CN108149334B - Method for preparing microfiber with complex shape based on microfluidic chip and special chip - Google Patents

Method for preparing microfiber with complex shape based on microfluidic chip and special chip Download PDF

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CN108149334B
CN108149334B CN201611102522.8A CN201611102522A CN108149334B CN 108149334 B CN108149334 B CN 108149334B CN 201611102522 A CN201611102522 A CN 201611102522A CN 108149334 B CN108149334 B CN 108149334B
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chip
fluid channel
microfibers
sample fluid
outlet
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CN108149334A (en
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秦建华
于跃
魏文博
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Dalian Institute of Chemical Physics of CAS
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/22—Formation of filaments, threads, or the like with a crimped or curled structure; with a special structure to simulate wool
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/04—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of alginates

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  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

The method for preparing the microfiber with the complex morphology based on the microfluidic chip comprises the following steps: and (2) introducing the curing liquid into the power fluid channel, introducing the fiber precursor solution into the sample flow channel, immersing a channel outlet on the side wall of the chip below the liquid level of a container containing the curing liquid, and introducing the fiber precursor solution into the curing liquid in the container through the sample flow channel outlet at a constant flow rate, so that the fiber precursor solution is subjected to a curing reaction at the moment of contacting the curing liquid, and the microfibers are generated. The invention also relates to a special chip for preparing the microfibers with the complex shapes based on the microfluidic chip. The microfiber preparation method and the special chip used by the microfiber preparation method are flexible and controllable, and can realize automatic preparation of microfibers with complex shapes; wide application, flexible method, simple operation, low equipment cost and being beneficial to commercialization.

Description

Method for preparing microfiber with complex shape based on microfluidic chip and special chip
Technical Field
The invention relates to the technical field of cross application of a novel material technology and a microfluidic technology, and particularly provides a method for preparing microfibers with complex shapes based on a microfluidic chip and a special chip.
Background
In the prior art, a microfluidic chip (also called lab-on-a-chip) refers to a technology that a basic operation unit of a conventional laboratory is integrated on a chip of several square centimeters (even smaller), and a network is formed by microchannels, so that a controllable fluid can penetrate through the whole system to replace various functions of the conventional laboratory.
Fiber materials are widely used in many industries, and the fiber materials often come into contact with daily life include synthetic chemical fibers and natural fibers required for clothes textile, optical fibers in the field of electronic communication, glass fibers added in the manufacturing industry for improving the mechanical properties of the materials, surgical suture fibers used in the medical field, and the like.
The micron-scale fiber material is particularly suitable for application in the biomedical field, such as the fiber material is required to be used as a cell scaffold when a strip-shaped or tubular three-dimensional tissue is constructed in vitro, and the fiber material is required to be used as a carrier for embedding cells and a barrier for resisting immunological rejection when functional cells are transplanted into a human body for disease treatment, and the like. Due to the characteristics of large specific surface area, flexible mechanical property, convenient operation of linear structure and the like, the microfiber material is widely used in research in many life science fields, such as scaffolds for three-dimensional cell culture, carriers for embedding and slowly releasing functional molecules, implant materials for real-time monitoring of physiological states and the like.
Conventional methods for preparing microfiber materials include wet spinning, dry spinning, melt spinning, electrospinning, and the like. These methods are very limited in the preparation of complex microfiber materials. Mainly because these methods have poor control over the morphology, structure, and composition of the microfiber material. The micro-fluidic technology for preparing the micron-sized polymer fiber is a current hot spot direction. By means of the characteristic that the micro-fluidic system can accurately control the fluid under the micron scale, the micro-fiber material with a complex morphological structure can be conveniently formed, and the micro-fiber material is one of the methods with development prospects in the preparation of the micro-fiber material.
People hope to obtain a method for preparing microfibers with complex shapes based on a microfluidic chip and a special chip with excellent technical effects.
Disclosure of Invention
The invention aims to provide a method for preparing microfibers with complex shapes based on a microfluidic chip and a special chip with excellent technical effects.
