CN106513068A - Solution used for bonding and surface modification of micro-fluidic chips made from polymer and application thereof - Google Patents

Solution used for bonding and surface modification of micro-fluidic chips made from polymer and application thereof Download PDF

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Publication number
CN106513068A
CN106513068A CN201610941525.4A CN201610941525A CN106513068A CN 106513068 A CN106513068 A CN 106513068A CN 201610941525 A CN201610941525 A CN 201610941525A CN 106513068 A CN106513068 A CN 106513068A
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bonding
chip
solution
micro
modified
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CN106513068B (en
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郭永
苏世圣
杨文军
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Beijing Xinyi Biotechnology Co Ltd
Tsinghua University
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Beijing Tianjian Wellcome Biotechnology Co Ltd
Tsinghua University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • B01L3/502707Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Hematology (AREA)
  • Clinical Laboratory Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

The invention discloses a solution used for bonding and surface modification of micro-fluidic chips made from polymer, and the solution comprises a solution buffering composition, a bonding composition and a surface modification composition; the solution buffering composition, the bonding composition and the surface modification composition are mutually soluble, reaction doesn't occur, and the chip cannot be corroded simultaneously. The solution used for bonding and surface modification of the micro-fluidic chips made from the polymer is suitable for large scale chip bonding, and the production flux is high; the bonding dead zones are few, and the strength is high; the equipment is simple, and the production cost is low; and after bonding, the pipeline deformation is small.

