CN111073302A - Preparation method of full-flexible stretching sensor suitable for 3D printing - Google Patents

Preparation method of full-flexible stretching sensor suitable for 3D printing Download PDF

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CN111073302A
CN111073302A CN201911340637.4A CN201911340637A CN111073302A CN 111073302 A CN111073302 A CN 111073302A CN 201911340637 A CN201911340637 A CN 201911340637A CN 111073302 A CN111073302 A CN 111073302A
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CN111073302B (en
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夏志东
赵陈
王雪龙
林健
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Beijing University of Technology
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    • 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
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Abstract

A method for preparing a full-flexible stretching sensor suitable for 3D printing belongs to the technical field of manufacturing of flexible electronic devices and is characterized in that a conductive material in a ① composite material is a fibrous filler, the material filling amount is low, ② a rigid conductive material and solid flexible particles are compounded, so that the printing material has good printing performance, meanwhile, the prepared sensor has stable sensing performance, ③ material preparation and printing processes are simple and convenient, the printing material preparation time is less than 1h, only ten minutes are needed for printing and forming, 3D printed products obtained by ④ are good in flexibility, the Shore hardness is lower than 80, the tensile strength is greater than 2MPa, the elongation is greater than 200%, ⑤ the sensor prepared by the method has the advantages that the resistance change rate can reach 100% when the sensor is subjected to 10% strain, the performance is stable under the cyclic loading of more than 600 times, the resistance response is close to linear change, ⑥ preparation is safe, and the used raw materials are non-toxic and pollution-free silicon rubber and the filler.

Description

Preparation method of full-flexible stretching sensor suitable for 3D printing
Technical Field
Belongs to the technical field of flexible electronic device manufacturing, and aims to ensure the flexible intelligent development of the electronic industry.
Background
Flexible stretch sensors are a major focus of research today, wherein flexible stretch sensors made of flexible conductive composites possess good elasticity and conductivity, which is one of the main directions of sensor research at present.
The flexible conductive composite material is formed by adding a conductive material into a flexible substrate, so that the flexible conductive composite material has excellent elasticity and certain conductivity. When the conductive composite material is deformed by external load, the electrical property of the conductive composite material can respond, and the conductive composite material can be used as a mechanical sensor. The flexible stretching sensor with high fineness and a complex shape can be obtained by utilizing a 3D printing technology, and the preparation process is a novel preparation process, but the research on the material and the performance of the printable flexible stretching sensor is still few at present.
Patent CN110294932A (application date 3/29/2019 and publication date 10/1/2019) discloses a 3D printing flexible composite pressure-sensitive material, which is printed by adopting 90-110 parts of silicone rubber (PDMS), 1.8-8.8 parts of conductive particles, 1-4 parts of nano modified material, 198 parts of diluent solvent 162 and silane coupling agent 3-12 parts to obtain a flexible sensor with a microstructure. The patent has the following limitations: 1) the sensor is a pressure-sensitive sensor and is not suitable for tensile load; 2) this patent lacks pressure sensitive performance response studies.3) SiO used2The modified powder is in nanometer level (20-25nm), the powder is harmful to human body, and the DMF and TEOS solvents have toxicity.
Patent CN109354873A (application date 2018, 9 and 13, and publication date 2019, 2 and 19) discloses a formula of a low-temperature 3D printing flexible pressure sensor and a preparation method thereof. The printing formula of the sensor consists of silicon rubber (PDMS), octamethylcyclotetrasiloxane, multi-walled carbon nanotubes and paraxylene. The preparation method comprises the steps of firstly ultrasonically dispersing the multi-walled carbon nano-tube in p-xylene, then magnetically stirring and mixing liquid silicon rubber and octamethylcyclotetrasiloxane, mixing the two solutions, carrying out ball milling, and finally carrying out suction filtration, vacuum filtration and screening out large particles to obtain the required slurry. The patent has the following characteristics or limitations: 1) this patent lacks performance parameters such as elongation, conductivity, degree of formation (shape retention) for the resulting material 3D printed article; 2) the sensor is a pressure-sensitive sensor and is not suitable for tensile load; 3) this patent lacks a study of sensor performance; 4) the formulations used have some toxicity to p-xylene and octamethylcyclotetrasiloxane.
