CN110496657B - Microfluidic chip capable of forming liquid metal droplets and preparation method thereof - Google Patents

Microfluidic chip capable of forming liquid metal droplets and preparation method thereof Download PDF

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CN110496657B
CN110496657B CN201910861630.0A CN201910861630A CN110496657B CN 110496657 B CN110496657 B CN 110496657B CN 201910861630 A CN201910861630 A CN 201910861630A CN 110496657 B CN110496657 B CN 110496657B
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micro
channel
liquid metal
narrow opening
droplets
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CN110496657A (en
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杨浩
蔡逸凡
程亮
李相鹏
朱姝燚
仇铭劼
苏焱
孙飞
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Suzhou University
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Suzhou 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)
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  • Clinical Laboratory Science (AREA)
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Abstract

The invention relates to a micro-fluidic chip for forming liquid metal micron-scale droplets. The method comprises the following steps: a substrate; a micro-channel layer is arranged on the substrate; the micro-channel layer comprises a first micro-channel, a second micro-channel, a narrow opening and a third micro-channel; the first micro-channel is communicated with the second micro-channel through the narrow opening; the width of the first micro-channel and the second micro-channel is far larger than that of the narrow opening; the central axes of the first micro-channel and the second micro-channel in the length direction are on the same straight line; the included angle between the third micro-channel and the first micro-channel is 30 degrees; the first microchannel, the second microchannel, and the third microchannel are used for flowing of liquid metal, generated liquid metal droplets, and a solution, respectively. The micro-fluidic chip and the liquid metal droplet generation method provided by the invention are simple and convenient to operate, the size of the generated droplet is convenient to control, and the cost is low.

