CN114735678B - Preparation method and application of graphene/SiC composite material - Google Patents
Preparation method and application of graphene/SiC composite material Download PDFInfo
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Abstract
The application discloses a preparation method of a graphene/SiC composite material, which comprises the following steps: 1) Pre-oxidizing the fiber material to obtain an amorphous carbon material; 2) Embedding an amorphous carbon material into a flexible matrix material to obtain a matrix material embedded with the amorphous carbon material; 3) And carrying out laser induction on the matrix material embedded with the amorphous carbon material to obtain the graphene/SiC composite material. According to the application, the pre-oxidized fiber material is directly induced to form a graphene structure by a laser induction technology, and the depth of embedding the pre-oxidized fiber material into the flexible matrix material is controlled, so that the molding quality of the prepared graphene/SiC composite material and the mechanical property of the flexible matrix material are controlled. The preparation method of the graphene/SiC composite material can be widely applied to manufacturing of sensors or biological signal detection devices.
Description
Technical Field
The application belongs to the field of materials, and particularly relates to a preparation method and application of a graphene/SiC composite material.
Background
The appearance of flexible wearable sensing provides great convenience for people to detect vital signs of themselves, and a base material applied to the flexible wearable system should have functions of bending, curling, stretching and the like, and be combined with corresponding nano materials or nano technologies. The flexible wearable sensor has the characteristics of good conductivity, larger specific surface area, durability, comfort and the like in face of different application requirements; graphene materials have been widely used in flexible wearable sensing systems because of their excellent properties in these respects.
Graphene is used as a two-dimensional conductive material with excellent performance, and is widely applied to a wearable sensing system, but the traditional manufacturing process of graphene, such as a mechanical stripping method, a chemical vapor deposition method, a SiC high Wen Tui fire method, a graphene oxide reduction method and the like, has the common problems of complex procedures, severe process conditions, pollution in the manufacturing process, low graphene performance and the like. Based on the wide application of graphene materials in flexible wearable sensing systems, the graphene preparation method in the prior art still cannot meet the huge demands of the industry on the graphene materials, researchers develop various processing and manufacturing processes of graphene for solving the problems, wherein Polyimide (PI) is successfully induced to generate three-dimensional porous graphene (Jian L, peng Z, liu Y, et al laser-induced porous graphene films from commercial polymers [ J ]. Nature Communications,2014, 5:5714.) under the air atmosphere by a carbon dioxide laser, and a new way is created for manufacturing the flexible wearable sensing matrix material. However, PI materials are costly, limiting their application in flexible wearable sensors, and therefore a new method for preparing graphene materials is necessary.
Disclosure of Invention
In order to overcome the problems in the prior art, one of the purposes of the present application is to provide a preparation method of a graphene/SiC composite material; the second purpose of the application is to provide the application of the preparation method of the graphene/SiC composite material; the application further aims to provide an application of the graphene/SiC composite material prepared by the preparation method of the graphene/SiC composite material.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
the first aspect of the application provides a preparation method of a graphene/SiC composite material, which comprises the following steps:
1) Pre-oxidizing the fiber material to obtain an amorphous carbon material;
2) Embedding an amorphous carbon material into organic silicon to obtain a matrix material embedded with the amorphous carbon material;
3) And carrying out laser induction on the matrix material embedded with the amorphous carbon material to obtain the graphene/SiC composite material.
Preferably, the fiber material comprises at least one of a natural fiber material and a synthetic fiber material; further preferably, the fiber material comprises at least one of cotton fiber, bamboo fiber, wood fiber, terylene, chinlon, acrylon, polypropylene fiber, vinylon and chlorfiber; still further preferably, the fibrous material comprises at least one of cotton, cotton paper; still more preferably, the fibrous material is cotton cloth.
Preferably, in the case that the fiber material is cotton cloth or cotton paper, the cotton content of the fiber material is 30-100% by mass; further preferably, the cotton-containing mass percentage of the fiber material is 50% -100%; still further preferred, the cotton-containing mass percent of the fibrous material is 80% to 100%.
Preferably, in the step 1), the pre-oxidation temperature is 270 ℃ to 330 ℃; further preferably, the pre-oxidation temperature is 280 ℃ to 320 ℃; still further preferred, the pre-oxidation temperature is 290 ℃ to 310 ℃.
Preferably, in the step 1), the pre-oxidation time is 1h-3h; further preferably, the pre-oxidation time is 1.5h to 2.5h.
Preferably, in the step 1), the temperature rising rate of the pre-oxidation is 1 ℃/min-3 ℃/min; further preferably, the temperature rising rate of the pre-oxidation is 1.5 ℃/min-2.5 ℃/min.
