CN114843006B - Three-dimensional flexible sensor material and preparation method and application thereof - Google Patents
Three-dimensional flexible sensor material and preparation method and application thereof Download PDFInfo
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- CN114843006B CN114843006B CN202210591962.3A CN202210591962A CN114843006B CN 114843006 B CN114843006 B CN 114843006B CN 202210591962 A CN202210591962 A CN 202210591962A CN 114843006 B CN114843006 B CN 114843006B
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- 239000000463 material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000007639 printing Methods 0.000 claims abstract description 51
- 239000006258 conductive agent Substances 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 238000010146 3D printing Methods 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- -1 polyoxyethylene Polymers 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000005018 casein Substances 0.000 claims description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 2
- 235000021240 caseins Nutrition 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000003623 enhancer Substances 0.000 claims 3
- 238000010339 medical test Methods 0.000 claims 1
- 238000010030 laminating Methods 0.000 abstract 1
- 210000000629 knee joint Anatomy 0.000 description 14
- 238000005452 bending Methods 0.000 description 9
- 230000033001 locomotion Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000002980 postoperative effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000011132 hemopoiesis Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 210000000697 sensory organ Anatomy 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/103—Detecting, measuring or recording devices for testing the shape, pattern, colour, size or movement of the body or parts thereof, for diagnostic purposes
- A61B5/107—Measuring physical dimensions, e.g. size of the entire body or parts thereof
- A61B5/1071—Measuring physical dimensions, e.g. size of the entire body or parts thereof measuring angles, e.g. using goniometers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/103—Detecting, measuring or recording devices for testing the shape, pattern, colour, size or movement of the body or parts thereof, for diagnostic purposes
- A61B5/11—Measuring movement of the entire body or parts thereof, e.g. head or hand tremor, mobility of a limb
- A61B5/1121—Determining geometric values, e.g. centre of rotation or angular range of movement
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/45—For evaluating or diagnosing the musculoskeletal system or teeth
- A61B5/4528—Joints
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/45—For evaluating or diagnosing the musculoskeletal system or teeth
- A61B5/4538—Evaluating a particular part of the muscoloskeletal system or a particular medical condition
- A61B5/4585—Evaluating the knee
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention provides a three-dimensional flexible sensor material, a preparation method and application thereof, wherein the preparation method of the sensor material is as follows: adding the conductive agent, the binder and the reinforcing agent into water, and uniformly dispersing to prepare printing ink; manufacturing the printing ink into a device in a 3D printing mode, and immersing the device in a cross-linking agent solution; drying the device containing the cross-linking agent by freeze drying. The flexible sensor can effectively solve the problems of large hardness and poor laminating degree of the existing sensor.
Description
Technical Field
The invention belongs to the technical field of sensors, and particularly relates to a three-dimensional flexible sensor material, a preparation method and application thereof.
Background
A sensor is a device that converts non-electrical signals into electrical signals, a "sense organ" in modern life. Is widely applied to various fields in life, including the aspects of automobiles, household appliances, environmental protection, entertainment facilities and the like, and plays an important role.
Bones are important components of the human body, and play roles in protecting, supporting, hematopoiesis, exercise and the like in the human body. Among all skeletal joints of a human body, a knee joint is a large and complex buckling joint of the human body, bears great force, has stable and flexible structure, finishes the load transmission of the human body, and plays an important role in the movement of the human body. When the knee joint of the human body is injured, not only the treatment is needed, but also the postoperative rehabilitation is important. The degree of postoperative recovery requires a criterion to evaluate. At present, patients can only go to hospitals for rehabilitation, and rehabilitation is performed through the guidance of doctors. In this process, due to the shortage of medical resources, there are problems of difficulty in seeing a doctor, difficulty in registering and time-consuming for a patient to perform rehabilitation, and a flexible rehabilitation method is needed to solve the problem.
At present, a sensor capable of helping a patient to perform self-help rehabilitation is needed to monitor the recovery condition of the patient, so that the patient can be not limited to a hospital when performing rehabilitation, and then the effect of performing self-help rehabilitation at home and outdoors is achieved, and in addition, the traditional rehabilitation devices are more devices with higher hardness of metal/semiconductor types, and the degree of fit and comfort of the injured part do not reach an ideal state.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a three-dimensional flexible sensor material, a preparation method and application thereof, and the sensor can effectively solve the problems of high hardness and poor fitting degree of the existing sensor.
