CN108855260B - Paraffin micro-valve forming and packaging method thereof - Google Patents

Paraffin micro-valve forming and packaging method thereof Download PDF

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Publication number
CN108855260B
CN108855260B CN201810624744.9A CN201810624744A CN108855260B CN 108855260 B CN108855260 B CN 108855260B CN 201810624744 A CN201810624744 A CN 201810624744A CN 108855260 B CN108855260 B CN 108855260B
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paraffin
cavity
micro
heating
air
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CN108855260A (en
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王光辉
杨佳辰
王夷惠
谭杰
刘伉伉
李忠文
张畅斌
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Nanjing Dieguang Biotechnology Co ltd
Nanjing University
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Nanjing Dieguang Biotechnology Co ltd
Nanjing 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
    • B01L3/502738Containers 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 integrated valves
    • 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

Abstract

A paraffin micro valve forming and fast packaging method comprises a paraffin micro valve forming device and a paraffin micro valve packaging method. On the basis of static encapsulation, a method of adding an air cavity outside a cavity (namely a solid paraffin storage cavity) in which paraffin is encapsulated is utilized, the air cavity and the solid paraffin storage cavity are heated, so that air in the air cavity is heated and expanded, the generated force pushes the paraffin which is heated into a molten state at the moment to enter the cavity to be encapsulated, and the paraffin encapsulation of the cavity is completed after the paraffin in the cavity is completely cooled.

Description

Paraffin micro-valve forming and packaging method thereof
Technical Field
The invention relates to a paraffin valve rapid packaging method, in particular to a paraffin micro-valve forming device and a paraffin micro-valve rapid packaging method based on electric heating.
Background
In a micro-fluidic chip system, a micro valve is used as a component capable of controlling the closed and open states of a micro channel, can control the circulation condition of liquid, influences the integration level of a chip and plays an important role. Bevan first proposed a phase change valve in 1995, which allowed active cooling of the microfluid when it was necessary to close the valve, so that part of the microfluid rapidly freezes within a very short time to block the microchannel, and when it was necessary to open the valve, the frozen microfluid was heated to melt it, so that the valve was opened. The paraffin valve belongs to one of phase change valves, and in the development process of the phase change valve, paraffin is widely applied due to the advantages of low melting point, strong plasticity, simple manufacturing operation and the like. Because the size of the micro valve is generally in millimeter level or even micron level, the traditional paraffin production process can not meet the requirement, the existing mode mainly adopts a mode of singly molding a high-precision injector in a laboratory, the efficiency is low, and the paraffin phase change valve can not be produced in large scale.
Disclosure of Invention
The invention aims to provide a paraffin micro-valve forming and packaging method which is simple in structure, convenient to use, high in efficiency and convenient to operate.
In order to achieve the purpose, the invention adopts the following technical scheme:
the paraffin wax micro-valve with the same specification is produced in batches by using a mould, then the paraffin wax micro-ball is placed in the micro-valve to be packaged corresponding to the chip, the chip is packaged, the paraffin wax is slightly melted by utilizing resistance heating, and is formed again after being cooled and is tightly combined with the channel wall to form the well-sealed paraffin wax micro-valve.
The paraffin wax microsphere forming device comprises a mould, a heating module, a filling tool and tweezers.
In order to further realize the purpose of the invention, the following technical scheme can be adopted: the paraffin microvalve forming device comprises a die, wherein the die is a cylindrical shell with a certain thickness, and a plurality of paraffin valve-shaped die cavities penetrate through the die. The lower bottom of the mould is provided with a heating module. When in use, the solid paraffin particles are melted by heating, the liquid paraffin is injected into and filled in the die cavity by a pouring tool at a certain temperature, speed and pressure, and the paraffin product with a certain shape and size is obtained by die stripping after compaction, cooling and shaping.
In order to realize the rapid encapsulation of the paraffin microvalve, the molded paraffin microspheres are placed on the corresponding positions of the phase change valves on the chip to encapsulate the chip, at the moment, because of the micro-type property of the channel and other reasons, a certain gap still exists between the paraffin microspheres and the microvalve to be encapsulated, and the microvalve can not be completely closed, so that the paraffin is slightly melted by matching short-time heating, and the paraffin after being cooled and molded again can be tightly attached to the channel wall to form the well-sealed paraffin microvalve.