Preferably, in the step 1), the pre-oxidizing atmosphere is an oxygen-containing atmosphere; further preferably, in the step 1), the pre-oxidizing atmosphere is air.
Preferably, in the step 1), the amorphous carbon material has a thickness of 200 μm to 400 μm; further preferably, in the step 1), the amorphous carbon material has a thickness of 200 μm to 300 μm.
Optionally, in the step 1), the amorphous carbon material has a length of 10mm to 30mm; further 15mm-25mm.
Optionally, in the step 1), the amorphous carbon material has a width of 10mm to 30mm; further preferably, in the step 1), the amorphous carbon material has a width of 15mm to 25mm.
Preferably, in the step 2), the depth of the amorphous carbon material embedded in the organic silicon is not more than 80% of the thickness of the amorphous carbon material; further preferably, in the step 2), the depth of embedding of the amorphous carbon material into the organic silicon is not more than 80% of 20% of the amorphous carbon material; for example, in the case where the amorphous carbon material has a thickness of 200 μm to 400 μm, the depth of the intercalation may be 50 μm to 200 μm; further preferably 70 μm to 150 μm; still more preferably 80 μm to 120. Mu.m. The depth of the amorphous carbon material embedded into the organic silicon is too deep, so that the organic silicon can completely cover the amorphous carbon material, and at the moment, most of the heat of the laser can be absorbed by the organic silicon on the surface of the amorphous carbon material, so that the embedded amorphous carbon material can not reach the critical temperature required by induction, and the conversion from the amorphous carbon material to graphene can not be realized; the too shallow embedding depth can lead to the reduction of the thermal contact area between the amorphous carbon material and the organic silicon, so that heat is difficult to be conducted into the organic silicon through the amorphous carbon material, the quantity of SiC crystals generated by thermal decomposition of the organic silicon is limited, the protection effect on the amorphous carbon material cannot be realized, and the amorphous carbon material can damage the structure of the amorphous carbon material due to thermal shock and sudden rise of the temperature of laser in the laser processing process.
Optionally, in the step 2), the thickness of the base material is 0.5mm to 2.0mm; further 0.7mm to 1.5mm; still further 0.8mm to 1.2mm.
Optionally, in the step 2), the length of the matrix material is 10mm to 30mm; further 15mm-25mm.
Optionally, in the step 2), the width of the flexible matrix material is 10mm to 30mm; further 15mm-25mm.
Preferably, in the step 2), the organic silicon further includes silicate compound, and after the amorphous carbon material is embedded in the organic silicon, the organic silicon is further cured. The silicate compound is a silicon dioxide precursor and comprises at least one of tetraethoxysilane and tetramethylsilicate.
Preferably, in the organic silicon, the mass fraction of the silicate compound is 5% -10%.
Preferably, the molecular weight of the organosilicon is 100-3000; further preferably, the molecular weight of the silicone is 162-3000.
Preferably, the method of curing includes a heat curing method.
Preferably, the temperature of the curing heat is 60 ℃ to 100 ℃; further preferably, the curing heat is at a temperature of 70 ℃ to 90 ℃.
Preferably, the curing and heating time is 40min-80min; further preferably, the curing and heating time is 50min-70min.
Preferably, in the step 2), before the amorphous carbon material is embedded in the silicone, the step of pre-curing the silicone is further included.
Preferably, the pre-curing method includes a heat curing method.
Preferably, the temperature of the pre-curing heating is 60 ℃ to 100 ℃; further preferably, the temperature of the pre-curing heat is from 70 ℃ to 90 ℃.
Preferably, the time of pre-curing and heating is 2-9 min; further preferably, the time of the pre-curing heating is 4min-8min.
Preferably, the organic silicon comprises at least one of polydimethylsiloxane, polymethyl hydrogen-containing siloxane and polymethyl phenyl siloxane; further preferably, the silicone comprises polydimethylsiloxane.
Preferably, in the step 3), the laser light source is a carbon dioxide laser.
Preferably, in the step 3), the laser power is 1W to 30W; further preferably, the laser power is 1.5W-10W; further preferably, the laser power is 2W-5W.
Preferably, in the step 3), the laser scanning rate is 1mm/s-100mm/s; further preferably, the laser scanning rate is 3mm/s to 50mm/s; still further preferably, the laser scanning rate is 8mm/s to 20mm/s.
Preferably, in the step 3), the laser wavelength is 6 μm to 20 μm; further preferably, the laser wavelength is 8 μm to 15 μm.
Preferably, in the step 3), the diameter of the light spot in the focusing state of the laser is 200 μm to 300 μm; further preferably, the spot diameter in the laser focusing state is 230 μm to 270 μm.