Patent CN110237781A (application date 2019, 6 and 17 days, publication date 2019, 9 and 17 days) discloses a preparation method of a novel high-sensitivity 3D printing flexible sensor, in which PDMS + Ag powder is used as a first-phase liquid, IL is used as a second-phase solution, and the first-phase liquid and the IL are mixed by a mixer, and finally, a sensor colloid is obtained through deaeration. The colloid is printed out by the 3D printer and is conformed to the structure sensor. The patent has the following characteristics or limitations: 1) the yield stress of the sensor is small and ranges from 5000 Pa to 10000Pa (10 rubber is used daily)6Pa or so), the steel plate is easy to break under the influence of the outside; 2) the pure silver powder is expensive, the filling amount of the formula reaches more than 54 wt%, the cost is high, and the application value is not high.
Patent CN106751908A (application date 2017,1 month and 9 days, publication date 2017, 5 months and 31 days) discloses a 3D printing flexible conductive composite material and a preparation method thereof. The composite material is prepared by mixing 30-60 wt% of liquid silicone rubber, 2-6 wt% of plasticizer, 30-60 wt% of conductive filler and 4-7 wt% of thixotropic agent, and is printed by a desktop extrusion 3D printer to obtain any shapeA conductive rubber in the form of a rubber. The patent has the following characteristics or limitations: 1) the metal powder used in the formula has large filling amount and metal powder density (more than 3 g/cm)3) Much larger than that of silicon rubber (1.2 g/cm)3) Sedimentation easily occurs in a pure liquid state to affect printing performance; 2) the patent lacks a study on commercialization of a flexible conductive material (circuit electrode sensor, etc.).
Patent CN108690190A (application date 5 and 14 in 2018, and publication date 2018 and 10 and 23 in 2018) prepares a flexible electronic sensor for 3D printed skin and a preparation method thereof. In the patent, a composite pressure sensing membrane prepared from polyaniline and a multi-walled carbon nanotube is arranged on the inner sides of two ultrathin PDMS membranes, and an electrode is led out between the pressure sensing membrane and the PDMS membrane to prepare a flexible electronic sensor. The patent has the following characteristics and limitations: 1) the sensor is a pressure sensor and is not suitable for tensile load; 2) the elasticity of the sensor is mainly provided by the PDMS film, and the elasticity of the sensing film is low; 3) this patent lacks testing of pressure sensing performance parameters.
Patent CN105623215B (application date 2016, 2/2016, publication date 2016, 6/1/2016) discloses a flexible circuit conductive composition and a method for 3D printing flexible circuits. In the patent, a thermoplastic matrix and conductive filler are melted and blended by an internal mixer, melted and extruded by an extruder to form conductive wire materials, and finally, a heating printing head is used for printing the conductive wire materials on a flexible substrate to prepare a flexible circuit. The patent has the following characteristics or limitations: 1) printing wires are made of thermoplastic materials, and an extrusion head is required to be heated at high temperature during printing; 2) the flexible circuit provides flexibility with a flexible substrate, and the conductive material has no flexibility; 3) during preparation, dangerous chemicals such as concentrated sulfuric acid are adopted.
US10350329B2, graphene-based ink compositions for the same-dimensional printing applications (application date 2015, 10-15 days, publication date 2019, 6-16 days) discloses printable flexible conductive inks filled with a high molecular weight elastomeric polymer with graphite fillers. The ink may include polyester, polymethacrylate, polyacrylate, polyethylene glycol, or any combination thereof, polylactic acid, glycolic acid. The graphene content is at least 20 wt%. The printing product is extruded by a needle cylinder to be directly printed and formed by writing (DIW), and the applicable stretching amount is 60%. It has the following features and limitations: 1) the graphene density is low, so that the graphene filling charge used by the material is high; 2) the material only tests resistance response, is not used for a sensor, and lacks the research of response stability.