The invention provides a method for preparing microfibers with complex shapes based on a microfluidic chip, which is characterized by comprising the following steps of: the method uses a special chip to prepare the microfiber with complex morphology; the substrate material of the special chip is provided with the following structures: a straight sample fluid channel and a power fluid channel distributed in parallel around the sample fluid channel; the sample fluid channel and the dynamic fluid channel inlet are both positioned on the upper surface of the chip; the outlets are all positioned on the same side wall of the chip; on the side wall of the chip provided with the outlet, the outlets of the dynamic fluid channels are uniformly distributed around the outlets of the sample fluid channels by taking the outlets of the sample fluid channels as centers; at the position close to the outlet, all the power fluid channels bend towards the direction of the sample fluid channel and form a fixed angle with the sample fluid channel, namely the angles formed by all the power fluid channels on the same special chip and the sample fluid channel are the same; the fixed angle formed between the motive fluid channel and the sample fluid channel is adjustable in the range of 0 ° to 90 ° at a position proximate the outlet;
the requirements for the preparation of microfibers of complex morphology using specialized chips are: and (2) introducing the curing liquid into the power fluid channel, introducing the fiber precursor solution into the sample flow channel, immersing a channel outlet on the side wall of the chip below the liquid level of a container containing the curing liquid, and introducing the fiber precursor solution into the curing liquid in the container through the sample flow channel outlet at a constant flow rate, so that the fiber precursor solution is subjected to a curing reaction at the moment of contacting the curing liquid, and the microfibers are generated.
The method for preparing the microfiber with the complex morphology based on the microfluidic chip is characterized by comprising the following steps of: during the process of continuously generating the microfibers, the solidifying liquid in the power fluid channel is controlled to be led into the container through the outlet of the power fluid channel, a jet flow is generated, the solidified microfibers are disturbed, the microfibers are bent and deformed, and the microfibers with complex shapes are generated through further solidification.
The method for preparing the microfiber with the complex morphology based on the microfluidic chip is characterized by comprising the following steps of: the flow and stop of the curing liquid in each power fluid channel are accurately controlled by using an electromagnetic valve and program control equipment, so that the form of the microfiber is controlled; so as to prepare the microfibers with various morphologies with controllable sizes, wherein the fiber morphology is one or the combination of the following: wavy, helical, ball-and-socket, etc.
In the special chip, the number of the power fluid channels is adjustable, the power fluid channels are uniformly arranged around the sample fluid channels, and the overall array form is one of the following concentrated macroscopic patterns: linear, triangular, square, circular.
The invention also claims a special chip of the method for preparing the microfiber with complex shape based on the microfluidic chip, which is the microfluidic chip; the method is characterized in that: the substrate material of the special chip is provided with the following structures: a straight sample fluid channel and a power fluid channel distributed in parallel around the sample fluid channel; the sample fluid channel and the dynamic fluid channel inlet are both positioned on the upper surface of the chip; the outlets are all positioned on the same side wall of the chip; on the side wall of the chip provided with the outlet, the outlets of the dynamic fluid channels are uniformly distributed around the outlets of the sample fluid channels by taking the outlets of the sample fluid channels as centers; at the position close to the outlet, all the power fluid channels bend towards the direction of the sample fluid channel and form a fixed angle with the sample fluid channel, namely the angles formed by all the power fluid channels on the same special chip and the sample fluid channel are the same; the fixed angle formed between the motive fluid channel and the sample fluid channel is adjustable in the range of 0 ° to 90 ° at a position proximate the outlet;
the special chip of the method for preparing the microfiber with the complex shape based on the microfluidic chip is characterized in that: one or a combination of the following auxiliary devices is also provided:
firstly, a device for controlling the solidification liquid in the power fluid channel to be introduced into the container through the outlet of the power fluid channel so as to generate a jet flow in the process of continuously generating the microfibers;
secondly, the device for disturbing the solidified microfibers to make the microfibers bend and deform is used, and then the microfibers with complex morphology can be generated through further solidification.
Thirdly, the electromagnetic valve and/or the program control equipment: so as to accurately control the flowing and stopping of the curing liquid in each power fluid channel, thereby realizing the control of the morphology of the microfibers; so as to prepare the microfibers with various morphologies with controllable sizes, wherein the fiber morphology is one or the combination of the following: wavy, helical, ball-and-socket, etc.
The special chip of the method for preparing the microfiber with the complex shape based on the microfluidic chip is characterized in that: in the special chip, the number of the power fluid channels is adjustable, the power fluid channels are uniformly arranged around the sample fluid channels, and the overall array form is one of the following concentrated macroscopic patterns: linear, triangular, square, circular.
