CN113308015B - Preparation method of 3D printing pressure-sensitive device - Google Patents
Preparation method of 3D printing pressure-sensitive device Download PDFInfo
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- CN113308015B CN113308015B CN202110539253.6A CN202110539253A CN113308015B CN 113308015 B CN113308015 B CN 113308015B CN 202110539253 A CN202110539253 A CN 202110539253A CN 113308015 B CN113308015 B CN 113308015B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/20—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L9/00—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means
- G01L9/02—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means by making use of variations in ohmic resistance, e.g. of potentiometers, electric circuits therefor, e.g. bridges, amplifiers or signal conditioning
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- C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
- C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a preparation method of a 3D printing pressure-sensitive device, which comprises the steps of carrying out 3D printing on a solution by taking a formic acid solution of polyvinyl formate as a raw material and taking an ethanol, water or sodium hydroxide solution as a coagulating bath, and carrying out pyrrole polymerization on a printed sample to obtain the pressure-sensitive device. The preparation method is simple in process and low in cost, the 3D printing method is adopted, the forming is convenient, and the obtained pressure sensing device can be applied to the wearable field and used for monitoring various motions of the feet of the human body.
Description
Technical Field
The invention relates to a preparation method of a 3D printing pressure sensing device, and belongs to the technical field of crossing of 3D printing and pressure sensing.
Background
The principle of the resistive sensor is to convert the resistance change of the conductive material in the device into an electrical signal under the action of external pressure. The change in electrical signal is mainly due to the contact resistance between the two conductive materials when pressure is applied. The resistive sensor is widely researched due to the simple response device structure, the signal conversion mechanism, the low power consumption and the high-density lattice potential, and can be divided into a strain type sensor and a piezoresistive type sensor according to different working mechanisms. The detection principle of the piezoresistive pressure-sensitive device is based on the piezoresistive effect of materials, detection is usually carried out by the resistance change of a tunnel between conductive filling particles, and obvious deformation does not exist; strain gauge pressure sensitive devices detect changes in resistance based on a reduction in cross-sectional area caused by deformation of a material when it is stretched or compressed.
The pressure sensitive material of the existing pressure sensor is a polymer conductive composite material, namely the polymer composite material with the conductive capability is formed after the conductive medium material and the polymer matrix are mixed and processed. The resistivity of the polymer conductive material has obvious pressure dependence, and pressure sensors with different sensitivities and different measuring ranges can be obtained by changing the content of the doped conductive medium. The filler in the polymer conductive composite may be metal, ceramic, carbon black, graphite, and the like. Such conductive composite materials usually require a larger conductive medium filling amount to reach the percolation threshold, and the mechanical properties of the polymer are difficult to ensure at high filling amounts, and the piezoresistive sensitivity of the sensor is generally smaller and the repeatability is not high. In order to improve the sensitivity and the measuring range of the sensor, the surface of the pressure-sensitive material can be subjected to micro-nano treatment to enable the surface of the pressure-sensitive material to have a certain micro-nano structure, so that the output performance of the sensor is improved.
Disclosure of Invention
The invention aims to solve the problems of high manufacturing cost, complex process and the like of a pressure-sensitive device in the prior art, and provides a preparation method of a 3D printing pressure-sensitive device.
In order to achieve the purpose, the invention provides a preparation method of a 3D printing pressure-sensitive device, the preparation method comprises the steps of taking a formic acid solution of polyvinyl formate as a raw material, taking an ethanol, water or sodium hydroxide solution as a coagulating bath, carrying out 3D printing on the solution, and carrying out pyrrole polymerization on a printed sample to obtain the pressure-sensitive device.
More specifically, the preparation method comprises the following steps:
(1) preparation of printing inks
Formic acid is used as a solvent and a reactant, polyvinyl alcohol is added, water bath heating and stirring are carried out, and after complete reaction, the mixture is cooled to room temperature;
(2)3D printing
Taking ethanol, water or sodium hydroxide solution as a coagulating bath, and performing 3D printing on the solution;
(3) pyrrole polymerization
And (3) immersing the 3D printed sample into an organic solvent containing pyrrole, and then adding a surfactant and an initiator to carry out in-situ polymerization.
Wherein, the adding proportion of the formic acid and the polyvinyl alcohol in the step (1) is as follows: 93ml to 120ml of formic acid and 20g to 30g of polyvinyl alcohol; the molecular weight of the polyvinyl alcohol is 67000-200000; the formic acid is anhydrous formic acid or methanol solution with mass concentration not less than 88%.