Preferably, in the step 3), the laser-induced atmosphere is an oxygen-containing atmosphere.
Preferably, the oxygen-containing atmosphere has an oxygen content of 10% to 100%; further preferably, the oxygen-containing atmosphere has an oxygen content of 20% to 50%.
Preferably, in the step 3), the laser-induced atmosphere is air.
Preferably, in the step 2), the method of embedding the amorphous carbon material in the flexible matrix material includes pressurizing the amorphous carbon material to be embedded in the flexible matrix material.
Preferably, the pressure of the pressurization is 2000Pa-8000Pa; further preferably, the pressure of the pressurization is 4000Pa-6000Pa.
Preferably, the pressurizing time is 3min-10min; further preferably, the pressurizing time is 5min-8min.
Preferably, the pressurization is uniform pressurization.
The second aspect of the application provides an application of the preparation method of the graphene/SiC composite material in preparing a sensor or a biological signal detection device.
Preferably, the sensor comprises a wearable sensor; further preferably, the sensor comprises a flexible wearable sensor.
Preferably, the biological signal comprises at least one of swallowing, hand grasping, foot pressure, elbow bending, wrist pulse, finger heart rate, pharyngeal sounding, breathing.
The third aspect of the application provides an application of the graphene/SiC composite material prepared by the preparation method of the graphene/SiC composite material in biological signal detection.
The beneficial effects of the application are as follows:
according to the application, the pre-oxidized fiber material is directly induced to form a graphene structure by a laser induction technology, and the depth of embedding the pre-oxidized fiber material into the flexible matrix material is controlled, so that the molding quality of the prepared graphene/SiC composite material and the mechanical property of the flexible matrix material are controlled. Compared with the traditional graphene production and manufacturing process, the graphene/SiC composite material preparation method disclosed by the application has the advantages of simple raw materials, wide sources and low cost, a graphene structure can be generated by a laser direct writing method, the production efficiency is high, and the graphene/SiC composite material preparation method can be widely applied to manufacturing sensors or biological signal detection devices.
In particular, the application has the following advantages:
1) Compared with the traditional method for producing the three-dimensional porous graphene/SiC composite material by performing laser processing induction by taking PI as a precursor, the cotton fabric adopted by the application has the advantages of simple raw materials, wide sources and low cost; according to the application, the carbon dioxide laser is used as a laser heat source, the amorphous carbon material is used as an induced precursor for laser processing to induce the three-dimensional porous graphene structure, and compared with the traditional graphene production and manufacturing method (physical coating, chemical vapor deposition and the like), the three-dimensional porous graphene structure is more convenient and faster, and the cost of the processing mode is lower. Compared with the existing method for preparing graphene by using a laser-induced polymer, the method for preparing graphene by using the cotton fiber material and embedding the flexible matrix material has the advantages that the prepared graphene/SiC composite material has better skin-friendly property and flexibility; by adopting the method of embedding the amorphous carbon material into the matrix material, the molding quality of the prepared porous graphene/SiC composite material and the mechanical property of the manufactured flexible pressure sensor can be controlled by controlling the embedding depth.
2) The method comprises the steps of pre-oxidizing a fiber material to generate amorphous carbon, embedding the amorphous carbon into organic silicon to a certain depth, and generating a porous graphene/SiC composite material structure from the pre-oxidized fiber material by utilizing a carbon dioxide laser direct-writing technology; the depth of embedding the preoxidized fiber material into the organic silicon can be controlled, so that the forming quality of the prepared porous graphene/SiC composite material and the mechanical property of the manufactured flexible pressure sensor can be controlled. The carbonized fiber material without the embedded organic silicon can reach the ignition point of the carbonized fiber material under the air atmosphere to burn, so that the integrity of a final sample and the generation quality of the three-dimensional porous graphene are greatly influenced; according to the application, the carbonized fiber material is embedded into the organic silicon, wherein the organic silicon also serves as a flame retardant, and the combustion of the carbonized fiber material in the induction process is inhibited, so that the ideal processing effect is achieved. Compared with the traditional graphene production and manufacturing process (chemical vapor deposition, physical vapor deposition, coating method and the like), the graphene preparation method disclosed by the application has the advantages of simple raw materials, low cost, capability of generating various structures through the characteristics of laser direct writing, and high production efficiency.
3) The preparation method of the graphene/SiC composite material disclosed by the application can be widely applied to manufacturing of sensors or biological signal detection devices, in particular to flexible wearable sensors; the flexible pressure sensor is manufactured by utilizing the generated porous graphene/SiC composite material structure and a Polydimethylsiloxane (PMDS) flexible substrate for packaging, and compared with the flexible pressure sensor manufactured by directly doping graphene, the flexible pressure sensor is simpler, more efficient and lower in cost in process, and can be widely applied to biological signal detection.
