CN109878071B - Method for preparing ionic pressure array sensor based on 3D printing - Google Patents
Method for preparing ionic pressure array sensor based on 3D printing Download PDFInfo
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- CN109878071B CN109878071B CN201910156271.9A CN201910156271A CN109878071B CN 109878071 B CN109878071 B CN 109878071B CN 201910156271 A CN201910156271 A CN 201910156271A CN 109878071 B CN109878071 B CN 109878071B
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- 229920000831 ionic polymer Polymers 0.000 claims abstract description 34
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- 229920000642 polymer Polymers 0.000 claims abstract description 11
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
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- 238000001125 extrusion Methods 0.000 claims description 15
- 229920001983 poloxamer Polymers 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
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Abstract
The invention discloses a method for preparing an ionic pressure array sensor based on 3D printing, which takes ionic polymer solution Nafion and a high-boiling point solvent as ionic sensing raw materials, takes Pluronic F127 as a printing support layer raw material, and prepares the ionic pressure array sensor by 3D composite printing. The method combines the Nafion printing solution and the support printing gel F-127, solves the problem of manufacturing an array structure by simply printing the Nafion solution, is suitable for manufacturing different types of Nafion polymer microstructure arrays, and has important application potential in the fields of artificial skin, flexible sensing and the like.
Description
Technical Field
The invention belongs to the technical field of 3D printing, and particularly relates to a method for preparing an ionic pressure array sensor based on 3D printing.
Background
An ionic electroactive polymer (iEAP) material is a typical flexible intelligent material with sensing-driving bidirectional functions, and is usually in a sandwich composite film structure of electrode-ionic polymer-electrode, the ionic polymer usually adopts a Nafion solution or Nafion film, and the polymer contains movable ions and water molecules. Under the action of external force, the iEAP material is bent, and the movable cations are transferred to the outer side of the bend by the elastic stress gradient generated in the iEAP material, so that space charge gradient distribution is formed, and a potential difference is formed between the two electrodes. Compared with the traditional piezoelectric polymer material, the material has the outstanding advantages of light weight, lower mechanical impedance and acoustic impedance, various processing techniques, natural bionic advantage and the like, and has wide application prospect in the fields of flexible robots, consumer electronics, human medical health monitoring and the like.
However, the method for preparing the sensor by using the ionic polymer adopts a casting film process, SO that the prepared structure is simple, and the popularization and the utilization of the material are not facilitated, the ionic polymer precursor material is printed by melting 3D to prepare the ionic polymer sensor, the printing method needs to hydrolyze a printed Nafion precursor polymeric side chain SO2 group into an SO3 group, the process is complicated, and the array sensor with the microstructure is difficult to prepare by adopting a pure direct-writing printing Nafion solution for manufacturing the sensor.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing an ionic pressure array sensor based on 3D printing, which combines a Nafion printing solution and a support printing gel F-127, solves the problem of manufacturing an array structure by simply printing the Nafion solution, is suitable for manufacturing a Nafion polymer micro-structure array, and has important application potential in the fields of artificial skin, flexible sensing and the like.
The invention adopts the following technical scheme:
a method for preparing an ionic pressure array sensor based on 3D printing is characterized in that an ionic polymer solution Nafion and a high-boiling-point solvent are used as ionic sensing raw materials, Pluronic F127 is used as a printing support layer raw material, and the ionic pressure array sensor is prepared through 3D composite printing.
Specifically, a Nafion solution with the mass fraction of 5% and a high-boiling point solvent are mixed, heated and magnetically stirred until the concentration of the Nafion solution is 40-60%.
Further, the mass ratio of the Nafion solution to the high boiling point solvent is 1: (1-4).
Specifically, the high boiling point solvent is one of dimethylacetamide, dimethylformamide or ethylene glycol.
Specifically, the Pluronic powder is dissolved in water at 4 ℃, and is stirred into a uniform gel state by a planetary stirrer, wherein the mixing mass ratio of the Pluronic powder to the water is 1 (1-2.5).
Specifically, the composite printing specifically comprises:
s301, firstly, loading the ionic polymer ink and the Pluronic F127 gel into a direct-writing printer with double nozzles, and respectively adjusting the extrusion air pressure for printing the ionic polymer ink and the F127 gel to ensure that the nozzles uniformly discharge filaments;
s302, running a G code of the array model, and printing an F127 gel structure layer with the thickness of 0.2-1 mm;
and S303, after the printing of the gel layer is finished, printing a layer of polymer Nafion solution with the thickness of 0.2-1 mm on the surface of the F127 gel layer.