Description

For polymerizable material micro-fluidic chip bonding with surface be modified solution and its Using
Technical field
The present invention relates to a kind of micro-fluidic chip field, and in particular to a kind of micro-fluidic chip key for polymerizable material Close the solution and its application being modified with surface.
Background technology
Microfluidic chip technology feature is, based on micro-processing technology, will to realize sample feeding, mixing, reaction and detect Etc. function structure assembly in several square centimeters of chip.In field of biochemistry detection, microfluidic chip technology has logical Measure high high, detection sensitivity, low cost and be easy to the potential advantages such as automatization, thus with very wide application prospect.
Chip bonding is an important step in micro-fluidic chip process of manufacture.Chip bonding is referred to by micro- The structures such as micro- raceway groove, micro- hole and through hole that processing is obtained, are packaged into closed microchannel, microcavity body and sample import and export etc..With Polymer has thermocompression bonding, mono-/bis-face glue bonding and organic solution auxiliary for the conventional bonding method of the micro-fluidic chip of material Bonding.
(1) mode of thermocompression bonding is adapted to the bonding between polymer chip, is by applying certain temperature to bonding face Degree, temperature close on or reach polymer glass temperature, allow bonding face to reach the state of softening, while apply certain pressure, Allow bonding face that fusion occurs, complete chip bonding.Thermocompression bonding has bond strength high, without the need for extra auxiliary reagent, thus Noresidue in pipeline.But being disadvantageous in that needs higher temperature;And due to the problem of heat transfer, often thermocompression bonding needs Longer time;Stress control also has certain requirement.
(2) glue bonding in mono-/bis-face referred to and acted on bonding face using mono-/bis-face glue, the method for making chip bonding.It is this Requirement of the method to mono-/bis-face glue is relatively more, and the compatibility of the intensity, biological sample that are such as bonded, hydrophilic and hydrophobic etc. are required.This Plant method bonding process simple, it is easy to large-scale production.But compared with other bonding patterns, bond strength is not often high;Glue Composition is easily formed to biochemical reaction and is disturbed;Most of glue all easily produces background fluorescence, optical detection is formed and is disturbed.
(3) organic solution auxiliary bonding is that have infiltration, the effect for softening to polymer chip substrate using organic solution, So that bonding face permeates each other in bonding process, after organic solvent volatilization, bonding face is hardened again and is bonded together, and is completed Bonding.Organic solution auxiliary bonding is high with bond strength, and bonding blind area is few, and bonding speed is fast, low cost and remains without reagent The advantages of, it is particularly suitable for large-scale production process.But traditional organic solvent easily corrodes chip structure so that chip structure is sent out Raw deformation, affects the work of chip.
It is another important link in micro-fluidic chip production that surface is modified.Modified the referring in surface is keeping chip material On the premise of originality energy, give its surface new performance.Due to the characteristic of chip base material, such as hydrophobe characteristic, often without Method meets requirement, so that surface is carried out to its pipe surface being modified, the conventional process for modifying surface of micro-fluidic chip has wet Method is modified and vapour deposition both approaches.
(1) it is wet-process modified by liquid reagent process chip pipeline, change its hydrophobe characteristic.This method has very extensive Application, especially in micro-fluidic chip academic research field, principle is by the liquid reagent micro-fluidic chip made of injection It is interior so as to hydrophilic or hydrophobic functional layer is formed on inner-walls of duct, reach the purpose of modification surface characteristic.This method has Reagent cost is low, be adapted to manual operation the advantages of.But in large-scale production, wet treatment needs for reagent to lead to every chip Pipeline in, this just becomes very poorly efficient, limits production flux.
(2) vapour deposition be using the physics, chemical process occurred in gas phase, chip pipe surface formed feature or Ornamental metal, nonmetallic or compound coat.Vapour deposition can process large batch of chip simultaneously, thus relatively be adapted to big Scale processes.But as vapour deposition generally requires the environment of vacuum, therefore equipment cost is very high.Meanwhile, to control The modified concordance in good surface everywhere, it is also desirable to very complicated control.
The content of the invention
The present invention is in order to solve the above problems, there is provided a kind of micro-fluidic chip bonding for polymerizable material is changed with surface The solution of property, the solution include following components:Buffer components, linked component and surface-modifying component, the buffer components, key Charge-coupled point dissolves each other with surface-modifying component, and does not react, while chip will not be corroded;The buffer components control key is charge-coupled Divide the softening rate to chip so that can realize that chip bonding softens chip again not too much, the buffer components are molten with described The volume range of liquid is 20%~90%, it is therefore preferable to 30%~80%, more preferably 40%-70%;The bonding group Divide and cause chip surface to become to soften, after its evaporation, bonding, the linked component and the solution are realized in chip bonding face Volume range is 10%~90%, it is therefore preferable to 20%~80%, more preferably 30%-60%;It is modified with the surface Component is hydrophobic silane, and its molecular structure isWherein halogen can be F, Cl, Br, I atom, halogen Prime number amount is 1 to 3, and the carbon number of alkane chain is 1 to 20, and the H atom of alkane chain can be partly or entirely by halogen substiuted;Institute The volume range that surface-modifying component is stated with the solution is 0%~20%;Preferably 5%~15%, more preferably 8%-12%.
In one embodiment, buffer components are selected from pentane, hexane, octane, amylene, hexene, octene and nonene one Plant or various.
In one embodiment, linked component is in the middle of acetone, dichloromethane, chloroform, toluene, benzene Plant or various.
In one embodiment, surface-modifying component is selected from dimethylchlorosilane, trim,ethylchlorosilane, diformazan bromide Silane, bromotrimethylsilane, dimethyl iodine silane, Iodotrimethylsilane, hexadecyl trichlorosilane, trichlorine (octyl group) silane and One or more in the middle of trichlorine (1H, 1H, 2H, 2H- perfluoro capryl) silane.
In one embodiment, polymerizable material be Merlon, polymethyl methacrylate, polydimethylsiloxanes Alkane or polystyrene.
In one embodiment, the present invention is provided a kind of micro-fluidic chip bonding for polymerizable material and is changed with surface Property method, the method comprising the steps of:
Step 1:The solution that the above-mentioned micro-fluidic chip bonding for polymerizable material of configuration is modified with surface;
Step 2:The bonding face that needs of the micro-fluidic chip of polymerizable material is fully infiltrated into configured in step 1 molten In liquid;
Step 3:By the chip bonding infiltrated in step 2 in the face of neat assembling, be bonded, control bonding temperature 10~ 120 DEG C, bonding time is controlled at 10 seconds~20 minutes;
Step 4:After the completion of bonding, the solution remained in chip is blown off with dry air.Beneficial effects of the present invention:
1. produce flux high, be adapted to monster chip bonding.As, in monster chip production process, surface is modified past It is past more time-consuming.The present invention is bonded polymer chip and surface the two important processing environments that are modified unite two into one, Surface is carried out while bonding to be modified, the wet-process modified problem for being not suitable for large-scale production process is not only solved, while also Eliminating individually carries out the modified production link of chip surface, therefore greatly improves the flux of production.