Compared with the static paraffin encapsulation method, the dynamic encapsulation method of the paraffin microvalve is derived on the basis of the static paraffin encapsulation method. The method specifically comprises the following steps: the micro-pipeline is respectively communicated with the air cavity and the to-be-packaged cavity, preferably, the air cavity and the to-be-packaged cavity are located on two sides of the solid paraffin storage cavity and are respectively connected with the air cavity and the to-be-packaged cavity, the to-be-packaged cavity can be used as a common cavity (such as a sample introduction cavity, a reaction cavity and the like) before being packaged, when the to-be-packaged paraffin wax storage cavity needs to be packaged, the air cavity and the solid paraffin wax storage cavity are respectively heated, the paraffin wax which is heated to be molten state is pushed into the to-be-packaged cavity by utilizing thrust generated by expansion of gas in the air cavity when being heated, and the paraffin wax is.
The invention has the advantages that: the production process is simple, the paraffin solid raw material is injected into a mold of the paraffin microsphere forming device through a high-precision filling tool after being melted, the heating module is used for heating after the paraffin is cooled, so that the paraffin block is separated from the lower bottom of the mold, and the paraffin microspheres are demoulded through the cooperation of the tweezers, so that the production efficiency and the appearance quality of the paraffin microspheres are further improved. In the static packaging process of paraffin, the molded paraffin microspheres are placed in the corresponding micro-valves to be packaged of the chip, the paraffin is slightly melted by heating, and the paraffin can be tightly attached to the channel wall after being cooled, so that the packaging process of the paraffin valve is greatly simplified, and the large-scale production of the paraffin valve is facilitated; in the paraffin dynamic packaging process, through heating, the thrust generated by the expansion of gas under heating pushes the molten paraffin to complete the transfer from one cavity to another cavity, and the flexible and dynamic paraffin packaging is realized on a packaged mature chip on the premise of not damaging the chip structure, so that multiple effects of one cavity are realized. The invention also has the advantages of simple and compact structure, low manufacturing cost, science, practicality, convenient use and the like, and has wide popularization value.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic side view of a paraffin micro-valve molding device.
Fig. 2 is a schematic cross-sectional view of a mold of the paraffin micro-valve molding device.
Fig. 3 is a schematic diagram of the rapid packaging principle of the paraffin valve.
Fig. 4 is a schematic cross-sectional view of a microfluidic chip.
FIG. 5 is a schematic view of the principle of dynamic encapsulation of paraffin microvalves, in which (1) is dynamic encapsulation driven by centrifugal force; (2) dynamic encapsulation of air cavity air pressure drive.
Fig. 6 is a schematic diagram of the specific application of the paraffin micro valve dynamic package.
Fig. 7 is a partial sample package structure diagram. Wherein, the diagram (a) is a chip structure schematic diagram before paraffin packaging, and the diagram (b) is a chip structure schematic diagram after paraffin packaging is completed.
FIG. 8 is a schematic flow diagram of reagent pre-encapsulation.
FIG. 9 is a view of a paraffin encapsulated object.
In the figure: 1, molding; 2 heating the module; 3, molding a die cavity; 4 heating a resistor; 5 phase change valve to be packaged; 6 a phase change valve packaged with paraffin; 7, an air cavity; 8, a solid paraffin storage cavity; 9 air holes (sampling holes); 10 a cavity to be packaged; 11 air cavity heating zone; 12 paraffin heating zone; 13 packaged paraffin microvalve; 14 a sample storage chamber.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
The first embodiment is as follows:
the rapid paraffin micro-valve molding and static packaging system comprises a paraffin micro-valve molding device and a static packaging device as shown in fig. 1, fig. 2 and fig. 3.
The paraffin wax microsphere forming device comprises a die 1, wherein the die 1 is a cylindrical shell with a certain thickness and a die cavity 3 in the shape of a plurality of paraffin wax valves penetrates through the die 1, the shape of the die cavity 3 can be correspondingly adjusted according to the specific shape of a required phase change valve, and the thickness of the die 1 can also be correspondingly adjusted according to the depth of the required paraffin wax microvalve. The lower bottom of the mold 1 is provided with a heating sheet as a heating module 2 in the embodiment.
When the paraffin injection mold is used, solid paraffin particles are heated and melted into a liquid state in advance and are injected into the injection tool, the injection tool in the embodiment is an injector, the injector is pushed to inject the solid paraffin particles into the mold cavity 3 of the mold 1, after the paraffin is compacted and completely cooled, the heating sheet is heated, the paraffin block is partially melted by contacting with the heating sheet, and therefore the paraffin block is conveniently separated from the heating sheet. After the paraffin block is separated from the lower bottom of the mold, the paraffin block is separated from the side periphery adhesion part of the mold cavity by prying and loosening by using tweezers, and the paraffin block is demolded by using the tweezers, so that the separation of the paraffin block and the mold 1 can be completed, and paraffin microspheres with the same specification can be obtained in batches.