The microfiber preparation method and the special chip used by the microfiber preparation method are flexibly controllable, and have the following advantages:
1. the shape of the microfiber is controlled by a program, and the automatic preparation of the microfiber with a complex shape is realized;
2. the fiber preparation method is flexible, simple and convenient to operate, low in equipment cost and beneficial to commercialization;
3. the prepared fiber material has various types and shapes and wide application.
Drawings
The invention is described in further detail below with reference to the following figures and embodiments:
FIG. 1 is a schematic diagram of a microfluidic chip with four power fluid channels;
FIG. 2 is a schematic front view of a slave microfluidic chip channel structure corresponding to FIG. 1;
FIG. 3 is a left side view of the channel structure of the slave microfluidic chip corresponding to FIG. 1;
FIG. 4 is a schematic top view of the channel structure of the slave microfluidic chip corresponding to FIG. 1;
FIG. 5 is a schematic of the preparation of straight microfibers using a microfluidic chip;
FIG. 6 is one of the schematic illustrations of the preparation of curved microfibers using a microfluidic chip;
fig. 7 is a second schematic diagram of the preparation of curved microfibers using a microfluidic chip.
Detailed Description
The reference numerals in figures 1, 2 have the following meanings:
in fig. 1: I1-I5 are five channel inlets A, B, C and E, O1-O5 are five channel outlets A, B, C, D and E, II is used for introducing fiber precursor solution, I2-I5 is used for introducing curing liquid, O1 is a spinneret orifice, and 02-05 is a jet flow outlet;
in FIGS. 2-4: observing the schematic diagram of the channel structure of the microfluidic chip from three directions of top view, side view and front view, wherein O1-O5 is five channel outlets, namely a channel outlet A, a channel outlet B, a channel outlet C, a channel outlet D and a channel outlet E, O1 is a spinneret orifice, and 02-05 is an injection outflow orifice;
in FIGS. 5-7: the microfibers under curing are subjected to flexural deformation by the action of the jet and the flexural form is fixed after curing.
Example 1
A method for preparing microfibers with complex morphology based on a microfluidic chip uses a special chip to prepare microfibers with complex morphology; the substrate material of the special chip is provided with the following structures: a straight sample fluid channel and a power fluid channel distributed in parallel around the sample fluid channel; the sample fluid channel and the dynamic fluid channel inlet are both positioned on the upper surface of the chip; the outlets are all positioned on the same side wall of the chip; on the side wall of the chip provided with the outlet, the outlets of the dynamic fluid channels are uniformly distributed around the outlets of the sample fluid channels by taking the outlets of the sample fluid channels as centers; at the position close to the outlet, all the power fluid channels bend towards the direction of the sample fluid channel and form a fixed angle with the sample fluid channel, namely the angles formed by all the power fluid channels on the same special chip and the sample fluid channel are the same; the fixed angle formed between the motive fluid channel and the sample fluid channel is adjustable in the range of 0 ° to 90 ° at a position proximate the outlet;
the requirements for the preparation of microfibers of complex morphology using specialized chips are: and (2) introducing the curing liquid into the power fluid channel, introducing the fiber precursor solution into the sample flow channel, immersing a channel outlet on the side wall of the chip below the liquid level of a container containing the curing liquid, and introducing the fiber precursor solution into the curing liquid in the container through the sample flow channel outlet at a constant flow rate, so that the fiber precursor solution is subjected to a curing reaction at the moment of contacting the curing liquid, and the microfibers are generated.
During the process of continuously generating the microfibers, the solidifying liquid in the power fluid channel is controlled to be led into the container through the outlet of the power fluid channel, a jet flow is generated, the solidified microfibers are disturbed, the microfibers are bent and deformed, and the microfibers with complex shapes are generated through further solidification.
By using the electromagnetic valve and the program control equipment, the flow and the stop of the curing liquid in each power fluid channel can be accurately controlled, so that the form of the microfiber can be controlled; so as to prepare the microfibers with various morphologies with controllable sizes, wherein the fiber morphology is one or the combination of the following: wavy, helical, ball-and-socket, etc.
In the special chip, the number of the power fluid channels is adjustable, the power fluid channels are uniformly arranged around the sample fluid channels, and the overall array form is one of the following concentrated macroscopic patterns: linear, triangular, square, circular.