Further, in step S301, the extrusion pressure of the Pluronic F127 is 0.02-0.3 MPa, the scanning speed is 5-35 mm/S, the height of the nozzle from the forming plate is 0.2-0.5 mm, and the thickness of the printer layer is set to be 0.165-0.25 mm.
Specifically, the composite printed composite structure is placed in vacuum at 130 ℃ and heated to be cured, the composite structure is placed in water at 4-20 ℃ and removed, and the Plannike F127 supporting layer is used to obtain the array Nafion ionic polymer.
Further, a layer of conductive electrode foil is respectively attached to the upper surface and the lower surface of the ionic polymer forming array structure by conductive silver paste, so that the array type ionic pressure sensor with the electrode-ionic polymer-electrode sandwich composite structure is formed.
Further, conductive silver paste is used to connect with the array unit, so as to form the distributed sensor.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention relates to a 3D printing method of an ionic pressure array sensor, which is a method for preparing an array pressure sensor by composite printing by taking an ionic polymer solution Nafion and a high-boiling-point solvent as ionic sensing raw materials and taking Plannik (F127) as a printing support layer raw material. The basic principle is that Pluronic (F127) can form gel in 30-40% concentration water solution, the printed gel line has good stability and high precision, the array microstructure is easy to print, the printed structure can be dissolved in cold water, the direct-writing printing support layer is suitable for being used for the direct-writing printing support layer, the direct-writing printing Nafion solution is combined with the F127, the Nafion complex structure forming can be realized, and the direct-writing printing support layer is particularly suitable for printing array pressure sensors.
Further, the Nafion solution with the mass fraction of 5% and the high-boiling-point solvent are mixed and then are heated and magnetically stirred until the concentration of the Nafion solution is 40-60%, the prepared F127 ink has the shear thinning property, the printed lines are good in continuity and high in precision, the printed lines are not prone to flowing, and the shapes of the lines can be kept.
Furthermore, the dimethyl acetamide, the dimethyl formamide and the ethylene glycol can prevent lines from cracking due to heating in the printing process.
Further, the pluronic powder is dissolved in water at 4 ℃, and is stirred into uniform gel by a planetary stirrer, the current situation of lines can be kept in the gel printing process, and the solution can be bootstrapped and is suitable for printing.
Furthermore, the printing process parameters are set, and the subsequent printing treatment process is selected, so that the printed F127 structure and the Nafion membrane structure can be complementary.
Furthermore, the Nafion layer can be ensured to be cured through heating treatment, and the cured structure has toughness.
Furthermore, the extrusion pressure of the Plannik F127 is 0.02-0.3 MPa, the scanning speed is 5-35 mm/s, the height of the spray head from the forming plate is 0.2-0.5 mm, the thickness of the printer layer is set to be 0.165-025 mm, and the lines in the printing process can be guaranteed to be uniform and stable.
Furthermore, the conductive silver paste is adopted to connect the upper surface and the lower surface of the sensor, so that the conductive material can be ensured to be in good contact with the Nafion sensing layer.
In conclusion, the method combines the Nafion printing solution and the support printing gel F-127, solves the problem of manufacturing an array structure by simply printing the Nafion solution, is suitable for manufacturing different types of Nafion polymer microstructure arrays, and has important application potential in the fields of artificial skin, flexible sensing and the like.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a schematic view of a printed gel structure layer according to the present invention;
FIG. 2 is a schematic view of a Nafion printing polymer solution according to the present invention;
FIG. 3 is a schematic view of an arrayed Nafion ionomer of the present invention;
fig. 4 is a schematic diagram of a distributed sensor made in accordance with the present invention.
Detailed Description
The invention provides a method for preparing an ionic pressure array sensor based on 3D printing, which takes ionic polymer solution Nafion and a high-boiling point solvent (dimethylacetamide, dimethylformamide or ethylene glycol) as ionic sensing raw materials, takes Pluronic (F127) as a printing support layer raw material, and prepares the array pressure sensor by composite printing, and comprises the following steps:
s1, preparing a Nafion solution;
firstly, mixing a Nafion solution with a mass fraction of 5% with a high-boiling-point solution, wherein the mass ratio of Nafion to the high-boiling-point solvent is 1: (1-4); heating and stirring uniformly by magnetic force, heating and concentrating until the concentration of Nafion solution reaches 40-60%, and using the Nafion solution as the ionic polymer ink for direct-writing printing;
s2, preparing Pluronic gel;
dissolving Pluronic powder in water at 4 ℃, wherein the mixing mass ratio of the Pluronic (F127) to the water is 1 (1-2.5), and stirring the mixture into uniform gel by adopting a planetary stirrer;
s3, performing composite printing;
s301, firstly, loading the ionic polymer ink and the F127 gel into a direct-writing printer with double spray heads, and respectively adjusting the extrusion air pressure for printing the ionic polymer ink and the F127 gel to ensure that the spray heads uniformly discharge filaments;
the extruding air pressure of the F127 is 0.02-0.3 MPa, the scanning speed is 5-35 mm/s, the height of the spray head from the forming plate is 0.2-0.5 mm, the thickness of the printer layer is set to be 0.165-0.25 mm, and the thickness of the printer layer is matched with the extruding air pressure.