As shown in fig. 3, the paraffin wax microspheres obtained in the above steps are placed in the recessed microvalve positions 5 corresponding to the chip, and the chip is packaged, at this time, due to reasons such as manual operation and micro-type property of the microfluidic channel, a gap still exists between the paraffin wax microspheres and the microvalve to be packaged, and the paraffin wax microvalve is not completely closed, so that the paraffin wax needs to be heated for a short time by using the heating resistor 4 arranged below the chip, the temperature of the paraffin wax is 0-5 ℃ higher than the melting point of the paraffin wax, the paraffin wax is in a micro-molten state, and then the micro-flow dynamic state actively diffuses and fills the gap, and the paraffin wax microspheres can be shaped and molded by being cooled again to be tightly combined with the walls of the channel, so that the paraffin wax microvalve can.
Example two:
a paraffin wax micro-valve dynamic packaging system is shown in figure 5(1), and comprises a solid paraffin wax storage cavity 8 and a cavity to be packaged 10, wherein a paraffin wax block with the same size as the cavity is packaged in the solid paraffin wax storage cavity 8 in advance by adopting a static paraffin wax packaging method in the first embodiment, a heating area 12 is arranged at the lower part of the solid paraffin wax storage cavity 8, and an air hole (sample inlet hole) 9 is arranged on the cavity to be packaged 10.
Before waiting that encapsulation chamber 10 does not encapsulate paraffin, can be nimble as ordinary chamber such as appearance chamber, liquid reaction chamber use, in case need it to possess the effect of micro-valve, can heat solid paraffin storage chamber 8 through zone of heating 12, until the paraffin melting in storage chamber 8 becomes liquid, make the interior molten paraffin of solid paraffin storage chamber 8 flow into waiting to encapsulate the chamber 10 with the help of centrifugal force, stop heating when 10 in paraffin tend to saturate, wait that after the paraffin cooling solidification in encapsulation chamber 10, wait that encapsulation chamber 10 has just accomplished paraffin encapsulation and become paraffin micro-valve 13, and solid paraffin storage chamber 8 opens, becomes accessible state.
The paraffin micro valve dynamic packaging method can freely change cavities, valves and channels in the experimental process, and is dynamic and flexible.
Example three:
a paraffin wax micro-valve dynamic packaging system is shown in figure 5(2), and comprises an air cavity 7, a solid paraffin wax storage cavity 8 and a cavity to be packaged 10, wherein a paraffin wax block with the same size as the cavity is packaged in the solid paraffin wax storage cavity 8 in advance by adopting a static paraffin wax packaging method in the first embodiment, heating areas 11 and 12 are respectively arranged below the air cavity 7 and the solid paraffin wax storage cavity 8, and an air hole (sample inlet hole) 9 is arranged in the cavity to be packaged 10.
Before waiting that encapsulation chamber 10 does not encapsulate paraffin, can be nimble as ordinary chamber such as advance a kind chamber, liquid reaction chamber use, in case need it to possess the effect of micro-valve, can be through heating zone 11 to air cavity 7, heating zone 12 heats solid paraffin storage chamber 8 respectively, paraffin in the storage chamber 8 melts into the liquid state, continue to heat, at this moment, because of the thermal expansion of gas in the confined air cavity 7, atmospheric pressure sharply strengthens, the thrust that produces promotes in the solid paraffin storage chamber 8 that the molten paraffin constantly flows into waiting to encapsulate in the chamber 10, stop heating when paraffin among 10 tends to saturate, wait to encapsulate the chamber 10 after paraffin cooling solidification, wait to encapsulate the chamber 10 and just accomplished paraffin encapsulation and become paraffin micro-valve 13.
The paraffin micro valve dynamic packaging method can freely change the cavity and the valve in the experimental process, and is more dynamic and flexible.