Drawings
FIG. 1 is a process flow diagram of an embodiment.
FIG. 2 is a diagram of cotton pre-oxidation.
Fig. 3 is a three-dimensional schematic view of a mold structure.
Fig. 4 is a carbon dioxide laser processing diagram.
FIG. 5 is a cross-sectional electron microscope scan of a carbonized cotton cloth embedded in PDMS.
Fig. 6 is a transmission electron microscope test chart of the three-dimensional porous graphene/SiC composite of example 1.
Fig. 7 is a raman spectrum test chart and an X-ray diffraction test chart of the three-dimensional porous graphene/SiC composite material of example 1.
Fig. 8 is a pictorial view of the flexible pressure sensor after encapsulation is completed.
Fig. 9 is a diagram of a flexible pressure sensor back of hand grip induction test.
FIG. 10 is a graph of flexible pressure sensor elbow bending sensing.
Fig. 11 is a flexible pressure sensor respiration and swallowing monitoring diagram.
Fig. 12 is a wrist pulse monitoring diagram of a flexible pressure sensor.
Fig. 13 is a graph of flexible pressure sensor finger heart rate monitoring.
Fig. 14 is a sound test chart of the flexible pressure sensor.
Fig. 15 is an audio test chart of a flexible pressure sensor.
FIG. 16 is a graph of a flexible pressure sensor plantar pressure test method.
FIG. 17 is a graph of the plantar pressure test results of the flexible pressure sensor.
FIG. 18 is a graph showing the mechanical response sensitivity curve of a LIG/SiC flexible pressure sensor with an embedding depth of 120 μm.
FIG. 19 is a graph showing the mechanical response sensitivity curve of LIG/SiC flexible pressure sensor with an embedding depth of 70 μm.
FIG. 20 is a graph showing the mechanical response sensitivity curve of LIG/SiC flexible pressure sensor with an embedding depth of 0 μm.
FIG. 21 is a graphical representation of cyclic loading test results of a flexible pressure sensor.
Detailed Description
The following examples are presented to further illustrate the practice of the application, but are not intended to limit the practice and protection of the application. It should be noted that the following processes, if not specifically described in detail, can be realized or understood by those skilled in the art with reference to the prior art. The reagents or instruments used did not identify the manufacturer and were considered conventional products available commercially.
FIG. 1 is a process flow diagram of an embodiment, and the present application is further described below with reference to FIG. 1 in conjunction with specific steps.
Example 1
The method for preparing the graphene/SiC composite material by using the laser-induced fabric comprises the following steps:
1) Cutting cotton cloth (containing 95% cotton by mass and having a cotton cloth thickness of 300+ -40 μm) into suitable size, placing in absolute ethanol, ultrasonically cleaning for 20min, taking out, oven drying in a vacuum oven, and setting the drying time to 2h; and (3) placing the pretreated cotton cloth in a muffle furnace cavity, setting the heating rate of the muffle furnace to be 2 ℃/min, the heat preservation temperature to be 300 ℃, the heat preservation time to be 2h, and naturally cooling to room temperature in the pre-oxidized atmosphere to obtain carbonized cotton cloth (the thickness is 250+/-40 mu m). Fig. 2 is a diagram of pre-oxidation of cotton cloth, wherein fig. 2 (a) is a diagram of pre-oxidation of cotton cloth waiting in a muffle furnace chamber, and fig. 2 (b) is a diagram of a real object after pre-oxidation of cotton cloth.
2) Polydimethyl siloxane (PDMS) was prepared according to agent a: agent B = 10:1 (agent A is polydimethylsiloxane PDMS as main agent, available from Dow Corning company, CAS number: 9006-65-9, molecular weight of 162.378, agent B is curing agent tetraethyl orthosilicate, which is a substance or mixture for enhancing or controlling curing reaction, and substances capable of playing a role of crosslinking can be used as curing agent), stirring uniformly for 15min, removing excessive bubbles in a vacuum deaerator, and taking out; then pouring the prepared Polydimethylsiloxane (PDMS) reagent into a specific mold to fill the lowest layer of the mold; the treated Polydimethylsiloxane (PDMS) and the mold were placed on a heating table and preheated for 7min, and then removed. Fig. 3 is a three-dimensional schematic diagram of a mold structure, wherein the length, width and depth of the grooves at the bottom layer of the mold are 20mm by 1mm, and the length, width and depth of the grooves at the upper layer of the mold are 25mm by 1mm.
3) Cutting the pre-oxidized carbonized cotton cloth in the step 1) into square shapes with the length of 20mm multiplied by 20mm, placing the square shapes on Polydimethylsiloxane (PDMS) and a mould processed in the step 2), and applying 5000Pa pressure to uniformly embed the carbonized cotton cloth into the PDMS.