Preparation and Performance of Flexible Ag-clad Cu-based conductive circuits [ J ] by Shendan et al (Shendan, Suxiaepi, Min-Wen, et al]Electronic components and materials, 2019, 38 (7): 37-41) silver-coated copper powder is used as a conductive filler, and polyurethane modified acrylic resin is used as matrix resin to prepare the flexible conductive circuit through screen printing. The lowest resistivity of the prepared conductive composite material can reach 1.06 multiplied by 10-3Omega cm. When the material is bent in a circuit, the small bulb to be tested can be darkened, namely, the material has a deformation sensing function. The material has the following limitations: 1) the material preparation is screen printing, and the preparation of any shape cannot be realized; 2) lack of research on the flexible elongation and the electrical property response of the material, 3) higher filling amount which reaches more than 60 percent
Zhao Musen et al (Zhao Musen, in sea wave, Sun Lina, et al. wearable flexible sensors prepared based on graphene/PEDOT: PSS composite [ J ] China science: technical science, 2019(7): 851. 860.) use a graphene dispersion in PEDOT: in the PSS, the multi-component composite ink sensor is prepared through dispensing extrusion printing, and the influence of the printing speed and the printing height on the size and the resistance of the printing sensor is researched. The material has the following limitations: 1) the sensor recognizes the load as a bending load, and has no stretchability; 2) the flexible sensor fails when the load sensor is bent by more than 75 degrees, and the flexibility is low.
Muth et al (Muth J T, Vogt D M, Truby R L, et al embedded 3 printing of strain sensors with high strain reactors [ J ] advanced materials,2014,26(36):6307-12.) use a carbon black filled resin as the 3D printing material to print the flexible sensor embedded in a liquid PDMS substrate by an extrusion type 3D printer. The sensor does not need to be packaged, and the preparation process is quick, simple and convenient. However, there are several limitations: 1) the sensing material embedded in the sensor is liquid and has no elasticity; 2) the conductive path of the material is damaged after multiple cycles, and the stability is poor.
shuiQi Liu et al (Liu S, Lin Y, Wei Y, et al. A High Performance Self-sealing string Sensor with synergistic Networks of Poly (. However, the following limitations exist: 1) the material conducting layer has no elasticity, and the elasticity is provided by the flexible substrate; 2) the sensor can not be prepared in a conformal manner, and the cutting sample preparation precision is low.
In summary, the research and patents on the high-flexibility stretching sensor suitable for 3D printing are still lacking, and the following limitation problems exist in the current technology of the flexible sensor:
(1) most of the currently prepared flexible sensors are pressure-sensitive sensors, some of the sensors are bending sensors, some of the existing flexible stretching sensor sensing materials are inflexible, and the preparation and performance research of the fully flexible stretching sensor is lacked.
(2) Most of the sensor products in the patent lack the report of sensor performance, and even have no research on the sensor stability
(3) Solvents and fillers used by a plurality of materials suitable for 3D printing have certain toxicity, and are easy to damage the health of people during operation.
Disclosure of Invention
The invention provides a preparation method of a conductive composite material of a flexible tension sensor suitable for 3D printing based on the technical weaknesses, which is characterized in that ① composite material is made of conductive material selected from fibrous filler, the material filling amount is low, ② is a formula of compounding rigid conductive material and solid flexible particles, so that the printing material has good printing performance, the prepared sensor has stable sensing performance, ③ material preparation and printing process are simple and convenient, the preparation time of the printing material is less than 1h, only ten minutes is needed for printing and forming, 3D printed products obtained by ④ have good flexibility, the Shore hardness is lower than 80, the tensile strength is higher than 2MPa, the elongation is higher than 200%, ⑤ the sensor prepared by the method has the advantages of resistance change rate of 100% in 10% strain, stable performance in more than 600 times of cyclic loading, close to linear change in resistance response and the like, ⑥ preparation is safe, and the used raw materials are non-toxic and non-pollution silicone rubber and filler.
1. A preparation method of a flexible conductive material suitable for 3D printing is characterized in that the composite material is prepared by mixing 55-65 wt% of liquid silicone rubber, 25-35 wt% of fiber conductive filler, 2-6 wt% of solid flexible particles, 1-6 wt% of polymerization agent and 1-3 wt% of diluent, wherein the mass ratio of the fiber conductive filler to the solid flexible particles is 5:1-15: 1.
2. Further, it is characterized in that the liquid silicone rubber used is vinyl-terminated polydimethylsiloxane having a viscosity of 5 to 20 pas and a density of 1.2g/cm 3.
3. Further, the method is characterized in that the liquid silicone rubber viscosity test conditions are as follows: ambient temperature was 25 ℃ and stirring rate 5 RPM.