2 bonding blind areas are few, and intensity is high.The method of the bonding chip of the present invention is that the side of bonding is aided in based on organic solution Method, thus also inherit its bonding blind area it is few, the high advantage of bond strength.
3 equipment are simple, low production cost.The present invention by it is wet-process modified be integrated in organic solution auxiliary bonding during, Thus required device systems are fairly simple.Simultaneously as wet-process modified and organic solution auxiliary bonding all has production cost Low advantage, thus the present invention similarly has the advantages that low production cost.
After 4 bondings, the deformation of pipeline is little.Due to containing buffer components in the present invention, chip pipeline configuration can be formed and be protected Shield, reduces impact of the linked component to pipeline form so that the deformation of pipeline is little after bonding.
Description of the drawings
For the technical scheme being illustrated more clearly that in the embodiment of the present application, below by to be used needed for embodiment Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments described in the application, right For those of ordinary skill in the art, on the premise of not paying creative work, can be obtaining which according to these accompanying drawings Its accompanying drawing.
The Contact-angle measurement figure of PMMA chip surfaces of the Fig. 1 to process without mixed solution in embodiment 1;
The Contact-angle measurement figure of PMMA chip surfaces of the Fig. 2 to process through mixed solution in embodiment 1;
The result figure of drop formation chip production drops of the Fig. 3 to be bonded by mixed solution A in embodiment 2;With
The result figure of drop formation chip production drops of the Fig. 4 to be bonded by mixed solution B in embodiment 2.
Specific embodiment
In order that art technology field personnel more fully understand the technical scheme in the application, below in conjunction with following knot The invention will be further described to close embodiment, it is clear that described embodiment is only some embodiments of the present application, and not It is whole embodiments.Based on the embodiment in the application, those of ordinary skill in the art are not before creative work is made The all other embodiment for being obtained is put, should all belong to the scope of the application protection.Below in conjunction with the accompanying drawings and instantiation The invention will be further described.
Change of one mixed solution of embodiment to PMMA material hydrophilic and hydrophobics
Step one:The PMMA chips of two panels surfacing are taken, length and width are respectively about 3cm, thickness 5mm;It is positioned in pure water, Cleaned with supersonic cleaning machine, and dried.
Step 2:Configuration 1ml mixed solutions, wherein 500 μ l of buffer components, 400 μ l of linked component, surface-modifying component 100μl.Wherein, buffer components composition is normal hexane, and linked component is chloroform, surface-modifying component be trichlorine (1H, 1H, 2H, 2H- perfluoro capryl) silane, its structural formula isThen stir.
Step 3:Oxygen plasma process, process time 60 seconds are carried out to the two panels PMMA chip in step one.
Step 4:Two panels PMMA chip is kept flat, by 1ml mixed solutions uniform application a piece of PMMA chip lists wherein Face, another is not processed.Two panels chip is each positioned in ventilated container, in container, temperature is set to 50 DEG C.Treat 30 points Take out after clock, and the solution that will be remained on processed chip is blown away with dry air, stand 10 minutes.
Step 5:Two panels chip is positioned on contact angle measurement, respectively the distilled water water droplet of 2 μ l of Deca, is clapped after 5 seconds Contact angle photo is taken the photograph, and is measured with goniometry.Untreated PMMA chip surfaces contact angle is 72 °, as a result such as Fig. 1.It is mixed The PMMA chip surfaces contact angle for closing solution process is 113 °, and contact angle increased 41 °, as a result such as Fig. 2.
Embodiment two is bonded the generation that PC chips realize drop using mixed solution
Step one:The PC chip two panels with cross pipeline is taken, chip length and width are 3cm, and pipeline is deep 100 μm, wide 100 μ M, four branches ends of cross pipeline have been all connected with through hole, and through hole can be used by the gateway as fluid.Separately take and do not contain pipe The PC chips of road and through-hole structure, length and width are 3cm.Four chips are cleaned with supersonic cleaning machine, and is dried.
Step 2:Configuration mixed solution A 1ml, including 500 μ l of buffer components, 400 μ l of linked component, surface-modifying component 100μl.Wherein, buffer components composition is 1- hexenes, and linked component is dichloromethane, surface-modifying component be trichlorine (1H, 1H, 2H, 2H- perfluoro capryl) silane.Configure the mixed solution B1ml without surface treatment component, including 600 μ l of buffer components, bonding 400 μ l of component.Wherein, buffer components are 1- hexenes, and linked component is dichloromethane.
Step 3:Oxygen plasma process, process time 60 seconds are carried out to four PC chips in step one.
Step 4:The PC chips that two panels does not contain pipeline configuration are kept flat, by 1ml mixed solution As uniform application wherein A piece of PC chip surfaces, mixed solution B uniform applications are on another surface.After standing 10 seconds, by other two panels PC chip belt pipe Road structure faces down, and the face for smearing mixed solution with other two panels PC chip closely forces together, pressure is 50N.Keep Pressure is simultaneously placed them in ventilated container, and in container, temperature is set to 80 DEG C.Took out after ten minutes.Now chip has been Bonding is finished, and obtains two complete chips.
Step 5:The solution remained in chip is blown away with dry air, 10 minutes are stood.
Step 6:Utilizing syringe to inject water and mineral oil in two panels chip respectively is used to generate drop.Wherein, cross One pipeline injection water of pipeline, flow velocity is 800 μ l/h, and its two adjacent pipeline injection mineral oil, flow velocity are 600 μ l/ H, water and mineral oil converge at cross, then flow to remaining pipeline together, and flow out from outlet.In such cases, drop Generation need pipeline that there is certain hydrophobicity.The interaction process of cross intersection water and mineral oil is used under the microscope High speed camera is recorded, as a result such as Fig. 3, Fig. 4.With the chip of mixed solution A bonding due to containing surface treatment agent, inner-walls of duct It is with hydrophobic, therefore, it is possible to generate the drop of size uniformity.And the chip being bonded with mixed solution B does not carry out pipeline Surface is modified, and unmodified pipeline hydrophobicity not enough, thus cannot generate drop.Whole process chip sealing is good, and mixed The chip of conjunction solution A bonding can carry out surface and be modified to pipeline, illustrate that the present invention is provided simultaneously with bonding chip and is modified with surface Ability.Jing is measured, and the chip bonding intensity of mixed solution A bonding is up to 113N/cm2, the chip bonding of mixed solution B bondings Intensity is up to 152N/cm2
It should be understood that the present invention for disclosing is not limited only to specific method, scheme and the material for describing, because these Equal alterable.It will also be understood that purpose of the terminology used here just for the sake of the specific embodiment scheme of description, rather than It is intended to limit the scope of the present invention, the scope of the present invention is limited solely by appended claim.
Those skilled in the art will also be appreciated that or be able to confirm that and use no more than normal experiment, institute herein Many equivalents of the specific embodiment of the present invention for stating.These equivalents are also contained in appended claim.