4) Continuously placing the sample with the carbonized cotton cloth embedded into PDMS in the step 3) on a heating table, wherein the temperature of the heating table is 80 ℃, and the heating time is 1h; placing the heated sample under a carbon dioxide laser, setting the laser scanning speed to be 15mm/s, the laser power to be 2.2W, the laser wavelength to be 10.6 mu m, and the spot diameter to be 250 mu m in a laser focusing state; and (3) carrying out reciprocating scanning processing under focused processing conditions, wherein the processing atmosphere is air atmosphere, the carbonized cotton cloth which is not embedded with PDMS is completely combusted in the air, and the carbonized cotton cloth embedded with PDMS is subjected to laser induction to obtain the graphene/SiC composite material prepared in the embodiment. Fig. 4 is a carbon dioxide laser processing diagram.
Example 2
The method for preparing the graphene/SiC composite material by using the laser-induced fabric in the embodiment is different from the embodiment 1 only in that polydimethylsiloxane and a die in the step 2) are placed on a heating table to be preheated for 4min and then taken down, and the rest steps are completely the same as the embodiment 1.
Example 3
The method for preparing the graphene/SiC composite material by using the laser-induced fabric in the embodiment is different from the embodiment 1 only in that polydimethylsiloxane and a die in the step 2) are placed on a heating table to be preheated for 5min and then taken down, and the rest steps are completely the same as the embodiment 1.
Example 4
The method for preparing the graphene/SiC composite material by using the laser-induced fabric in the embodiment is different from the embodiment 1 only in that polydimethylsiloxane and a die in the step 2) are placed on a heating table to be preheated for 6min and then taken down, and the rest steps are completely the same as the embodiment 1.
Example 5
The method for preparing the graphene/SiC composite material by using the laser-induced fabric in the embodiment is different from the embodiment 1 only in that polydimethylsiloxane and a die in the step 2) are placed on a heating table to be preheated for 8min and then taken down, and the rest steps are completely the same as the embodiment 1.
Example 6
The method for preparing the graphene/SiC composite material by using the laser-induced fabric in the embodiment is different from the embodiment 1 only in that polydimethylsiloxane and a die in the step 2) are placed on a heating table to be preheated for 9min and then taken down, and the rest steps are completely the same as the embodiment 1.
Performance testing
1. Electron microscope testing
The samples obtained in steps 1 to 6) were subjected to a cross-sectional scanning electron microscopy test, respectively, in which fig. 5 is a cross-sectional electron microscopy scan after embedding the carbonized cotton cloth into PDMS, wherein fig. 5 (a) is a cross-sectional electron microscopy scan after embedding the carbonized cotton cloth into PDMS of example 2, the carbonized cotton cloth embedding depth is 340±10 μm, wherein fig. 5 (b) is a cross-sectional electron microscopy scan after embedding the carbonized cotton cloth into PDMS of example 3, the carbonized cotton cloth embedding depth is 300±10 μm, fig. 5 (c) is a cross-sectional electron microscopy scan after embedding the carbonized cotton cloth into PDMS of example 4, the carbonized cotton cloth embedding depth is 120±10 μm, fig. 5 (d) is a cross-sectional electron microscopy scan after embedding the carbonized cotton cloth into PDMS of example 1, the carbonized cotton cloth embedding depth is 70±10 μm, fig. 5 (e) is a cross-sectional electron microscopy scan after embedding the carbonized cotton cloth of example 5, the carbonized cotton cloth embedding depth is 40±10 μm, and fig. 5 (f) is a cross-sectional electron microscopy scan after embedding the carbonized cotton cloth of PDMS of example 6. As can be seen from fig. 5, as the pre-curing heating time of the prepared polydimethylsiloxane increases, the hardness of the polydimethylsiloxane gradually increases, and the depth of embedding the carbonized cotton cloth into PDMS gradually decreases. Therefore, the depth of embedding the carbonized cotton cloth into the PDMS can be controlled by controlling the heating time of the pre-curing of the prepared polydimethylsiloxane.
The three-dimensional porous graphene/SiC composite material prepared in step 4) of example 1 was subjected to a transmission electron microscope test, and fig. 6 is a transmission electron microscope test chart of the three-dimensional porous graphene/SiC composite material of example 1, wherein fig. 6 (a) is a small magnification test chart of the transmission electron microscope of the three-dimensional porous graphene/SiC composite material of example 1, and fig. 6 (b) is a large magnification test chart of the transmission electron microscope of the three-dimensional porous graphene/SiC composite material of example 1. The crystalline structure of the multilayer graphene is evident from the transmission electron microscopy test chart shown in fig. 6, demonstrating that a three-dimensional porous graphene structure is produced.