S302, operating the G code of the array model, and firstly printing an F127 gel structure layer with the thickness of 0.2-1 mm, as shown in figure 1;
s303, after the printing of the gel layer is finished, printing a layer of polymer Nafion solution with the thickness of 0.2-1 mm on the surface of the F127 gel layer, as shown in figure 2.
S4, placing the printed composite structure in vacuum at 130 ℃, heating and curing, placing the whole structure in water at 4-20 ℃ to remove the F127 supporting layer, and obtaining an array Nafion ionic polymer layer as shown in figure 3;
s5, respectively attaching a layer of conductive electrode foil to the upper surface and the lower surface of the ionic polymer forming array structure by conductive silver paste to form an array type ionic pressure sensor with an electrode-ionic polymer-electrode sandwich composite structure; or connected with the array unit by conductive silver adhesive to form a distributed sensor, as shown in fig. 4.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1) Solution preparation;
taking 40ml of Nafion solution with the mass fraction of 5% and 10ml of Dimethylacetamide (DMAC) by adopting a measuring cylinder, mixing, magnetically stirring, heating and concentrating until the concentration of Nafion is 40%;
2) preparing a Pluronic gel;
weighing 4g F-127 white powder, dissolving in 6g water, stirring with a planetary stirrer to obtain transparent gel, and performing preliminary inspection with a printing head to obtain gel capable of being extruded into uniform thread;
3) a composite printing process;
s301, firstly, loading the ionic polymer ink and the F127 gel into a direct-writing printer with double spray heads, and respectively adjusting the extrusion air pressure for printing the ionic polymer ink and the F127 gel to ensure that the spray heads uniformly discharge filaments;
s302, operating a G code of the array model, setting printer parameters to be 0.25mm in layer thickness, 35mm/S in scanning speed and 0.3MPa in extrusion pressure, and firstly printing an F127 gel structure layer with the thickness of 1 mm;
s303, after the printing of the gel layer is finished, printing a layer of polymer Nafion ink with the thickness of 1mm on the surface of the F127 gel layer, wherein the printing parameters are set to be 0.25mm of layer thickness, the scanning speed is 35mm/S, and the extrusion air pressure is 0.3 MPa;
4) and (3) placing the printed composite structure in vacuum at 130 ℃, heating and curing for 2h, then slowly cooling to room temperature, and then placing the whole structure in water at 12 ℃ to remove the F127 supporting layer, thereby obtaining the array Nafion ionic polymer layer.
5) Material surface electrode manufacturing and post-treatment
And respectively attaching a layer of conductive copper electrode foil to the upper surface and the lower surface of the ionic polymer forming array structure by conductive silver paste to form the array ionic pressure sensor with the electrode-ionic polymer-electrode sandwich composite structure.
Example 2
1) Solution preparation;
taking 20ml of Nafion solution with the mass fraction of 5% and 10ml of Dimethylformamide (DMF) by adopting a measuring cylinder, mixing, magnetically stirring, heating and concentrating until the concentration of Nafion is 60%
2) Preparing a Pluronic gel;
weighing 3g F-127 white powder, dissolving in 7g water, stirring with a planetary stirrer to obtain transparent gel, and performing preliminary inspection with a printing head to obtain gel capable of being extruded into uniform thread;
3) a composite printing process;
s301, firstly, loading the ionic polymer ink and the F127 gel into a direct-writing printer with double spray heads, and respectively adjusting the extrusion air pressure for printing the ionic polymer ink and the F127 gel to ensure that the spray heads uniformly discharge filaments;
s302, operating a G code of the array model, setting printer parameters to be 0.165mm in layer thickness, 5mm/S in scanning speed and 0.02MPa in extrusion pressure, and firstly printing an F127 gel structure layer with the thickness of 0.2 mm;
s303, after the printing of the gel layer is finished, printing a layer of polymer Nafion ink with the thickness of 0.2mm on the surface of the F127 gel layer, wherein the printing parameters are set to be 0.165mm in layer thickness, the scanning speed is 5mm/S, and the extrusion air pressure is 0.02 MPa;
4) and (3) placing the printed composite structure in vacuum at 130 ℃, heating and curing for 2h, then slowly cooling to room temperature, and placing the whole structure in water at 4 ℃ to remove the F127 supporting layer to obtain the array Nafion ionic polymer layer, as shown in figure 3.