Description

Microfluidic chip capable of forming liquid metal droplets and preparation method thereof
Technical Field
The invention relates to the technical field of electrocapillarity, in particular to a micro-fluidic chip capable of forming liquid metal droplets and a preparation method thereof.
Background
At present, the method for making liquid metal droplets is mainly a method for making droplets by using a micro-flow focusing device. The method has many advantages in manufacturing liquid drops, but the manufacturing process is relatively complicated and the operation is complex. Since the prior art mainly uses a fluid shearing force to make liquid metal droplets, another liquid (mostly a mixed solution of glycerol and NaOH) which is immiscible with the liquid metal and has a relatively high viscosity is required for shearing the liquid metal. And two microflow pumps are needed to control the flow rate ratio of the liquid metal and the glycerol-NaOH solution, so that the operation is complicated.
Disclosure of Invention
In view of the above, the present invention provides a method for forming liquid metal droplets and a micro-fluidic chip capable of forming liquid metal droplets, which do not require adjustment and control of the flow rate ratio between the liquid metal and the glycerol-NaOH solution, and thus simplify the operation and process.
In order to solve the above problems, the present invention provides a microfluidic chip capable of forming liquid metal droplets, comprising:
a substrate;
a micro-channel layer is arranged on the substrate;
the micro-channel layer comprises a first micro-channel, a second micro-channel, a narrow opening and a third micro-channel; the first micro-channel is communicated with the second micro-channel through a narrow opening; the width of the first micro-channel and the second micro-channel is far larger than that of the narrow opening; the central axes of the first micro-channel and the second micro-channel in the length direction are on the same straight line; the included angle between the third micro-channel and the first micro-channel is 30 degrees; the first micro-channel, the second micro-channel and the third micro-channel are respectively used for flowing of liquid metal, generated liquid metal droplets and solution;
the micro-channel layer is also provided with through holes which are respectively used for injecting and discharging liquid in the first micro-channel, the second micro-channel and the third micro-channel.
Preferably, the micro flow channel layer is formed of Polydimethylsiloxane (PDMS).
Preferably, the substrate is a glass sheet or a quartz sheet.
A method for preparing a microfluidic chip capable of forming liquid metal droplets comprises the following steps:
providing a substrate;
providing a micro-channel layer, wherein the micro-channel layer comprises a first micro-channel, a second micro-channel, a narrow opening and a third micro-channel; the first micro-channel is communicated with the second micro-channel through a narrow opening; the width of the first micro-channel and the second micro-channel is far larger than that of the narrow opening; the central axes of the first micro-channel and the second micro-channel in the length direction are on the same straight line; the included angle between the third micro-channel and the first micro-channel is 30 degrees; the first micro-channel, the second micro-channel and the third micro-channel are respectively used for flowing of liquid metal, generated liquid metal droplets and solution;
the micro-channel layer is also provided with through holes which are respectively used for injecting and discharging liquid in the first micro-channel, the second micro-channel and the third micro-channel;
and aligning and sealing the substrate with the micro-channel layer provided with the first micro-channel, the second micro-channel, the narrow opening, the third micro-channel and the through hole to obtain the micro-fluidic chip.
Preferably, the specific method for manufacturing the first microchannel, the second microchannel, the narrow opening and the third microchannel comprises:
coating photoresist on a silicon wafer;
baking the silicon wafer coated with the photoresist;
carrying out photoetching process on the baked silicon wafer through a preset mask plate to obtain a micro-channel mold;
enclosing the periphery of the silicon wafer to form a box-shaped cavity;
pouring resin solution into the box-shaped cavity;
and after the resin solution is solidified, separating the resin solution from the silicon chip to obtain a micro-channel layer containing a first micro-channel, a second micro-channel, a narrow opening and a third micro-channel.
Preferably, the alignment is to align the substrate with the corresponding micro flow channel position.
Use of a microfluidic chip capable of forming droplets of liquid metal, comprising:
injecting partial NaOH solution into the first microchannel and the third microchannel through the through hole, and then introducing liquid metal into the liquid first microchannel at the flow rate of 5 mu L/min;
when the liquid metal is close to the narrow opening, reducing the flow rate of the liquid metal to be 2 mu L/min, and slowly moving the liquid metal to the narrow opening; then NaOH solution is introduced into the third micro-channel at the flow rate of 30 mu L/min;
and applying square wave signals to two sides of the through holes of the first micro-channel and the second micro-channel to form liquid metal droplets, wherein the liquid droplets enter the second micro-channel.
Preferably, after the step of extracting the liquid metal, the liquid metal is extracted through the through hole and recycled.
Preferably, the frequency of the square wave signal is: 1 Hz; voltage: 5 Vpp; d, direct current bias: 2.5 Vpp; waveform: square waves; duty ratio: 50 percent.
The primary improvement of the present invention is to provide a microfluidic chip capable of generating liquid metal droplets, comprising: a substrate; a micro-channel layer is arranged on the substrate; the micro-channel layer comprises a first micro-channel, a second micro-channel, a narrow opening and a third micro-channel; the first micro-channel is communicated with the second micro-channel through a narrow opening; the width of the first micro-channel and the second micro-channel is far larger than that of the narrow opening; the central axes of the first micro-channel and the second micro-channel in the length direction are on the same straight line; the included angle between the third micro-channel and the first micro-channel is 30 degrees; the first micro-channel, the second micro-channel and the third micro-channel are respectively used for flowing of liquid metal, generated liquid metal droplets and solution; the micro-channel layer is also provided with through holes which are respectively used for injecting and discharging liquid in the first micro-channel, the second micro-channel and the third micro-channel. In the microfluidic chip provided by the invention, the first microchannel and the second microchannel are communicated through the narrow opening by designing the flow channel, and the width of the first microchannel and the width of the second microchannel are far larger than that of the narrow opening, so that the liquid metal can move towards the direction of the narrow opening under the drive of an electric capillary phenomenon, and once the liquid metal overcomes the surface tension of the liquid metal, a small part of liquid can reach the second microchannel of liquid drops through the narrow opening. Since the liquid metal is no longer physically constrained by the two sidewalls of the throat, the liquid metal gradually expands after leaving the throat. Under the influence of surface tension, the liquid metal flowing out can break up and eventually form spherical droplets.
Secondly, because the material of micro-flow path layer selection is PDMS, the electric field can not penetrate PDMS, and the dielectric constant of PDMS is only 2.76, has increased insulating nature. And finally, as the through hole is also arranged, the liquid metal or the solution can be conveniently led into the micro-channel, and simultaneously, the liquid metal and the solution can be recovered through the through hole, so that the aim of recycling is fulfilled.
The invention also provides a preparation method of the microfluidic chip, the photoetching shape is simple, the preparation process and the packaging are simpler by combining the properties of the material, and the manufacturing cost of the microfluidic chip similar to the product is reduced.