4. Further, the conductive fiber filler is silver-plated glass fiber powder or nickel-plated carbon fiber powder.
5. Further characterized in that the solid compliant particles are carbon fibers.
6. Further, the polymerization agent is castor oil or 1, 2-propylene glycol.
7. Further, it is characterized in that the diluent is simethicone.
8. Further, it is characterized in that the printing step comprises the following points: 1) a liquid silicone rubber substrate is prepared. 2) And embedding the needle head into the liquid matrix, printing the conductive rubber according to a set printing path, and exposing the sensing resistance wire from the matrix at the electrode needing to be led out. 3) After printing, the needle head is drawn out of the substrate, and the flexible stretching sensor with good encapsulation is obtained after vulcanization at 120 ℃ for 10 minutes.
1. Solid compliant particle (carbon fiber) -polymerizer synergy mechanism: the carbon fiber is completely dispersed in the single liquid silicone rubber, after the polymerizing agent is added into the silicone rubber solution with the uniformly distributed carbon fiber, the insoluble polymerizing agent is dispersed in the solution, and after the dispersed carbon fiber is contacted with the polymerizing agent, the surface tension of the polymerizing agent enables the carbon fiber to be wetted, and a polymerizing agent layer is formed on the surface of the carbon fiber. The carbon fibers with the polymerizing agent layers touch each other after further stirring, the fibers are polymerized by the surface tension of the two polymerizing agent layers, the spherical polymers are scattered into a tree shape under the action of the stirring mechanical energy, and the spherical polymers are bridged with each other to form a frame structure after the stirring is finished. The framework structure has excellent effect of inhibiting the sedimentation of the high-density filler and ensures that the material has certain shape retention property in a liquid state. During printing extrusion, the carbon fiber is easy to deflect at an extrusion opening, and the printing performance is further improved.
2. The conductivity mechanism: compared with spherical and dendritic conductive fillers, the fibrous fillers in the liquid silicone rubber can form more point contacts, and can achieve better conductivity at lower filling amount. When the composite material is printed and extruded, the fibrous fillers are oriented and arranged under the action of fluid force, the solid flexible particles are influenced by the surface tension of the polymerization agent, so that the metal fillers with poor compatibility with the silicon rubber are mutually extruded and contacted to form a new conductive path, and meanwhile, the carbon fiber flexible particles have certain conductivity, so that the conductivity of the composite material is further improved.
3. Sensing stability: the polymer material such as rubber has viscoelasticity, the bonding property of the metal fiber and the matrix is not high, the micro hysteresis deformation generated during the deformation of the matrix has small influence on the motion of the filler, and the electrical property recovery process is not obvious. The solid flexible particles such as carbon fibers and the like are well combined with the matrix, when the particles are loaded for a long time, the stress between the metal fillers and the matrix are replaced by the particles to bear, the internal conductive path and the rubber matrix are kept stable, and the service life of the material is prolonged. The synergistic effect of the two different particles enables the sensor to have better electrical response performance and service life.
4. Mixing sequence: the conductive rubber is prepared by sequentially mixing liquid silicone rubber, conductive filler, solid soft particles, polymerization agent and diluent. The addition of the polymerization agent first causes surface tension in the solid pliable particles resulting in uneven agitation. After the synergistic effect occurs, the conductive filler is added, and the surface tension of the conductive filler can prevent the filler and the soft particles from being uniformly dispersed, so that the final performance is influenced.
5. The proportioning mechanism is as follows: the proportion of the two components is required to be within the range of claim 1, and the synergistic effect is weakened due to the fact that the proportion of the conductive filler is too high, the sedimentation of the material is accelerated, the resistivity of the material is reduced, and the service life of the material is shortened. The material resistivity is reduced due to the fact that the solid compliant particle proportion is too high, and the sensor response has high hysteresis.
Drawings
FIG. 1 resistance response and load spectrum of a compound flexible tension sensor
FIG. 2 is a resistance response curve (10% strain) for a built flexible tensile sensor over 100 cycles.