In order to achieve the above purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a three-dimensional flexible sensor material comprises the following steps:
(1) Adding the conductive agent, the binder and the reinforcing agent into water, and uniformly dispersing to prepare printing ink;
(2) Manufacturing the printing ink into a device in a 3D printing mode, and immersing the device in a cross-linking agent solution;
(3) Drying the device containing the cross-linking agent by freeze drying.
Further, in the step (1), the dosage ratio of the conductive agent, the binder and the reinforcing agent is 1:0.2-2:0.1-0.5, and the solid content in the printing ink is 10-15%.
Further, the conductive agent in the step (1) includes one of carbon nanotubes, graphene, conductive carbon black and carbon fibers.
Further, the binder in the step (1) comprises one of cellulose, chitosan, polyethylene glycol, sodium alginate, water-soluble silicon dioxide, polyacrylamide, sodium alginate, casein, sodium polyacrylate and polyoxyethylene.
Further, the reinforcing agent in the step (1) comprises graphene oxide.
Further, the preparation method of the printing ink in the step (1) is as follows: firstly, adding a binder into water, and dispersing for 8-12min by adopting ultrasonic waves; adding the reinforcing agent, and dispersing for 20-40min at 5000-20000rad/min by using a high-speed dispersing instrument; finally, adding the conductive agent into the solution, and continuing to disperse for 50-70min by adopting a high-speed dispersing instrument, wherein the rotating speed is 1000-30000rad/min.
Further, the specific printing mode is as follows: the printing ink is placed in a needle cylinder, a glass plate is used as a receiver and is placed on a triaxial platform below, the printing pressure is set to be 10-30 psi, the diameter of a printing needle head is set to be 0.34-1.0 mm, and the moving speed of the triaxial platform is set to be 5-20 mm/min.
Further, the number of sample layers is 1-4, and the strand spacing in each layer is consistent with the diameter of the printed pinhead.
Further, in the step (2), the cross-linking agent is a high-valence metal ion, the high-valence metal ion is divalent and trivalent, and the cross-linking agent comprises one of copper ion, iron ion, aluminum ion and calcium ion.
Further, the concentration of the crosslinking agent in the step (2) is 0.1 to 2M.
Further, the high-valence metal ion is derived from at least one of its chloride, sulfate and nitrate.
Further, the freeze-drying operation is as follows: the printed device was frozen in liquid nitrogen and then transferred to a freeze dryer and dried in vacuo for 24 hours.
A three-dimensional flexible sensor comprises the material prepared by the method.
The three-dimensional flexible sensor is used for medical treatment in medical detection and joint detection.
The beneficial effects of the invention are as follows:
1. the conductive agent and the binder adopted in the invention have the characteristic of high length-diameter ratio, and are mutually intertwined to form a substrate with certain mechanical properties, and the conductive agent forms a conductive network inside the substrate.
2. The binder, the conductive agent and the reinforcing agent adopted in the invention have rich polar functional groups, can be complexed with high-valence metal ions, realize the reinforcing effect of a three-dimensional network, combine a pore structure endowed by a three-dimensional structure with a freeze drying technology, realize the structure of multistage pores, and rapidly release stress when being extruded by the outside, thereby ensuring better flexibility.
3. The three-dimensional flexible sensing device prepared by the invention has obvious resistance change, high sensitivity and high accuracy under the state of compression and the like, and can be used as a piezoresistive sensing device.
4. The 3D printing technology adopted by the invention can easily realize the preparation of customized devices, meets the requirements of users with variability, and has wide application prospects in the medical fields of knee joint movement detection and the like.
Drawings
FIG. 1 is a shear thinning performance characterization of the 3D printing ink of example 1;
FIG. 2 is a storage modulus/loss modulus performance characterization of the 3D printing ink of example 1;
FIG. 3 is a graphical representation of the fork structure for knee joint motion monitoring prepared by 3D printing technique in example 1;
FIG. 4 is a pictorial illustration of the sensing device for knee joint motion monitoring prepared by 3D printing technique in example 1 with the knees straightened and bent;
FIG. 5 is an internal Scanning Electron Microscope (SEM) image of the sensor material prepared by 3D printing technique in example 1;
fig. 6 is a signal profile for knee joint motion monitoring prepared by 3D printing technique in example 1.