2. Raman spectrum and X-ray diffraction test
The three-dimensional porous graphene/SiC composite material prepared in step 4) of example 1 was subjected to raman spectrum test and X-ray diffraction test, and fig. 7 is a raman spectrum test chart and an X-ray diffraction test chart of the three-dimensional porous Dan Danmo graphene/SiC composite material of example 1, wherein fig. 7 (a) is the three-dimensional porous graphene/Si of example 1The raman spectrum test chart of the C composite material is the raman shift on the abscissa, the signal intensity on the ordinate, and fig. 7 (b) is the X-ray diffraction test chart of the three-dimensional porous graphene/SiC composite material of example 1, the abscissa is the 2θ angle, and the ordinate is the signal intensity. As is evident from the Raman spectrum of FIG. 7 (a), 1350cm -1 、1580cm -1 、2680cm -1 Strong graphene characteristic peaks exist nearby, and the corresponding characteristic peaks are more obvious with the increase of the preheating time; it can be seen from the X-ray diffraction pattern of fig. 7 (b) that the two characteristic peaks corresponding to the graphene planes after the apparent transformation from amorphous carbon to graphene are at 25.9 ° and 42.9 °. The results of the raman spectrum test, the X-ray diffraction test and the transmission electron microscope test are combined, so that the graphene in the graphene/SiC composite material prepared in example 1 can be proved to be a three-dimensional porous graphene material.
3. Application testing of flexible pressure sensors
The three-dimensional porous graphene/SiC composite material prepared in the embodiment 1 is applied to a flexible pressure sensor, and the preparation method comprises the following specific steps:
1) Coating the sample (graphene embedded with PDMS) prepared in the step 4) of example 1 with conductive silver paste, controlling the width of the conductive silver paste to be 2mm and the length to be 20mm, and connecting copper foil with the length of 2mm multiplied by 40mm as an electrode; and placing the sample coated with the conductive silver paste on a heating table, setting the heating temperature to be 80 ℃ and the heating time to be 30min, so that the conductive silver paste is completely solidified.
2) And (3) mixing the agent A: agent B = 10: 1) pouring the polydimethyl siloxane prepared in proportion into the upper layer of the sample prepared in the step 1) to fill the upper layer of the die; the sample filled in the upper layer of the mold was placed on a heating table and heated for 1h at 80℃to completely cure the PDMS.
3) And 2) taking the sample obtained after the heat curing in the step 2) out of the die, and properly cutting to obtain the flexible pressure sensor. Fig. 8 is a pictorial view of the flexible pressure sensor after encapsulation is completed.
The prepared flexible pressure sensor is tested in the aspects of monitoring vital signs of human body, monitoring related vibration and the like, and fig. 9 is a schematic diagram of the back of hand of the flexible pressure sensorThe grip sensing test chart, fig. 10 is a flexible pressure sensor elbow bending sensing chart, the greater the bending amplitude, the stronger the response. For monitoring weak vital sign signals of a human body, fig. 11 is a flexible pressure sensor respiration and swallowing monitoring chart, fig. 12 is a flexible pressure sensor wrist pulse monitoring chart, and fig. 13 is a flexible pressure sensor finger heart rate monitoring chart. To monitor different frequency signals, fig. 14 is a sound test chart of the flexible pressure sensor, and fig. 15 is an audio test chart of the flexible pressure sensor. For monitoring a large-range pressure signal, fig. 16 is a graph of a sole pressure test method of the flexible pressure sensor, total 8 detection points P1-P8 are arranged on the sole in fig. 16, and fig. 17 is a graph of a sole pressure test result of the flexible pressure sensor. The above test results show that the flexible pressure sensor prepared in example 1 has excellent test effect on human body monitoring, wherein the ordinate DeltaR/R 0 (%) all represent the percent change rate of resistance of the flexible pressure sensor.
Due to the characteristics of the sensor in the processing process, the carbonized fabric piezoresistive layer can be embedded into PDMS to a certain depth, so that the piezoresistive layer has good connection performance with the PDMS substrate, good stability in the sensing application process is caused, and the sensor has good test effect on weak signals and large-range pressure signals.