FIG. 3 resistance response curve (10% strain) for a silver coated fiberglass type flexible tensile sensor over 100 cycles
FIG. 4 resistance response curve (10% strain) for 100 cycles of a carbon fiber-based flexible tensile sensor
Detailed Description
The effects of the present invention are illustrated below by specific examples:
example 1
The formula of the liquid conductive rubber comprises 63 wt% of liquid silicone rubber and 27 wt% of silver-plated glass fiber (the silver plating amount is 18 wt%, the length-diameter ratio is 200 mu m: 8 mu m), 4 wt% of carbon fiber, 4 wt% of 1,2 propylene glycol and 2 wt% of dimethyl silicone oil, the preparation method comprises the following steps of ① mixing, adding the prepared materials according to the liquid silicone rubber, the silver-plated glass fiber, the carbon fiber, the 1,2 propylene glycol and the dimethyl silicone oil in sequence, mixing uniformly, ② degassing and canning, namely injecting the mixed liquid conductive rubber into a degassing printing syringe after vacuum degassing, injecting the liquid conductive rubber into the printing syringe, conducting ③ printing and forming, wherein the inner diameter of an extrusion needle is 0.42mm, the pressure is 0.5MPa, the printing speed is 8cm/s, the embedding depth is 0.3mm, ④ curing is carried out, and the curing temperature is 120.
The finished product is prepared, the printing material has the volume resistivity of 0.085 omega cm, the tensile strength of 3.1MPa, the elongation at break of 265 percent and the sensitivity (resistance change rate/strain) of 17, and the performance is stable in 600 continuous loading periods. The resistance response curve and the load spectrum are shown in figure 1, the cyclic load curve is shown in figure 2, and figures 3 and 4 are respectively a performance test of a flexible sensor control group prepared by single silver-plated glass fiber and carbon fiber.
Example 2
The formula of the liquid conductive rubber comprises 60 wt% of liquid silicone rubber and 32 wt% of silver-plated glass fiber (the silver plating amount is 18 wt% and the length-diameter ratio is 200 mu m: 8 mu m), 3 wt% of carbon fiber, 3 wt% of 1,2 propylene glycol and 2 wt% of dimethyl silicone oil, the preparation method comprises the following steps of ① mixing, adding the prepared materials according to the liquid silicone rubber, the silver-plated glass fiber, the carbon fiber, the 1,2 propylene glycol and the dimethyl silicone oil in sequence, mixing uniformly, ② degassing and canning, namely injecting the mixed liquid conductive rubber into a degassing printing syringe after vacuum degassing, injecting the liquid conductive rubber into the printing syringe, conducting ③ printing and forming, wherein the inner diameter of an extrusion needle is 0.42mm, the pressure is 0.5MPa, the printing speed is 8cm/s, the embedding depth is 0.3mm, ④ curing is carried out, and the curing temperature is.
The finished product is prepared, the volume resistivity of the printing material is 0.021 omega cm, the tensile strength is 2.6MPa, the elongation at break is 243%, the sensitivity (resistance change rate/strain) is 14, and the performance is stable in 600 continuous loading periods.
Example 3
The formula of the liquid conductive rubber comprises 55 wt% of liquid silicone rubber, 35 wt% of silver-plated glass fiber (the silver plating amount is 18 wt% and the length-diameter ratio is 200 mu m: 8 mu m), 3 wt% of carbon fiber, 3 wt% of 1,2 propylene glycol and 4 wt% of diluent, and the liquid conductive rubber is prepared by ① mixing, sequentially adding the prepared materials according to the liquid silicone rubber, the silver-plated glass fiber, the carbon fiber, the 1,2 propylene glycol and dimethyl silicone oil and uniformly mixing, ② degassing and canning, namely injecting the mixed liquid conductive rubber into a printing syringe after vacuum degassing, degassing again after injecting, ③ printing and forming, wherein the inner diameter of an extrusion needle head is 0.42mm, the pressure is 0.5MPa, the printing speed is 8cm/s, the embedding depth is 0.3mm, ④ curing is carried out, and the curing temperature is 120 ℃ and 10 min.
The finished product is prepared, the printing material has the volume resistivity of 0.009 omega cm, the tensile strength of 2.4MPa, the elongation at break of 232 percent and the sensitivity (resistance change rate/strain) of 11, and the performance is stable within 600 continuous loading periods.