The temperature of the water bath in the step (1) is 30-90 ℃, and the stirring time is 1-5 hours.
The concentration of the sodium hydroxide solution in the step (2) is 0.1 mol/L-1 mol/L.
In the step (3), ethanol or dichloromethane is adopted as an organic solvent, tween 80 or sodium dodecyl sulfate is adopted as a surfactant, and a ferric sulfate solution is adopted as an initiator; the concentration of the ferric sulfate solution is 0.6-0.9 mol/L.
The adding proportion of the pyrrole, the organic solvent, the surfactant and the initiator is as follows: 4-5 ml of pyrrole, 150ml of organic solvent, 1ml of surfactant and 50-100 ml of initiator.
The solution 3D printing technology used in step (2) may adopt the existing technology, such as Ghosh and the like, using a solution 3D printing method to prepare a fibroin scaffold (adv. funct. mater, DOI: 10.1002/adfm.200800040), Cao and the like, using a solution 3D printing conductive fiber (adv. funct. mater, DOI: 10.1002/adfm.201905898), and the like.
Compared with the prior art, the invention has the following advantages:
according to the invention, a three-dimensional network structure is rapidly constructed by using a solution 3D printing method, and pyrrole is used for carrying out in-situ polymerization on the surface of a 3D printing sample, so that excellent sensing performance is obtained. The preparation method is simple in preparation flow and low in cost, the 3D printing method is adopted, the forming is convenient, and the obtained pressure sensing device can be applied to the wearable field and used for monitoring various motions of the feet of the human body.
Drawings
Fig. 1 is a 3D printed sample obtained in example 1 of the present invention;
fig. 2 is a pressure-sensitive device obtained in example 1 of the present invention;
fig. 3 is a graph showing the response of the pressure-sensitive device to different pressures in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but is not limited thereto. Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
According to the preparation method of the 3D printing pressure-sensitive device, PVA (polyvinyl alcohol) and formic acid are subjected to esterification reaction to generate a product polyvinyl formate which can be dissolved in formic acid but is not dissolved in water, ethanol and sodium hydroxide solution, and according to the characteristics, the solution 3D printing is carried out by using water, ethanol or sodium hydroxide solution as a coagulating bath, so that a three-dimensional integral structure can be obtained; the specific method comprises the following steps:
step 1: the corresponding three-dimensional model is manufactured through 3D modeling software, various forms such as a grid form, a ring form and the like can be adopted, and the three-dimensional model is sliced to convert the model into a corresponding numerical control program instruction.
Step 2: the printing ink is prepared, the main raw materials of the printing ink are polyvinyl alcohol and formic acid, the polyvinyl alcohol and the formic acid are subjected to esterification reaction, and the generated polyvinyl formate can be dissolved in the formic acid to form uniform viscous liquid.
And 3, 3D printing, namely inputting a numerical control program instruction into a printer, and performing 3D printing on the solution by using the solution (water, ethanol or sodium hydroxide solution) as a coagulating bath. The printed sample was soaked with distilled water to remove acid.
And 4, step 4: and (3) pyrrole polymerization, namely soaking the printed sample into an organic solvent containing pyrrole, adding a certain amount of initiator and a small amount of surfactant, and slowly polymerizing at low temperature. After 24 hours, the samples were washed and air dried.
Example 1
Step 1: a corresponding three-dimensional model with a grid structure is manufactured through 3D model design software, a grid form is adopted, the length of each grid is 2 mm, the height of each grid is 1 mm, and the width of each fiber is 0.65 mm. The length and width of the whole printing sample are both 5cm, and the height is 3 cm. One section has 25X25 grids, and the three-dimensional model is sliced to convert the model into corresponding numerical control program instructions.
Step 2: 20g of polyvinyl alcohol is added into a three-neck flask with the volume of 3L, 93ml of formic acid is slowly dripped and rapidly and mechanically stirred, the mixture is heated in a slow water bath to 50 ℃, and the ink is taken out after reaction for 3 hours. And cooling to room temperature.
And step 3: and inputting numerical control program instructions into a printer, and performing 3D printing on the solution by using distilled water as a coagulating bath. The printed sample was soaked with distilled water to remove acid.