Fig. 6 is a practical application case of the paraffin micro-valve dynamic packaging system based on the above. The micro-fluidic chip technology, as a novel technology combining multiple disciplines such as biology, medical treatment, sensing detection and the like, is developing rapidly in the aspect of biological detection at present and is developing towards industrialization with great advantages. The centrifugal force micro-fluidic chip is developed on the basis of the micro-fluidic chip, and the centrifugal force is used for driving the flow of fluid in a micro-channel. The encapsulation of the analysis detection reagent is an indispensable step in the realization of industrial development of the microfluidic chip, plays a vital role in the encapsulation and transportation of the microfluidic chip, and currently, the research on the aspect of the pre-encapsulation of the reagent in the microfluidic chip is less. As a mature product-level microfluidic chip available for users to use directly, a pre-packaging process of storing and packaging a sample (reaction solution) inside the chip before the chip leaves a factory, that is, the sample, is often required. In order to solve a series of problems of sample leakage and splashing in the sample adding and transporting processes, the structure shown in fig. 6 is adopted, and the structure comprises a paraffin dynamic packaging module a and a paraffin dynamic packaging module a' and a sample storage 14. The specific operation process is as follows: the paraffin blocks are stored in the paraffin storage cavity at first, a specific sample is injected into the sample storage cavity 14 through the sample inlet hole 9, after the sample injection step is completed, the two paraffin dynamic encapsulation modules a and a' are started, and the two paraffin micro valves are respectively encapsulated, so that the sample is completely sealed in the sample storage cavity. The packaging chip structure is a local amplification plate, can be used for storing and transporting samples when being used independently, and can be directly integrated into a specific micro-fluidic chip for realizing a specific function to be used as a pre-packaging part of a reagent in the chip.
Example four:
fig. 7 is a partial sample package structure diagram, and as shown in fig. 7 (a), 1 in the diagram is an air cavity, 2 is a paraffin cavity, 3 is a liquid inlet hole, 4 is a liquid storage cavity, 5 is a paraffin cavity, and 6 is an air outlet hole. In addition, the grey boxes represent the corresponding positions of the heating resistors. Inputting the micro-fluidic reagent prepackaging structure diagram into a 3D printer to carve out a prepackaging structure template, preparing a PDMS reagent, pouring the PDMS reagent into the template, placing the template in a dryer with the temperature of about 75 ℃ for drying, taking out the template when the reagent in the template is dried to be semi-dry, encapsulating paraffin particles in a paraffin cavity 2, firstly melting the solid paraffin particles by heating, injecting and filling liquid paraffin into and filling the cavity with a certain temperature, speed and pressure by a perfusion tool-an injector in the embodiment, compacting, cooling and shaping, and then reversing the mold to obtain the paraffin microsphere product with certain shape and size.
The prepared and molded paraffin microspheres are placed on the corresponding position of the phase change valve on the chip, namely the paraffin cavity 2, and the chip cover plate is packaged, at this time, because of the micro-type of the channel and other reasons, a certain gap still exists between the paraffin microspheres and the micro valve to be packaged, and the micro valve can not be completely closed, so that the paraffin is slightly melted by matching short-time heating, the paraffin after being cooled and molded again can be tightly attached to the channel wall to form a well-sealed paraffin micro valve, and as shown in fig. 7 (b), the yellow part shows that the paraffin is packaged completely. After paraffin encapsulation is finished, the pre-encapsulation structure is torn off from the template and is attached to a base plate which is also in a semi-dry state to form a cavity with a specific function, then the attached semi-dry pre-encapsulation structure is placed in a dryer at about 45 ℃ for drying, the temperature in the dryer is not higher than 45 ℃, otherwise, the encapsulated paraffin will be melted and flow to other micro-channels, and after the paraffin is completely dried, the encapsulated chip structure is finished. The packaging chip structure is a local amplification plate, can be used for storing and transporting samples when being used independently, and can be directly integrated into a specific micro-fluidic chip for realizing a specific function to be used as a pre-packaging part of a reagent in the chip.
Example five:
as an application of the paraffin micro-valve dynamic packaging technology, the reagent on the chip can be pre-packaged based on a paraffin micro-valve dynamic packaging system. A specific implementation flow diagram is shown in fig. 8. Firstly, preparing a micro-fluidic chip, wherein a paraffin micro valve is packaged in the prepared micro-fluidic chip, for example, the diagonal line shaded part in fig. 8 is the packaged paraffin micro valve, and a rectangular frame in the drawing indicates a heating resistor corresponding to each cavity. And secondly, injecting reagents, wherein the experiment realizes the pre-packaging of two reagents, so that the two reagents A and B are respectively injected into the reagent cavity from the two liquid inlet holes. And thirdly, packaging the reagent, opening a resistor to melt paraffin, heating the air cavity to enable air in the air cavity to expand by heating to push the melted paraffin to flow in the microchannel, enabling the paraffin to enter the packaging cavity of the paraffin, and sealing the liquid inlet hole and the opening of the sample opened channel after the paraffin is cooled and solidified to enable the reagent to be sealed in the reagent cavity.