The chip is a special chip for the method for preparing the microfiber with the complex shape based on the microfluidic chip, and is the microfluidic chip; the substrate material of the special chip is provided with the following structures: a straight sample fluid channel and a power fluid channel distributed in parallel around the sample fluid channel; the sample fluid channel and the dynamic fluid channel inlet are both positioned on the upper surface of the chip; the outlets are all positioned on the same side wall of the chip; on the side wall of the chip provided with the outlet, the outlets of the dynamic fluid channels are uniformly distributed around the outlets of the sample fluid channels by taking the outlets of the sample fluid channels as centers; at the position close to the outlet, all the power fluid channels bend towards the direction of the sample fluid channel and form a fixed angle with the sample fluid channel, namely the angles formed by all the power fluid channels on the same special chip and the sample fluid channel are the same; the fixed angle formed between the motive fluid channel and the sample fluid channel is adjustable in the range of 0 ° to 90 ° at a position proximate the outlet;
the special chip of the method for preparing the microfiber with the complex shape based on the microfluidic chip is also provided with one or the combination of the following auxiliary equipment:
firstly, a device for controlling the solidification liquid in the power fluid channel to be introduced into the container through the outlet of the power fluid channel so as to generate a jet flow in the process of continuously generating the microfibers;
secondly, the device for disturbing the solidified microfibers to make the microfibers bend and deform is used, and then the microfibers with complex morphology can be generated through further solidification.
Thirdly, the electromagnetic valve and/or the program control equipment: so as to accurately control the flowing and stopping of the curing liquid in each power fluid channel, thereby realizing the control of the morphology of the microfibers; so as to prepare the microfibers with various morphologies with controllable sizes, wherein the fiber morphology is one or the combination of the following: wavy, helical, ball-and-socket, etc.
The special chip of the method for preparing the microfiber with the complex shape based on the microfluidic chip is characterized in that: in the special chip, the number of the power fluid channels is adjustable, the power fluid channels are uniformly arranged around the sample fluid channels, and the overall array form is one of the following concentrated macroscopic patterns: linear, triangular, square, circular.
The microfiber preparation method and the special chip used by the microfiber preparation method provided by the embodiment are flexible and controllable, and have the following advantages:
1. the shape of the microfiber is controlled by a program, and the automatic preparation of the microfiber with a complex shape is realized;
2. the fiber preparation method is flexible, simple and convenient to operate, low in equipment cost and beneficial to commercialization;
3. the prepared fiber material has various types and shapes and wide application.
Example 2
Preparation of wavy calcium alginate microfibers: the wavy calcium alginate fibers were prepared using the microfluidic chip as shown in fig. 1, and the diameters of the outlets of the O1-O5 channels were all 100x100 um. Preparing sodium alginate aqueous solution (NaA, 2 wt%) and calcium chloride aqueous solution (CaCl)22 wt.%). The NaA solution is introduced into an inlet I1, CaCl is added2The solution was divided into four portions and passed to inlets I2-I5, respectively. Submerging the chip outlet into CaCl2In the aqueous solution, a NaA solution was continuously introduced at a flow rate of 2uL/min and passed through an O1 spinneret to form calcium alginate (CaA) microfibers. The CaCl was continuously added at a flow rate of 5uL/min2The solution is introduced into CaCl through the outlets of O2 and O3 channels2In the solution pool, a program-controlled solenoid valve is used for controlling CaCl passing through the outlets of O4 and O5 channels2The solution flows to spray the solution in the two channels to Ca at intervals of 'switching on and off' modeCl2In the solution pool (5uL/min flow rate), the interval time is 500ms, so that the microfibers are reversely bent every 500ms, and finally the wavy CaA fibers are formed.
Example 3
Preparation of spiral calcium alginate microfibers:
the wavy calcium alginate fibers were prepared using the microfluidic chip as shown in fig. 1, and the diameters of the outlets of the O1-O5 channels were all 100x100 um. Preparing sodium alginate aqueous solution (NaA, 2 wt%) and calcium chloride aqueous solution (CaCl)22 wt.%). The NaA solution is introduced into an inlet I1, CaCl is added2The solution was divided into four portions and passed to inlets I2-I5, respectively. Submerging the chip outlet into CaCl2In the aqueous solution, a NaA solution was continuously introduced at a flow rate of 2uL/min and passed through an O1 spinneret to form calcium alginate (CaA) microfibers. CaCl control through O1-O5 channel outlet using a programmable solenoid valve2The solution flows to ensure that the solutions in the four channels are sprayed on the CaCl in a circulating way in sequence2The solution tank (5uL/min flow rate) is separated by 500ms, so that the microfibers are bent every 500ms, and finally spiral CaA fibers are formed.