The invention also provides the application of the micro-fluidic chip, and the liquid metal micro-droplets can be effectively formed through the through holes and the micro-channels arranged in the newly designed structure, and can be used as core components in a micro-system, such as a micro-switch, a pump, a mixer and the like, and can also be used in a novel motor, an electrochemical sensor, a 3D microelectrode, a 3D printing structure, a conductive composite material, novel ink-jet printing ink and energy collection equipment. Furthermore, liquid metal droplets of uniform size can be assembled into periodic structures, which may make them useful in optical applications such as radio frequency resonators or reconfigurable optical diffraction gratings.
Drawings
FIG. 1 is a schematic diagram of a substrate provided in accordance with an embodiment of the present invention;
FIG. 2 is a schematic view of a micro channel layer according to an embodiment of the present invention;
FIG. 3 is a schematic view of a microfluidic chip according to an embodiment of the present invention;
fig. 4 is a schematic view of a microfluidic chip provided in an embodiment of the present invention during use.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the present invention will be further described in detail with reference to the following embodiments.
The noun explains:
liquid metal: liquid metal refers to an amorphous metal that can be viewed as a mixture of a positively ionic fluid and a free electron gas. Liquid metal is also a metal that is flowable at room temperature to a liquid state.
A micro-fluidic chip: the micro-fluidic chip technology integrates basic operation units of sample preparation, reaction, separation, detection and the like in the biological, chemical and medical analysis process into a micron-scale chip, and automatically completes the whole analysis process. Due to its great potential in the fields of biology, chemistry, medicine and the like, the method has been developed into a new research field crossing the disciplines of biology, chemistry, medicine, fluid, electronics, materials, machinery and the like.
Electric double layer: electric Double Layer (EDL), refers to the formation of an electric double layer by a liquid metal immersed in an electrolyte that generates a positive surface charge due to the transfer of ions at the interface boundaries, which attracts an opposite negative charge from the surrounding electrolyte.
Electrocapillary phenomenon: since the electrolyte is a semiconductor, a voltage gradient is generated when electricity is applied, and the voltage gradient causes a surface tension gradient, and this phenomenon in which the surface tension varies with the voltage is called an electrocapillary phenomenon. After the electrolyte solution containing the liquid metal is energized, the liquid metal moves from the cathode to the anode.
NaoH solution: the main components are as follows, 50mL of industrial distilled water, and 1g of NaOH. The solution has the following functions: first, a small amount of NaOH solution is injected into the microfluidic channel through the holes 8 and 9 before the experiment, so that the whole channel is internally conductive. Secondly, since the liquid metal itself undergoes oxidation, the liquid metal can be prevented from being oxidized when placed in the NaOH solution. Unless otherwise specified, the solutions in the present invention are all NaOH solutions.
The invention provides a micro-fluidic chip capable of forming liquid metal droplets, which comprises a substrate; a micro-channel layer is arranged on the substrate; the micro-channel layer comprises a first micro-channel, a second micro-channel, a narrow opening and a third micro-channel; the first micro-channel is communicated with the second micro-channel through a narrow opening; the width of the first micro-channel and the second micro-channel is far larger than that of the narrow opening; the central axes of the first micro-channel and the second micro-channel in the length direction are on the same straight line; the included angle between the third micro-channel and the first micro-channel is 30 degrees; the first micro-channel, the second micro-channel and the third micro-channel are respectively used for flowing of liquid metal, the generated liquid metal micro-droplets and solution; the micro-channel layer is also provided with through holes which are respectively used for injecting and discharging liquid in the first micro-channel, the second micro-channel and the third micro-channel.
According to the invention, as shown in fig. 1, comprising a substrate 1, the substrate 1 is a glass or quartz plate for holding things when observing them with a microscope, preferably rectangular, with a size of 76 × 26mm, thicker and better light transmission.
In the figure 2 is a microchannel made of PDMS, comprising a first microchannel 3 (into which liquid metal is introduced), a third microchannel 4 (into which a NaoH solution is introduced), a narrow opening 5 and a second microchannel 6 (into which droplets are generated), which have widths of 200 μm, 150 μm, 50 μm and 900 μm, respectively. And the outlet, the solution injection part and the inlet are respectively perforated with holes 7, 8 and 9 so as to insert capillaries, so that the liquid metal and the solution can flow in and out, and simultaneously, the liquid metal is convenient to recover and reuse so as to reduce the cost. The material used by the micro-flow channel layer is Polydimethylsiloxane (PDMS), which is one of organic silicon, and the PDMS is a polymer material widely applied to the fields of micro-flow control and the like due to the characteristics of low cost, simple use, good adhesion with a silicon wafer, good chemical inertness and the like.
According to the invention, the preparation process of the micro-flow channel layer preferably comprises the following steps: micro-channel photoetching and manufacturing processes: uniformly coating su-82050 photoresist on a silicon wafer at a rotating speed of 2500r/m in a clean room environment, then placing the uniformly coated silicon wafer on a baking table, baking at 65 ℃ for 2min, baking at 95 ℃ for 7min, then placing the silicon wafer under a photoetching machine, and passing through a designed mask plate at 12.4mJ/cm2Exposing for 8s, developing for 2min, drying with nitrogen, and adhering the silicon wafer with plate or double-sided tape to surround the silicon wafer (the silicon wafer is surrounded by the edge, which is equivalent to a glass sheet, and water is poured from the middle of the silicon wafer without leaking). Pouring 30g of PDMS (prepared according to the mass ratio of the curing agent to the PDMS being 1: 10) on a silicon chip, heating the silicon chip on a heating plate for 40min at 85 ℃, then taking down the silicon chip, tearing off the cured PDMS to obtain a micro-channel, and then punching holes at the outlet, the inlet and the solution injection part of the micro-channel to facilitate the connection of a catheter or a needle.
The substrate 1 is placed below and the PDMS channel 2 is placed above, aligned by the alignment platform, and tightly bonded to prevent liquid leakage.
According to the invention, the alignment is preferably carried out by placing the substrate and the micro-channel layer in a plasma cleaning machine for cleaning for 2min, taking out, pressing, and heating at 95 ℃ for 10min on a baking table. And after the micro-fluidic chip is taken down, inserting capillaries into the outlet hole 7, the inlet hole 9 and the solution injection hole 8 to obtain the final micro-fluidic chip.
When the microfluidic chip provided by the invention is used, as shown in figure 3, a small amount of NaOH solution is firstly injected into the first microchannel and the third microchannel through the through hole, and then liquid metal is introduced into the first microchannel 3 at the flow rate of 5 muL/min so that the liquid metal flows towards the direction of the narrow opening 5. When the liquid metal is close to the narrow opening 5, reducing the flow rate of the liquid metal to 2 mu L/min, and slowly moving the liquid metal to the narrow opening; then NaOH solution is introduced into the third micro-channel 4 at the flow rate of 30 mu L/min;
then, square wave signals (frequency: 1 Hz; voltage: 5 Vpp; DC bias: 2.5 Vpp; waveform: square wave; duty ratio: 50%) are applied across the entrance aperture 9 and the exit aperture 7. Driven by the electro-capillary phenomenon, the liquid metal will move towards the narrow opening 5, and once the liquid metal overcomes its surface tension, a small portion of the liquid will reach the second microchannel 6 of the droplet through the narrow opening 5. Since the liquid metal is no longer physically constrained by the two sidewalls of the throat, the liquid metal gradually expands after passing through the throat. The liquid metal will break up under the influence of surface tension and eventually become spherical droplets, forming liquid metal droplets as shown in fig. 4.
After the experiment is finished, the liquid metal can be recycled from the inlet by sucking air, and the cost is reduced.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (3)