Example 4
The formula of the liquid conductive rubber is 65 wt% of liquid silicone rubber and 25 wt% of silver-plated glass fiber (the silver plating amount is 18 wt%, the length-diameter ratio is 200 mu m: 8 mu m), 5 wt% of carbon fiber, 4 wt% of 1,2 propylene glycol and 1 wt% of dimethyl silicone oil, the preparation method comprises the following steps of ① mixing, adding the prepared materials according to the liquid silicone rubber, the silver-plated glass fiber, the carbon fiber, the 1,2 propylene glycol and the dimethyl silicone oil in sequence, mixing uniformly, ② degassing and canning, injecting the mixed liquid conductive rubber into a degassing printing syringe after vacuum degassing, injecting the liquid conductive rubber into the printing syringe, ③ printing and forming, wherein the inner diameter of the extrusion syringe needle is 0.42mm, the pressure is 0.5MPa, the printing speed is 8cm/s, the embedding depth is 0.3mm, ④ curing is carried out at the curing temperature of 120 ℃ for 10min, and the finished product is prepared, and the printing material has the volume resistivity of 0.004 cm, the tensile strength of 2.5MPa, the elongation at break, 224%, the resistance change rate/.
Example 5:
the formula of the liquid conductive rubber comprises 60 wt% of liquid silicone rubber, 30 wt% of nickel-plated carbon fiber (the nickel plating amount is 25 wt%, the length-diameter ratio is 200 mu m and is 8 mu m), 5 wt% of carbon fiber, 4 wt% of castor oil and 1 wt% of dimethyl silicone oil, the preparation method comprises the following steps of ① mixing, adding the prepared materials according to the liquid silicone rubber, the nickel-plated carbon fiber, the castor oil and the dimethyl silicone oil in sequence, uniformly mixing, ② degassing and canning, injecting the mixed liquid conductive rubber into a printing syringe after vacuum degassing, degassing again after injecting, ③ printing and forming, wherein the inner diameter of an extrusion needle head is 0.42mm, the pressure is 0.5MPa, the printing speed is 8cm/s, the embedding depth is 0.3mm, and ④ curing is carried out at the curing temperature of 120 ℃ for 10 min.
The finished product is prepared, the printing material has the volume resistivity of 0.48 omega cm, the tensile strength of 2.6MPa, the elongation at break of 225 percent and the sensitivity (resistance change rate/strain) of 13, and the performance is stable in 600 continuous loading periods.
Example 6:
the formula of the liquid conductive rubber comprises 58 wt% of liquid silicone rubber and 32 wt% of nickel-plated carbon fiber (the nickel plating amount is 25 wt%, the length-diameter ratio is 200 mu m and is 8 mu m), 4 wt% of carbon fiber, 4 wt% of 1,2 propylene glycol and 2 wt% of dimethyl silicone oil, the preparation method comprises the following steps of ① mixing, adding the prepared materials according to the liquid silicone rubber, the nickel-plated carbon fiber, the 1,2 propylene glycol and the dimethyl silicone oil in sequence, mixing uniformly, ② degassing and canning, namely injecting the mixed liquid conductive rubber into a printing syringe after vacuum degassing, degassing again after injecting, ③ printing and forming, wherein the inner diameter of an extrusion needle head is 0.42mm, the pressure is 0.5MPa, the printing speed is 8cm/s, the embedding depth is 0.3mm, ④ curing is carried out, and the curing temperature is 120 ℃ and 10 min.
The finished product is prepared, the printing material has the volume resistivity of 0.82 omega cm, the tensile strength of 2.8MPa, the elongation at break of 265 percent and the sensitivity (resistance change rate/strain) of 15, and the performance is stable within 600 continuous loading periods.
Example 7:
the formula of the liquid conductive rubber comprises 55 wt% of liquid silicone rubber and 35 wt% of nickel-plated carbon fiber (the nickel plating amount is 25 wt%, the length-diameter ratio is 200 mu m and is 8 mu m), 3 wt% of carbon fiber, 4 wt% of 1,2 propylene glycol and 3 wt% of dimethyl silicone oil, the preparation method comprises the following steps of ① mixing, adding the prepared materials according to the liquid silicone rubber, the nickel-plated carbon fiber, the 1,2 propylene glycol and the dimethyl silicone oil in sequence, mixing uniformly, ② degassing and canning, namely injecting the mixed liquid conductive rubber into a printing syringe after vacuum degassing, degassing again after injecting, ③ printing and forming, wherein the inner diameter of an extrusion needle is 0.42mm, the pressure is 0.5MPa, the printing speed is 8cm/s, the embedding depth is 0.3mm, ④ curing is carried out, and the curing temperature is 120 ℃ and 10 min.