Claims (6)

1. be used for polymerizable material micro-fluidic chip bonding with surface be modified solution, it is characterised in that the solution include with Lower component:Buffer components, linked component and surface-modifying component, the buffer components, linked component and surface-modifying component are mutual It is molten, and do not react, while chip will not be corroded;
The buffer components control softening rate of the linked component to chip so that can realize that chip bonding softens core again not too much Piece, it is 20%~90% with the volume range of the solution that the buffer components are, it is therefore preferable to 30%~80%, more preferably Ground is 40%-70%;
The linked component causes chip surface to become to soften, and after its evaporation, bonding, the bonding group are realized in chip bonding face The volume range with the solution is divided to be 10%~90%, it is therefore preferable to 20%~80%, more preferably 30%-60%; With
The surface-modifying component is hydrophobic silane, and its molecular structure isWherein halogen can be F, Cl, Br, I atom, halogen quantity are 1 to 3, and the carbon number of alkane chain is 1 to 20, the H atom of alkane chain can part or All by halogen substiuted;The surface-modifying component is 0%~20% with the volume range of the solution;Preferably 5% ~15%, more preferably 8%-12%.
2. the solution that the micro-fluidic chip bonding according to claim 1 is modified with surface, it is characterised in that the buffering group It is divided into selected from pentane, hexane, one or more of octane, amylene, hexene, octene and nonene.
3. the solution that the micro-fluidic chip bonding according to claim 1 is modified with surface, it is characterised in that the bonding group One or more be divided in the middle of acetone, dichloromethane, chloroform, toluene, benzene.
4. the solution that the micro-fluidic chip bonding according to claim 1 is modified with surface, it is characterised in that the surface changes Property component be selected from dimethylchlorosilane, trim,ethylchlorosilane, dimethyl bromo-silicane, bromotrimethylsilane, dimethyl iodine silane, Iodotrimethylsilane, hexadecyl trichlorosilane, trichlorine (octyl group) silane and trichlorine (1H, 1H, 2H, 2H- perfluoro capryl) silane Central one or more.
5. the solution that the micro-fluidic chip bonding according to claim 1 is modified with surface, it is characterised in that the polymer Material is Merlon, polymethyl methacrylate, polydimethylsiloxane or polystyrene.
6. a kind of micro-fluidic chip for polymerizable material is bonded and surface modifying method, it is characterised in that methods described includes Following steps:
Step 1:The solution of configuration claim 1;
Step 2:The bonding face that needs of the micro-fluidic chip of polymerizable material is fully infiltrated into the solution for being configured in step 1 In;
Step 3:By the chip bonding infiltrated in step 2 in the face of neat assembling, be bonded, bonding temperature is controlled at 10~120 DEG C, Bonding time is controlled at 10 seconds~20 minutes;
Step 4:After the completion of bonding, the solution remained in chip is blown off with dry air.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107262173A (en) * 2017-08-03 2017-10-20 广东顺德工业设计研究院(广东顺德创新设计研究院) PDMS micro-fluidic chips and the method that PDMS micro-fluidic chips are prepared based on wet etching
CN111167526A (en) * 2018-11-13 2020-05-19 中国科学院大连化学物理研究所 Sealing method of acrylic glass microfluidic chip

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CN111167526B (en) * 2018-11-13 2021-05-25 中国科学院大连化学物理研究所 Sealing method of acrylic glass microfluidic chip

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