Detailed Description
The principles and features of the present invention are described below in connection with the following examples, which are set forth to illustrate, but are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The preparation method of the three-dimensional flexible sensor comprises the following steps:
(1) Firstly, adding 1g of cellulose into 10mL of water, and dispersing for 10min by adopting ultrasonic; adding 0.1g of graphene oxide, and dispersing for 30min by a high-speed dispersing instrument at 20000rad/min; finally, adding 1g of carbon tube into the solution, and continuing to disperse for 1h by adopting a high-speed dispersing instrument, wherein the rotating speed is 30000rad/min to form printing ink;
(2) Placing the printing ink obtained in the step (1) in a 30CC cylinder, placing the printing ink in a lower triaxial platform by adopting a glass plate as a receiver, setting the printing pressure to be 30psi, setting the diameter of a printing needle to be 0.84mm, setting the moving speed of the triaxial platform to be 15mm/min, printing according to a preset program to obtain a fork-shaped sample, and setting the printing layer number to be 2;
(3) And (3) placing the printed sample obtained in the step (2) in a 0.5M copper chloride solution, crosslinking for 30 minutes, and transferring to a freeze dryer for freeze drying to obtain the printing material.
Example 2
The preparation method of the three-dimensional flexible sensor comprises the following steps:
(1) Firstly, adding 1g of chitosan into 12mL of water, and dispersing for 10min by adopting ultrasonic; adding 0.2g of graphene oxide, and dispersing for 30min by a high-speed dispersing instrument at the rotating speed of 25000rad/min; finally, adding 1g of graphene into the solution, and continuing to disperse for 1h by adopting a high-speed dispersing instrument, wherein the rotating speed is 30000rad/min to form printing ink;
(2) Placing the printing ink obtained in the step (1) in a 30CC cylinder, placing the printing ink in a lower triaxial platform by adopting a glass plate as a receiver, setting the printing pressure to be 20psi, setting the diameter of a printing needle to be 0.5mm, setting the moving speed of the triaxial platform to be 15mm/min, printing according to a preset program to obtain a fork-shaped sample, and setting the printing layer number to be 2;
(3) And (3) placing the printing sample obtained in the step (2) into a 0.5M copper nitrate solution, crosslinking for 30 minutes, and transferring to a freeze dryer for freeze drying to obtain the printing sample.
Example 3
The preparation method of the three-dimensional flexible sensor comprises the following steps:
(1) Firstly, 1g of sodium alginate is added into 10mL of water, and ultrasonic dispersion is adopted for 10min; adding 0.2g of graphene oxide, and dispersing for 60min by a high-speed dispersing instrument at 20000rad/min; finally, adding 1.5g of carbon fiber into the solution, and continuously dispersing for 2 hours by adopting a high-speed dispersing instrument, wherein the rotating speed is 30000rad/min to form printing ink;
(2) Placing the printing ink obtained in the step (1) in a 30CC cylinder, placing the printing ink in a lower triaxial platform by adopting a glass plate as a receiver, setting the printing pressure to be 20psi, setting the diameter of a printing needle to be 1mm, setting the moving speed of the triaxial platform to be 10mm/min, printing according to a preset program to obtain a fork-shaped sample, and setting the number of printing layers to be 2;
(3) And (3) placing the printed sample obtained in the step (2) in a 1M ferric chloride solution, crosslinking for 30 minutes, and then transferring to a freeze dryer for freeze drying to obtain the printing sample.
Example 4
The preparation method of the three-dimensional flexible sensor comprises the following steps:
(1) Firstly, adding 1g of cellulose into 10mL of water, and dispersing for 10min by adopting ultrasonic; adding 0.1g of graphene oxide, and dispersing for 30min by a high-speed dispersing instrument at the rotating speed of 10000rad/min; finally, adding 1.5g of carbon tube into the solution, and continuing to disperse for 1h by adopting a high-speed dispersing instrument, wherein the rotating speed is 30000rad/min to form printing ink;
(2) Placing the printing ink obtained in the step (1) in a 30CC cylinder, placing the printing ink in a lower triaxial platform by adopting a glass plate as a receiver, setting the printing pressure to be 20psi, setting the diameter of a printing needle to be 0.7mm, setting the moving speed of the triaxial platform to be 18mm/min, printing according to a preset program to obtain a fork-shaped sample, and setting the printing layer number to be 2;
(3) And (3) placing the printing sample obtained in the step (2) in a 1M aluminum chloride solution, crosslinking for 30 minutes, and then transferring to a freeze dryer for freeze drying to obtain the printing sample.