The finished product is prepared, the volume resistivity of the printing material is 0.2 omega cm, the tensile strength is 2.4MPa, the elongation at break is 213%, the sensitivity (resistance change rate/strain) is 10, and the performance is stable within 600 continuous loading periods.
Example 8:
the formula of the liquid conductive rubber comprises 63 wt% of liquid silicone rubber, 26 wt% of nickel-plated carbon fiber (the nickel plating amount is 25 wt%, the length-diameter ratio is 200 mu m and is 8 mu m), 5 wt% of carbon fiber, 4 wt% of castor oil and 2 wt% of dimethyl silicone oil, the preparation method comprises the following steps of ① mixing, adding the prepared materials according to the liquid silicone rubber, the nickel-plated carbon fiber, the castor oil and the dimethyl silicone oil in sequence, uniformly mixing, ② degassing and canning, injecting the mixed liquid conductive rubber into a printing syringe after vacuum degassing, degassing again after injecting, ③ printing and forming, wherein the inner diameter of an extrusion needle head is 0.42mm, the pressure is 0.5MPa, the printing speed is 8cm/s, the embedding depth is 0.3mm, and ④ curing is carried out at the curing temperature of 120 ℃ for 10 min.
The finished product is prepared, the volume resistivity of the printing material is 0.9 omega cm, the tensile strength is 2.6MPa, the elongation at break is 290%, the sensitivity (resistance change rate/strain) is 18, and the performance is stable within 600 continuous loading periods.
Example 9
The formula of the liquid conductive rubber comprises 62 wt% of liquid silicone rubber, 9 wt% of silver-plated glass fiber (the silver plating amount is 18 wt%, the length-diameter ratio is 200 mu m: 8 mu m), 20 wt% of nickel-plated carbon fiber (the nickel plating amount is 25 wt%, the length-diameter ratio is 200 mu m: 8 mu m), 4 wt% of carbon fiber, 4 wt% of 1, 2-propylene glycol and 1 wt% of dimethyl silicone oil, the liquid conductive rubber is prepared by mixing ①, the prepared materials are sequentially added and uniformly mixed according to the liquid silicone rubber, the silver-plated glass fiber, the nickel-plated carbon fiber, the carbon fiber, 1, 2-propylene glycol and dimethyl silicone oil, degassing and canning ②, wherein the mixed liquid conductive rubber is degassed after being injected into a printing syringe in vacuum, degassing is carried out again, ③ is printed and formed, the inner diameter of an extrusion needle is 0.42mm, the pressure is 0.5MPa, the printing speed is 8cm/s, the embedding depth is 0.3mm, ④ is cured, and.
The finished product is prepared, the printing material has the resistivity of 0.012 omega cm, the tensile strength of 3.2MPa, the elongation at break of 245 percent, the sensitivity (resistance change rate/strain) of 14 percent, and the performance is stable within 600 continuous loading periods.
Example 10
The formula of the liquid conductive rubber comprises 60 wt% of liquid silicone rubber, 10 wt% of silver-plated glass fiber (the silver plating amount is 18 wt%, the length-diameter ratio is 200 mu m: 8 mu m), 22 wt% of nickel-plated carbon fiber (the nickel plating amount is 25 wt%, the length-diameter ratio is 200 mu m: 8 mu m), 4 wt% of carbon fiber, 3 wt% of castor oil and 1 wt% of dimethyl silicone oil, and the liquid conductive rubber is prepared by the following steps of mixing ①, adding prepared materials into a printing needle cylinder according to the liquid silicone rubber, the silver-plated glass fiber, the nickel-plated carbon fiber, the castor oil and the dimethyl silicone oil in sequence, uniformly mixing, degassing after mixing, ② canning, injecting the mixed liquid conductive rubber into the printing needle cylinder after degassing in vacuum, degassing again after injecting, printing and molding by ③, extruding the inner diameter of the needle head to be 0.42mm, the pressure to be 0.5MPa, the printing speed to be 8cm/s, the.
The finished product is prepared, the volume resistivity of the printing material is 0.068 omega cm, the tensile strength is 2.9MPa, the elongation at break is 257%, the sensitivity (resistance change rate/strain) is 13, and the performance is stable within 600 continuous loading periods.