1. Use of a microfluidic chip capable of forming droplets of liquid metal, said microfluidic chip comprising:
a substrate;
a micro-channel layer is arranged on the substrate;
the micro-channel layer comprises a first micro-channel, a second micro-channel, a narrow opening and a third micro-channel; the first micro-channel is communicated with the second micro-channel through the narrow opening; the width of the first micro-channel and the second micro-channel is far larger than that of the narrow opening; the central axes of the first micro-channel and the second micro-channel in the length direction are on the same straight line; the included angle between the third micro-channel and the first micro-channel is 30 degrees; the first micro-channel, the second micro-channel and the third micro-channel are respectively used for flowing of liquid metal, the generated liquid metal micro-droplets and solution;
the micro-channel layer is provided with through holes which are respectively used for injecting and discharging liquid in the first micro-channel, the second micro-channel and the third micro-channel;
the application comprises the following steps:
injecting partial NaOH solution into the first microchannel and the third microchannel through the through hole, and then introducing liquid metal into the first microchannel at the flow rate of 5 mu L/min;
when the liquid metal is close to the narrow opening, reducing the flow rate of the liquid metal to be 2 mu L/min, and slowly moving the liquid metal to the narrow opening; then NaOH solution is introduced into the third micro-channel at the flow rate of 30 mu L/min;
and applying square wave signals to two sides of the through holes of the first micro-channel and the second micro-channel to form liquid metal droplets, wherein the droplets enter the second micro-channel.
2. The use of claim 1, further comprising, after completion, withdrawing liquid metal through said through-hole for recycling.
3. Use according to claim 1, characterised in that the frequency of the square wave signal is: 1 Hz; voltage: 5 Vpp; d, direct current bias: 2.5 Vpp; waveform: square waves; duty ratio: 50 percent.
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CN111135880B (en) * 2019-12-09 2021-10-15 中国科学院微电子研究所 Tractor, traction system and gravity measuring method thereof
CN111495454B (en) * 2020-05-27 2022-07-05 北京机械设备研究所 Liquid metal flow control structure and method based on electromagnetic drive
CN111849767A (en) * 2020-06-24 2020-10-30 东南大学 Three-dimensional micro-fluidic chip level cell culture case
CN114130440B (en) * 2021-11-26 2022-11-04 哈尔滨工业大学 Automatically controlled initiative lane pumping device based on gallium-based liquid metal liquid drop

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