerium salt.
4, method according to claim 1, it is characterized in that: described light irradiation processing is fixed on the glass sheet for the mask that will be carved with microchannel, liquid pool, micron hole pattern, utilize the 100W-500W ultraviolet source to glass radiation treatment 1-5 hour, the photoirradiation time at place, micron hole is microchannel, liquid pool exposure time 2 times.
5, method according to claim 1 is characterized in that: described glass pyroprocessing is incubated after 1.0-5.0 hour for the glass sheet behind the ultraviolet light irradiation is placed 400-800 ℃ high temperature, slowly cooling annealing.
6, method according to claim 1, it is characterized in that: described acid corrosion is for immersing the glass after the thermal treatment in the mixed solution of hydrofluorite and hydrochloric acid, etching time 3.0-10.0 hour, acquisition contained the chip material of required microchannel structure, liquid pool and micron Confucianism.
7, method according to claim 6 is characterized in that: HF content is 0.1mol/L in the described acid corrosion mixed solution, and HCl content is 0.12mol/L.
8, method according to claim 1, it is characterized in that: contain nickelous sulfate, cobaltous sulphate and/or ferrum sulfuricum oxydatum solutum in the preparation electrodeposit liquid of described CNT electrode, mixed solution with boric acid, nickelous sulfate, cobaltous sulphate or ferrum sulfuricum oxydatum solutum concentration are respectively 0.01-0.1mol/L, boric acid content is 0.03mol/L, electroplating voltage 10V, electroplating time 30 seconds, the catalyzer nickel film, cobalt film and/or the iron film thickness that are obtained are 10-200nm; Utilize microwave electron cyclotron resonance plasma chemical vapour deposition technique integrated nanometer carbon pipe electrode in the micron hole: microwave power 100-500W, coil magnetization electric current 5-30A, plasma chamber internal pressure 200-1000Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity, synthesising reacting time 10-30min; Or utilize hot filament CVD integrated nanometer carbon pipe electrode in the micron hole: heater power 100-2000W, synthetic cavity internal pressure 1000-4000Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity, generated time 10-30min; Or utilize high-temperature cracking method integrated nanometer carbon pipe electrode in the micron hole: synthesis temperature 400-600 ℃, cavity internal pressure 1000-4000Pa, 5 cubic centimetres of per minutes of methane flow, 200 cubic centimetres of per minutes of hydrogen flowing quantity, generated time 10-30min.
9, method according to claim 1 is characterized in that: described microchannel width is that 10-100 micron, the degree of depth are the 10-40 micron.
CNB2005100197203A 2005-11-03 2005-11-03 Method for producing miniflow control chip Expired - Fee Related CN100425984C (en)

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CN101294972B (en) * 2008-06-17 2011-08-31 浙江大学 Production method of glass micro-nano flow control integrated chip
CN102012414A (en) * 2010-06-28 2011-04-13 芜湖新兴铸管有限责任公司 Method for detecting total content of rare earth in high-content silicon rare earth alloy
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CN104587930A (en) * 2014-12-24 2015-05-06 东南大学 Synthesis of metal/carbon nanotube composite nanowires and special micro/nano reactor
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CN105567547A (en) * 2015-12-11 2016-05-11 武汉友芝友医疗科技股份有限公司 Manufacturing method of non-uniform equal-height gradient cell-capturing chip
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CN110937805A (en) * 2019-11-04 2020-03-31 中国建筑材料科学研究总院有限公司 Photoetching lithium-aluminum-silicon glass material and preparation method and application thereof
CN110937805B (en) * 2019-11-04 2022-03-11 中国建筑材料科学研究总院有限公司 Photoetching lithium-aluminum-silicon glass material and preparation method and application thereof

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