FIG. 18 is a graph showing the mechanical response sensitivity curve of a flexible pressure sensor with an embedding depth of 120 μm LIG/SiC (graphene/SiC composite); FIG. 19 is a graph showing the mechanical response sensitivity curve of LIG/SiC flexible pressure sensor with an embedding depth of 70 μm; FIG. 20 is a graph showing the mechanical response sensitivity curve of LIG/SiC flexible pressure sensor with an embedding depth of 0 μm; FIG. 21 is a schematic view of the cyclic loading test results of a flexible pressure sensor, wherein the ordinate ΔR/R 0 (%) all represent the percent change rate of resistance of the flexible pressure sensor. As can be seen from fig. 18 to 20, since the carbonized cotton cloth is embedded into PDMS to a certain depth before the start of the induction, the piezoresistive layer (carbonized cotton cloth after the induction) has a good bonding force with the substrate (PDMS), so that the manufactured flexible pressure sensor has a good mechanical stability, and can monitor a small range of pressure signals (pulse, respiration, heart rate, etc.) and a large range of pressure signals (plantar pressureForce, grip, etc.) are well behaved, which also widens the application range of the corresponding sensor. FIGS. 18-20 show sensitivity curves of the manufactured flexible pressure sensor at different preheat times, indicating that the final mechanical properties of the flexible pressure sensor can be controlled by controlling the preheat time, with a maximum detectable range of 200kPa; FIG. 21 is a result of a cyclic loading experiment performed on a tensile tester for a flexible pressure sensor with an amorphous carbon material embedded in a flexible matrix material and having a depth of 100 μm, wherein the test conditions are 200kPa pressure and the tensile tester speed is 20mm/s, and the result shows that the stability of the test is over 1600 times, and further shows that the flexible pressure sensor has a very high upper monitoring limit and stability.
According to the embodiment of the application, carbonized cotton cloth is used as a precursor of laser induction to process and manufacture three-dimensional porous graphene, and the induced sample is used for electrode connection and encapsulation to manufacture a flexible pressure sensor, so that the advantages of natural skin-friendly property, flexibility and the like of the fabric are exerted; and the embedding depth of carbonized cotton cloth can be controlled by controlling the preheating time of Polydimethylsiloxane (PDMS), so that the purposes of controlling the generation quality of the final three-dimensional porous graphene/SiC composite material and the mechanical property of the final flexible pressure sensor are achieved. The carbonized cotton cloth without embedded Polydimethylsiloxane (PDMS) can reach the ignition point of the carbonized cotton cloth under the air atmosphere to burn, so that the integrity of a final sample and the generation quality of the three-dimensional porous graphene are greatly influenced; according to the application, the carbonized cotton cloth is embedded into the Polydimethylsiloxane (PDMS), and the Polydimethylsiloxane (PDMS) of the embedded part also plays a role of a flame retardant to inhibit combustion of the carbonized cotton cloth in the induction process, so that an ideal processing effect is achieved.
In the application, cellulose materials with carbon as a main constituent element can be used as an induction precursor; the depth of embedding the carbonized cotton cloth into the polydimethylsiloxane in the embodiment of the application can be reasonably adjusted by the viscosity of the PDMS and the applied pressure, and the specific embedding depth can be estimated by utilizing a microscope.
The foregoing examples are illustrative of the present application and are not intended to be limiting, but rather, the application is intended to be limited to the specific embodiments shown, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the application are intended to be equivalent substitutes and modifications within the scope of the application.
Claims (5)
1. A preparation method of a graphene/SiC composite material is characterized by comprising the following steps: the method comprises the following steps:
1) Pre-oxidizing the fiber material to obtain an amorphous carbon material;
2) Embedding an amorphous carbon material into organic silicon to obtain a matrix material embedded with the amorphous carbon material;
3) Carrying out laser induction on the matrix material embedded with the amorphous carbon material to obtain the graphene/SiC composite material;
in the step 2), the depth of embedding the amorphous carbon material into the organic silicon exceeds 20% of the amorphous carbon material by no more than 80%;
the organic silicon also comprises a silicate compound, and after the amorphous carbon material is embedded into the organic silicon, the organic silicon is solidified;
in the step 1), the fiber material comprises at least one of cotton fiber, bamboo fiber, wood fiber, terylene, chinlon, acrylon, polypropylene fiber, vinylon and chloridion;
in the step 1), the pre-oxidation temperature is 270-330 ℃; the pre-oxidation time is 1h-3h; the temperature rising rate of the pre-oxidation is 1 ℃/min-3 ℃/min;
in the step 1), the thickness of the amorphous carbon material is 200-400 μm;
in the step 2), the thickness of the base material is 0.5mm-2.0mm.
2. The method of manufacturing according to claim 1, characterized in that: the organic silicon comprises at least one of polydimethylsiloxane, polymethylhydrosiloxane and polymethylphenylsiloxane.
3. The method of manufacturing according to claim 1, characterized in that: in the step 3), the atmosphere induced by the laser is an oxygen-containing atmosphere.