Fig. 9 is a diagram showing the paraffin encapsulation and reagent pre-encapsulation of the microfluidic chip in the above-described specific experiment. After the microfluidic chip base plate is dried to be half-dry in a dryer and taken out, the cover plate of the microfluidic chip which is dried to be full-dry and packaged with the paraffin microspheres is gently attached together from one side of the base plate, the positions of all cavities in the chip are required to correspond to the positions of heating resistors on a heating layer circuit board on the base plate, then the cover plate and the base plate are slowly attached, the base plate and the cover plate are completely attached through gentle pressing by tweezers, bubbles do not exist between the base plate and the cover plate, and the attached base plate and the cover plate are as shown in fig. 9 after the attachment. And then placing the bonded chip into a dryer to be dried completely, wherein the temperature of the dryer is adjusted to 45 ℃ at the moment because paraffin is packaged in the chip at the moment, so that the paraffin is prevented from melting, the chip is dried after one hour, and the cover plate and the bottom plate are completely bonded into a whole, namely the paraffin packaging is completed.
As an application of the paraffin micro-valve dynamic packaging technology, the reagent on the chip can be pre-packaged based on a paraffin micro-valve dynamic packaging system. The heating layer and the control layer on the centrifugal force microfluidic chip are connected together through a jumper wire, and the whole process adopts the air cavity to push melted paraffin to flow in the microfluidic channel to realize packaging without any external acting force. Firstly, a heating resistor corresponding to the air cavity is started to heat the air cavity, and the PID control temperature is about 70 ℃. After the air cavity is heated for 30 seconds, a heating resistor corresponding to the paraffin micro valve is opened to heat the paraffin micro valve, and PID (proportional integral differential) is also set, wherein PID is a mathematical physical term, proportional, integral and differential control, PID control for short and PID regulation for short, and the temperature is controlled to be about 70 ℃. And after the paraffin is pushed to flow into the liquid inlet hole and the paraffin cavity for packaging the reagent, the heating resistor corresponding to the air cavity is closed, and after the paraffin is cooled and solidified, the reagent is packaged in advance.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention is described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or some technical features of the present invention may be replaced. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. The paraffin micro valve is characterized by comprising a solid paraffin storage cavity, a to-be-packaged cavity, a heating module, a micro channel and an air cavity, wherein the to-be-packaged cavity is connected with the solid paraffin storage cavity through the micro channel, the air cavity is connected with the solid paraffin storage cavity through the micro channel, the heating module is arranged beside the air cavity and the solid paraffin storage cavity respectively, and the air cavity and the to-be-packaged cavity are positioned on two sides of the solid paraffin storage cavity.
2. The paraffin microvalve of claim 1, wherein the cavity to be encapsulated is provided with an air vent.
3. The paraffin microvalve of claim 1, wherein the heating modules are respectively disposed below the solid paraffin storage chamber or coated on the periphery of the solid paraffin storage chamber.
4. The paraffin microvalve according to any one of claims 1 to 3, wherein the heating modules are respectively disposed below the air cavity and the solid paraffin storage cavity, or respectively cover the peripheries of the air cavity and the solid paraffin storage cavity.
5. -any one of claims 1 to 3, characterised in that said heating module, using resistance heating.
6. A process for the preparation of a "paraffin microvalve" according to claims 1 to 5, comprising the steps of:
(1) placing the pre-prepared paraffin microspheres into a solid paraffin storage cavity;
(2) heating to melt the paraffin;
(3) cooling and molding the paraffin to make the paraffin closely fit with the cavity wall.
7. The method for manufacturing a paraffin microvalve according to claim 6, wherein the step (2) heats the paraffin to melt at a temperature of 0 to 5 degrees centigrade higher than the melting point of the paraffin used.
8. Use of a paraffin microvalve according to claims 1 to 5, characterized by the following steps:
(1) respectively heating the air cavity and the solid paraffin storage cavity, and pushing the paraffin which is heated to be in a molten state into the cavity to be packaged by utilizing the thrust generated by the expansion of the heated air in the air cavity;
(2) and cooling and molding the paraffin to finish packaging.
CN201810624744.9A 2018-06-16 2018-06-16 Paraffin micro-valve forming and packaging method thereof Active CN108855260B (en)

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CN110452802B (en) * 2019-08-07 2023-09-01 深圳市呈晖医疗科技有限公司 Full-extraction molecular diagnosis microfluidic chip and microfluidic system
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US20070178133A1 (en) * 2005-11-09 2007-08-02 Liquidia Technologies, Inc. Medical device, materials, and methods
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