5) Material surface electrode manufacturing and post-treatment
And respectively attaching a layer of conductive copper electrode foil to the upper surface and the lower surface of the ionic polymer forming array structure by conductive silver paste to form the array ionic pressure sensor with the electrode-ionic polymer-electrode sandwich composite structure.
Example 3
1) Solution preparation;
taking 10ml of Nafion solution with the mass fraction of 5% and 10ml of ethylene glycol (DMF) by adopting a measuring cylinder, mixing, magnetically stirring, heating and concentrating until the concentration of Nafion is 50%
2) Preparing a Pluronic gel;
weighing 3g F-127 white powder, dissolving in 7g water, stirring with a planetary stirrer to obtain transparent gel, and performing preliminary inspection with a printing head to obtain gel capable of being extruded into uniform thread;
3) a composite printing process;
s301, firstly, loading the ionic polymer ink and the F127 gel into a direct-writing printer with double spray heads, and respectively adjusting the extrusion air pressure for printing the ionic polymer ink and the F127 gel to ensure that the spray heads uniformly discharge filaments;
s302, operating a G code of the array model, setting printer parameters to be 0.2mm in layer thickness, 15mm/S in scanning speed and 0.15MPa in extrusion pressure, and firstly printing an F127 gel structure layer with the thickness of 0.6 mm;
s303, after the printing of the gel layer is finished, printing a layer of polymer Nafion ink with the thickness of 0.6mm on the surface of the F127 gel layer, wherein the printing parameters are set to be 0.2mm of layer thickness, the scanning speed is 15mm/S, and the extrusion air pressure is 0.15MPa
4) And (3) placing the printed composite structure in vacuum at 130 ℃, heating and curing for 3h, then slowly cooling to room temperature, and placing the whole structure in water at 20 ℃ to remove the F127 supporting layer to obtain the array Nafion ionic polymer layer, as shown in figure 3.
5) Material surface electrode manufacturing and post-treatment
And respectively attaching a layer of conductive copper electrode foil to the upper surface and the lower surface of the ionic polymer forming array structure by conductive silver paste to form the array ionic pressure sensor with the electrode-ionic polymer-electrode sandwich composite structure.
The invention can realize the rapid manufacture of the array pressure sensor, and can realize the manufacture of the pressure sensors with different structures, different sensitivities and different sizes by a 3D printing method, thereby widening the application of the material in flexible electronics, soft robots and the like.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (2)
1. The method for preparing the ionic pressure array sensor based on 3D printing is characterized in that an ionic polymer solution Nafion and a high-boiling-point solvent are used as ion sensing raw materials, the Nafion solution with the mass fraction of 5% and the high-boiling-point solvent are mixed and then heated and magnetically stirred until the concentration of the Nafion solution is 60%, and the mass ratio of the Nafion solution to the high-boiling-point solvent is 1: dissolving pluronic powder in water at 4 ℃, stirring the solution into uniform gel-like pluronic powder by using a planetary stirrer, wherein the mass ratio of the pluronic powder to the water is 1:2.5, taking the pluronic as a printing support layer raw material, preparing an ionic pressure array sensor by 3D composite printing, placing a composite structure obtained by composite printing in vacuum at 130 ℃ to be heated and solidified, placing the composite structure in water at 20 ℃ to remove the pluronic support layer to obtain an array Nafion ionic polymer, respectively attaching conductive silver paste to the upper surface and the lower surface of an ionic polymer forming array structure to form an array ionic pressure sensor of an electrode-ionic polymer-electrode sandwich composite structure, and connecting the array unit by using conductive silver paste to form a distributed sensor, wherein the composite printing specifically comprises the following steps:
s301, firstly, loading the ionic polymer ink and the Pluronic F127 gel on a direct-writing printer with double spray heads, and respectively adjusting the extrusion air pressure for printing the ionic polymer ink and the F127 to ensure that the filaments are uniformly discharged by the spray heads, wherein the extrusion air pressure of the Pluronic F127 is 0.3MPa, the scanning speed is 35mm/S, the height of the spray heads from a forming plate is 0.5mm, and the thickness of the printer layer is 0.25 mm;
s302, running a G code of the array model, and printing an F127 gel structure layer with the thickness of 1 mm;
and S303, after the printing of the gel layer is finished, printing a layer of polymer Nafion solution with the thickness of 0.2-1 mm on the surface of the F127 gel layer.
2. The method for preparing an ionic pressure array sensor based on 3D printing of claim 1, wherein the high boiling point solvent is one of dimethylacetamide, dimethylformamide or ethylene glycol.
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Granted publication date: 20201027 |