4. Use of the method for preparing a graphene/SiC composite material according to any one of claims 1 to 3 for preparing a sensor or a biosignal detection device.
5. Use of the graphene/SiC composite material prepared by the preparation method of the graphene/SiC composite material according to any one of claims 1 to 3 in biological signal detection.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015171968A (en) * | 2014-03-12 | 2015-10-01 | 日本電気株式会社 | Formation method of graphene-graphite film or composite film of nanocarbon and graphene-graphite |
| CN107244669A (en) * | 2017-06-14 | 2017-10-13 | 南开大学 | A kind of processing method and its system of induced with laser graphene micro-nano structure |
| CN108328595A (en) * | 2017-01-20 | 2018-07-27 | 中国科学院物理研究所 | A kind of carbon aerogels and preparation method thereof and pressure sensor |
| KR20190010287A (en) * | 2017-07-21 | 2019-01-30 | 성균관대학교산학협력단 | Graphene and preparing method thereof |
| CN111566046A (en) * | 2018-01-11 | 2020-08-21 | 帕拉格拉夫有限公司 | Method of manufacturing graphene layer structure |
| CN112479189A (en) * | 2014-02-17 | 2021-03-12 | 威廉马歇莱思大学 | Laser-induced graphene materials and their use in electronic devices |
| CN113247884A (en) * | 2021-03-24 | 2021-08-13 | 云南华谱量子材料有限公司 | Method for preparing graphene material by laser-induced industrial hemp |
| KR20210107945A (en) * | 2020-02-24 | 2021-09-02 | 주식회사 인포비온 | Preparation method of large-area graphene thin films by using energy-beam irradiation |
| CN113753880A (en) * | 2021-08-27 | 2021-12-07 | 北京航空航天大学 | Method for preparing three-dimensional graphene structure through 3D printing |
| CN113789033A (en) * | 2021-08-27 | 2021-12-14 | 北京航空航天大学 | Preparation method of three-dimensional graphene composite material |
| CN113999544A (en) * | 2021-11-09 | 2022-02-01 | 华东师范大学重庆研究院 | Preparation method and application of laser-induced coated graphene material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9725829B2 (en) * | 2013-03-15 | 2017-08-08 | Ut-Battelle, Llc | Magneto-carbonization method for production of carbon fiber, and high performance carbon fibers made thereby |
| CN109250707B (en) * | 2018-11-30 | 2020-05-05 | 浙江农林大学 | Graphene material prepared from waste tires and preparation method thereof |
| US11973211B2 (en) * | 2019-01-28 | 2024-04-30 | Honeycomb Battery Company | Process for producing metal nanowires and nanowire-graphene hybrid particulates |
-
2022
- 2022-03-15 CN CN202210252452.3A patent/CN114735678B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112479189A (en) * | 2014-02-17 | 2021-03-12 | 威廉马歇莱思大学 | Laser-induced graphene materials and their use in electronic devices |
| JP2015171968A (en) * | 2014-03-12 | 2015-10-01 | 日本電気株式会社 | Formation method of graphene-graphite film or composite film of nanocarbon and graphene-graphite |
| CN108328595A (en) * | 2017-01-20 | 2018-07-27 | 中国科学院物理研究所 | A kind of carbon aerogels and preparation method thereof and pressure sensor |
| CN107244669A (en) * | 2017-06-14 | 2017-10-13 | 南开大学 | A kind of processing method and its system of induced with laser graphene micro-nano structure |
| KR20190010287A (en) * | 2017-07-21 | 2019-01-30 | 성균관대학교산학협력단 | Graphene and preparing method thereof |
| CN111566046A (en) * | 2018-01-11 | 2020-08-21 | 帕拉格拉夫有限公司 | Method of manufacturing graphene layer structure |
| KR20210107945A (en) * | 2020-02-24 | 2021-09-02 | 주식회사 인포비온 | Preparation method of large-area graphene thin films by using energy-beam irradiation |
| CN113247884A (en) * | 2021-03-24 | 2021-08-13 | 云南华谱量子材料有限公司 | Method for preparing graphene material by laser-induced industrial hemp |
| CN113753880A (en) * | 2021-08-27 | 2021-12-07 | 北京航空航天大学 | Method for preparing three-dimensional graphene structure through 3D printing |
| CN113789033A (en) * | 2021-08-27 | 2021-12-14 | 北京航空航天大学 | Preparation method of three-dimensional graphene composite material |
| CN113999544A (en) * | 2021-11-09 | 2022-02-01 | 华东师范大学重庆研究院 | Preparation method and application of laser-induced coated graphene material |
Non-Patent Citations (1)
| Title |
|---|
| 石墨烯合成及应用研究进展;党民团等;渭南师范学院学报(04);18-23 * |
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