Claims (5)

1. The method for preparing the microfiber with the complex morphology based on the microfluidic chip is characterized by comprising the following steps of: the method uses a special chip to prepare the microfiber with complex morphology; the substrate material of the special chip is provided with the following structures: a straight sample fluid channel and a power fluid channel distributed in parallel around the sample fluid channel; the sample fluid channel inlet and the power fluid channel inlet are both positioned on the upper surface of the chip; the outlets are all positioned on the same side wall of the chip; on the side wall of the chip provided with the outlet, the outlets of the dynamic fluid channels are uniformly distributed around the outlets of the sample fluid channels by taking the outlets of the sample fluid channels as centers; at the position close to the outlet, all the power fluid channels bend towards the direction of the sample fluid channel and form a fixed angle with the sample fluid channel, namely the angles formed by all the power fluid channels on the same special chip and the sample fluid channel are the same; the fixed angle is between 0 DEG and 90 DEG;
the requirements for the preparation of microfibers of complex morphology using specialized chips are: introducing the curing liquid into the power fluid channel, introducing the fiber precursor solution into the sample flow channel, immersing a channel outlet on the side wall of the chip below the liquid level of a container containing the curing liquid, and introducing the fiber precursor solution into the curing liquid in the container through the sample flow channel outlet at a constant flow rate, so that the fiber precursor solution is subjected to a curing reaction at the moment of contacting the curing liquid, and microfibers are generated;
controlling the solidification liquid in the power fluid channel to be led into the container through the outlet of the power fluid channel in the process of continuously generating the microfibers, generating a jet flow, and disturbing the microfibers in solidification, so that the microfibers are bent and deformed, and the microfibers with complex shapes are generated through further solidification;
the flow and stop of the curing liquid in each power fluid channel are accurately controlled by using an electromagnetic valve and program control equipment, so that the form of the microfiber is controlled; so as to prepare the microfibers with various morphologies with controllable sizes, wherein the fiber morphology is one or the combination of the following: wave shape, spiral shape, ball joint shape.
2. The method for preparing microfibers of complex morphology according to claim 1, based on microfluidic chips, characterized in that: in the specialized chip, the kinetic fluid channels are uniformly arranged around the sample fluid channel and the overall array is in the form of one of the following concentrated macroscopic patterns: linear, triangular, square, circular.
3. A dedicated chip for the method for preparing microfibers of complex morphology based on a microfluidic chip according to claim 1 or 2, which is a microfluidic chip; the method is characterized in that: the substrate material of the special chip is provided with the following structures: a straight sample fluid channel and a power fluid channel distributed in parallel around the sample fluid channel; the sample fluid channel inlet and the power fluid channel inlet are both positioned on the upper surface of the chip; the outlets are all positioned on the same side wall of the chip; on the side wall of the chip provided with the outlet, the outlets of the dynamic fluid channels are uniformly distributed around the outlets of the sample fluid channels by taking the outlets of the sample fluid channels as centers; at the position close to the outlet, all the power fluid channels bend towards the direction of the sample fluid channel and form a fixed angle with the sample fluid channel, namely the angles formed by all the power fluid channels on the same special chip and the sample fluid channel are the same; the fixed angle is between 0 ° and 90 °.
4. A special chip for a method for preparing microfibers with complex morphology according to claim 3, characterized in that: one or a combination of the following auxiliary devices is also provided:
firstly, a device for controlling the solidification liquid in the power fluid channel to be introduced into the container through the outlet of the power fluid channel so as to generate a jet flow in the process of continuously generating the microfibers;
secondly, a device for disturbing the solidifying microfibers to enable the microfibers to be bent and deformed;
thirdly, the electromagnetic valve and/or the program control equipment: so as to precisely control the flow and stop of the curing liquid in each of the power fluid channels, thereby achieving control of the morphology of the microfibers.
5. The special chip for the method for preparing the microfibers with the complex morphology based on the microfluidic chip according to claim 4, wherein: in the specialized chip, the kinetic fluid channels are uniformly arranged around the sample fluid channel and the overall array is in the form of one of the following concentrated macroscopic patterns: linear, triangular, square, circular.
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