Test examples
The sensors are manufactured by encapsulating the devices prepared in examples 1-4 in VHB adhesive tape and attaching the devices to knee joints of human bodies, two ends of the sensors are clamped by positive and negative electrode clamps of a digital display source meter, resistance changes under action changes of different knee joints of human bodies are measured under constant voltage, and then health conditions of specific parts of human bodies are judged.
The sensor in example 1 has remarkable resistance continuous change capability under the conditions of bending movement of knee joint with bending angles of 30 degrees, 90 degrees and 120 degrees, and the resistance change rates are 220 percent, 750 percent and 2200 percent respectively;
the sensor in example 2 obtained the resistivity data of the sensing performance of 170%, 640%, 1900% respectively under the conditions of bending motion of knee joint at bending angles of 30 °, 90 °, 120 °;
the sensor in example 3 obtained the resistivity data of the sensing performance of 180%, 720% and 2000% respectively under the conditions of bending motion of knee joint at bending angles of 30 °, 90 ° and 120 °;
the sensor of example 4 obtained 165%, 600% and 1780% of the resistance change rate data of the sensing performance under the bending motion conditions of knee joint bending angles of 30 °, 90 ° and 120 °.
The rheological properties of the ink comprise shear thinning property and modulus, a rotary rheometer is adopted to carry out rheological test on the dispersed ink, the viscosity change of the ink is tested under a certain shear rate, and when the ink shows shear thinning behavior, the ink is proved to have the characteristic of being easy to extrude from a narrow needle under the action of air pressure. In addition, a higher storage modulus before critical shear pressure can ensure shape retention after printing, and when the air pressure reaches a critical point, it is shown that the ink can take the form of a liquid that can be extruded from a needle, with specific results shown in fig. 1 and 2.
As can be seen from fig. 1, the viscosity of the ink gradually decreases with the increase in shear time, and it is proved that the ink is easily extruded from a narrow needle to facilitate printing.
As can be seen from fig. 2, the ink has a high storage modulus before the critical pressure, which ensures shape retention of the sample after printing.
As can be seen from fig. 4, a large number of pore structures exist in the sensor material prepared in the application, so that the sensor material is loose, and when the knee joint is bent, the shape of the sensor material is changed, so that the resistance change of the sensor material is affected, and the detection of the health condition of a human body is realized.
As can be seen from fig. 5, the resistance of the sensor changes significantly after the knee joint bending angle is changed, so that the detection can be achieved.
While specific embodiments of the invention have been described in detail, it should not be construed as limiting the scope of the patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.
Claims (4)
1. The preparation method of the three-dimensional flexible sensor material is characterized by comprising the following steps of:
(1) Adding a conductive agent, a binder and an enhancer into water, uniformly dispersing to obtain printing ink, wherein the dosage ratio of the conductive agent to the binder to the enhancer is 1:0.2-2:0.1-0.5, the solid content in the printing ink is 10-15%, the conductive agent comprises one of carbon nano tubes, graphene, conductive carbon black and carbon fibers, the binder comprises one of cellulose, chitosan, polyethylene glycol, sodium alginate, water-soluble silicon dioxide, polyacrylamide, sodium alginate, casein, sodium polyacrylate and polyoxyethylene, and the enhancer comprises graphene oxide;
(2) Manufacturing the printing ink into a device in a 3D printing mode, and immersing the device in a cross-linking agent solution, wherein the concentration of the cross-linking agent is 0.1-2M;
(3) And drying the device containing the cross-linking agent in a freeze drying mode to obtain the high-valence metal ion cross-linking agent, wherein the cross-linking agent comprises one of copper ions, iron ions, aluminum ions and calcium ions.
2. The method of preparing a three-dimensional flexible sensor material according to claim 1, wherein the method of preparing the printing ink in step (1) comprises the steps of: firstly, adding a binder into water, and dispersing for 8-12min by adopting ultrasonic waves; adding the reinforcing agent, and dispersing for 20-40min at 5000-20000rad/min by using a high-speed dispersing instrument; finally, adding the conductive agent into the solution, and continuing to disperse for 50-70min by adopting a high-speed dispersing instrument, wherein the rotating speed is 1000-30000rad/min.
3. A three-dimensional flexible sensor comprising the sensor material made by the method of any one of claims 1-2.
4. Use of the three-dimensional flexible sensor of claim 3 in medical testing.
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