And 4, step 4: the printed sample was immersed in ethanol containing 5ml of pyrrole and 150ml of ethanol. Then, 80ml of 0.9mol/L ferric sulfate and 1ml Tween 80 were added, and polymerization was slowly carried out at low temperature. After 24 hours, the samples were washed and air dried.
As shown in fig. 1, is the printed sample obtained in step 3. It can be seen from fig. 1 that the 3D printed sample realizes precision processing of a grid structure, the grids of all the facets are arranged in order, and a certain height is seen in the longitudinal direction.
As shown in fig. 2, the sample after pyrrole polymerization in step 4. From a comparison of fig. 1 and fig. 2, it can be seen that the surface of the printed sample changes from white to black, which is a valid proof of pyrrole polymerization.
It can be seen from fig. 3 that the pressure sensitive device has different response values to different pressures applied thereto, and the material obtained by the present invention can be effectively used as a pressure sensitive device.
Claims (5)
1. A preparation method of a 3D printing pressure-sensitive device is characterized by comprising the following steps:
(1) preparation of printing inks
Formic acid is used as a solvent and a reactant, polyvinyl alcohol is added, water bath heating and stirring are carried out, and after complete reaction, the mixture is cooled to room temperature;
(2)3D printing
Taking ethanol, water or sodium hydroxide solution as a coagulating bath, and performing 3D printing on the solution;
(3) pyrrole polymerization
Immersing the 3D printed sample into an organic solvent containing pyrrole, and then adding a surfactant and an initiator to carry out in-situ polymerization;
the addition ratio of formic acid to polyvinyl alcohol in the step (1) is as follows: 93ml to 120ml of formic acid and 20g to 30g of polyvinyl alcohol; the molecular weight of the polyvinyl alcohol is 67000-200000; the formic acid is anhydrous formic acid or formic acid solution with mass concentration not less than 88%.
2. The preparation method according to claim 1, wherein the water bath temperature in the step (1) is 30 ℃ to 90 ℃ and the stirring time is 1 to 5 hours.
3. The method according to claim 2, wherein the concentration of the sodium hydroxide solution in the step (2) is 0.1 to 1 mol/L.
4. The preparation method according to claim 3, wherein in the step (3), ethanol or dichloromethane is used as the organic solvent, tween 80 or sodium dodecyl sulfate is used as the surfactant, and a ferric sulfate solution is used as the initiator; the concentration of the ferric sulfate solution is 0.6-0.9 mol/L.
5. The preparation method according to claim 4, wherein the pyrrole, the organic solvent, the surfactant and the initiator are added in the following ratio: 4-5 ml of pyrrole, 150ml of organic solvent, 1ml of surfactant and 50-100 ml of initiator.
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| CN202110539253.6A CN113308015B (en) | 2021-05-18 | 2021-05-18 | Preparation method of 3D printing pressure-sensitive device |
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| CN202110539253.6A CN113308015B (en) | 2021-05-18 | 2021-05-18 | Preparation method of 3D printing pressure-sensitive device |
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| CN113308015B true CN113308015B (en) | 2022-09-09 |
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| CN114295255B (en) * | 2021-12-29 | 2023-09-29 | 金陵科技学院 | Flexible pressure sensor based on 3D prints |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190017094A (en) * | 2017-08-09 | 2019-02-20 | 국민대학교산학협력단 | pressure sensor of manufacture method and manufacturing equipment and the pressure sensor |
| CN109401440A (en) * | 2018-08-28 | 2019-03-01 | 上海幂方电子科技有限公司 | A kind of solvent type conductive ink, preparation method and application |
| CN111086204A (en) * | 2019-12-11 | 2020-05-01 | 深圳烯湾科技有限公司 | 3D printing method |
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- 2021-05-18 CN CN202110539253.6A patent/CN113308015B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190017094A (en) * | 2017-08-09 | 2019-02-20 | 국민대학교산학협력단 | pressure sensor of manufacture method and manufacturing equipment and the pressure sensor |
| CN109401440A (en) * | 2018-08-28 | 2019-03-01 | 上海幂方电子科技有限公司 | A kind of solvent type conductive ink, preparation method and application |
| CN111086204A (en) * | 2019-12-11 | 2020-05-01 | 深圳烯湾科技有限公司 | 3D printing method |
Non-Patent Citations (1)
| Title |
|---|
| "3D wet-spinning printing of wearable flexible electronic sensors of polypyrrole@polyvinyl formate";Jun Qian et al.;《Journal of Industrial and Engineering Chemistry》;20220502;第490-498页 * |
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