Claims (8)

1. A preparation method of a flexible conductive material suitable for 3D printing is characterized in that the composite material is prepared by mixing 55-65 wt% of liquid silicone rubber, 25-35 wt% of fiber conductive filler, 2-6 wt% of solid flexible particles, 1-6 wt% of polymerization agent and 1-3 wt% of diluent, wherein the mass ratio of the fiber conductive filler to the solid flexible particles is 5:1-15:1, the preparation method comprises the steps of ① mixing, adding the materials in sequence according to the liquid silicone rubber, the fiber conductive filler, the solid flexible particles, the polymerization agent and the diluent, fully mixing uniformly to obtain liquid conductive rubber, ② vacuum processing, placing the liquid conductive rubber in ① in a vacuum environment for degassing, filling the liquid conductive rubber into a printing needle cylinder after the degassing is completed, placing the liquid conductive rubber in the vacuum environment again for degassing, printing and forming ③, preparing the liquid conductive rubber in a prepared liquid substrate according to a printing route to obtain a liquid sensor with a certain shape, and ④ curing and forming the liquid sensor at 120 ℃ for curing for 10min to obtain a final flexible sensor product.
2. The process according to claim 1, wherein the liquid silicone rubber used is vinyl-terminated polydimethylsiloxaneAn alkane having a viscosity of 5 to 20 pas and a density of 1.2g/cm3。
3. The method according to claim 2, wherein the liquid silicone rubber is subjected to the following conditions for the viscosity test: ambient temperature was 25 ℃ and stirring rate 5 RPM.
4. The method according to claim 1, wherein the conductive filler is silver-coated glass fiber powder or nickel-coated carbon fiber powder.
5. The method of claim 1, wherein the solid compliant particles are carbon fibers.
6. The method of claim 1, wherein the polymerization agent is castor oil or 1, 2-propanediol.
7. The method according to claim 1, wherein the diluent is dimethicone.
8. The manufacturing method according to claim 1, wherein the printing and forming includes the following points: 1) preparing a liquid silicon rubber substrate; 2) embedding a needle head into a liquid matrix, printing conductive rubber according to a set printing path, and exposing a sensing resistance wire from the matrix at an electrode needing to be led out; 3) and after printing is finished, the needle head is drawn out of the substrate, and the packaged flexible stretching sensor is obtained after vulcanization is carried out for 10 minutes at 120 degrees.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112113497A (en) * 2020-08-17 2020-12-22 华南理工大学 Self-healing resistance type strain sensor and preparation method and application thereof
CN112721147A (en) * 2020-12-03 2021-04-30 昆明理工大学 Method for preparing graphene-based flexible bionic sensing material through 3D printing
TWI749811B (en) * 2020-10-15 2021-12-11 國立中正大學 Laminated printing soft material containing plant fibers

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104231439A (en) * 2014-09-25 2014-12-24 中北大学 Polypropylene/nickel-plated glass fiber conductive composite material and preparation method thereof
CN106751908A (en) * 2017-01-09 2017-05-31 北京工业大学 A kind of 3D printing flexible conductive composite material and preparation method thereof
US20180361660A1 (en) * 2015-12-22 2018-12-20 Carbon, Inc. Dual cure additive manufacturing of rigid intermediates that generate semi-rigid, flexible, or elastic final products

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104231439A (en) * 2014-09-25 2014-12-24 中北大学 Polypropylene/nickel-plated glass fiber conductive composite material and preparation method thereof
US20180361660A1 (en) * 2015-12-22 2018-12-20 Carbon, Inc. Dual cure additive manufacturing of rigid intermediates that generate semi-rigid, flexible, or elastic final products
CN106751908A (en) * 2017-01-09 2017-05-31 北京工业大学 A kind of 3D printing flexible conductive composite material and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112113497A (en) * 2020-08-17 2020-12-22 华南理工大学 Self-healing resistance type strain sensor and preparation method and application thereof
CN112113497B (en) * 2020-08-17 2021-12-21 华南理工大学 Self-healing resistance type strain sensor and preparation method and application thereof
TWI749811B (en) * 2020-10-15 2021-12-11 國立中正大學 Laminated printing soft material containing plant fibers
CN112721147A (en) * 2020-12-03 2021-04-30 昆明理工大学 Method for preparing graphene-based flexible bionic sensing material through 3D printing

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