CN114427174A - A kind of preparation method of filter paper-based flexible sensor with antibacterial function - Google Patents
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/46—Pouring or allowing the fluid to flow in a continuous stream on to the surface, the entire stream being carried away by the paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/005—Mechanical treatment
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
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Abstract
Description
技术领域technical field
本发明涉及柔性电子技术领域,具体涉及到一种滤纸基具有抗菌功能的柔性传感器的制备方法。The invention relates to the technical field of flexible electronics, in particular to a preparation method of a filter paper-based flexible sensor with antibacterial function.
背景技术Background technique
近年来,柔性电子领域发展日新月异。柔性传感器正成为未来机器人,体外诊断和能量收集中的重要应用器件。柔性传感器作为可穿戴的重要组成部分,掀起了全球研究的热潮。但是在实际应用中,已开发的柔性传感器还存在许多问题,如:金属材料延展性差,有机材料稳定性差,无机材料导电性差,1D结构更适用于小变形,2D结构测量范围窄,3D结构更适用于大形变,使得它们很难被实际应用。In recent years, the field of flexible electronics has developed rapidly. Flexible sensors are becoming important applications in future robotics, in vitro diagnostics and energy harvesting. As an important part of wearable sensors, flexible sensors have set off a global research upsurge. However, in practical applications, the developed flexible sensors still have many problems, such as poor ductility of metal materials, poor stability of organic materials, poor conductivity of inorganic materials, 1D structure is more suitable for small deformation, 2D structure measurement range is narrow, 3D structure is more Suitable for large deformations, making them difficult to be practically applied.
石墨烯基材料具有优良的导电性、优异的机械性能以及高透光性,是一种理想的敏感材料。而AgNWS还改变rGO片层间的接触方式,增加导通路径,从而提高传感器的灵敏度。PDMS薄膜由于具有优异的弹性,此外,它还由于自身优异的生物相容性、本征的高拉伸性、化学惰性、稳定性以及可变的机械性能。Graphene-based materials have excellent electrical conductivity, excellent mechanical properties, and high light transmittance, making them an ideal sensitive material. The AgNWS also changes the contact mode between the rGO sheets and increases the conduction path, thereby improving the sensitivity of the sensor. PDMS films are due to their excellent elasticity, in addition to their excellent biocompatibility, intrinsically high stretchability, chemical inertness, stability, and variable mechanical properties.
经过发展,柔性传感器的应用范围越来广泛的应用到各种领域,例如仿生机器、人体等等。这就需要一种可以随不同待测物体而可以完美的贴合其上边且对其不会造成影响。此外附着在人体皮肤任意部位,在使用过程中,会沾上汗液、皮脂以及其它各种人体分泌物,也会被环境中的污物所沾污。这些污物是各种微生物的良好营养源,尤其在恒温潮湿条件下,成为各种微生物繁殖的良好环境。由此,Ag-rGO-PDMS柔性传感器中Ag成分极好的抑制了细菌的繁殖。After development, the application range of flexible sensors is more and more widely used in various fields, such as bionic machines, human body and so on. This requires a method that can perfectly fit on the top of different objects to be tested without affecting it. In addition, it is attached to any part of human skin. During use, it will be stained with sweat, sebum and other various human secretions, and it will also be contaminated by dirt in the environment. These dirts are a good source of nutrients for various microorganisms, especially under constant temperature and humidity conditions, and become a good environment for the reproduction of various microorganisms. As a result, the Ag component in the Ag-rGO-PDMS flexible sensor excellently inhibited the reproduction of bacteria.
发明内容SUMMARY OF THE INVENTION
为了克服上述现有技术中的缺陷,本发明提供了一种滤纸基具有抗菌功能的柔性传感器的制备方法,既有极高的生物相容性、很大压缩性的微结构,可以保证传感器具有稳定的高灵敏度,又可以抑制细菌的繁殖及增长,制作方法操作简单、成本较低、对操作环境的要求较低,为柔性传感器微结构的制备工艺开辟了新的道路。In order to overcome the above-mentioned defects in the prior art, the present invention provides a preparation method of a filter paper-based flexible sensor with antibacterial function, which has a microstructure with extremely high biocompatibility and great compressibility, and can ensure that the sensor has The stable and high sensitivity can also inhibit the reproduction and growth of bacteria. The fabrication method is simple to operate, low in cost, and has low requirements on the operating environment, which opens up a new way for the fabrication of flexible sensor microstructures.
技术方案Technical solutions
一种滤纸基具有抗菌功能的柔性传感器的制备方法,包括如下步骤:A preparation method of a filter paper-based flexible sensor with antibacterial function, comprising the following steps:
(1)一步溶剂水热法制备Ag-rGO复合溶液:配制氧化石墨烯溶液和AgNWS水溶液,将抗坏血酸(AA)和氧化石墨烯溶液混合搅拌均匀后加入到AgNWS水溶液到得到混合溶液;(1) Ag-rGO composite solution is prepared by one-step solvent hydrothermal method: graphene oxide solution and AgNWS aqueous solution are prepared, ascorbic acid (AA) and graphene oxide solution are mixed and stirred evenly and then added to the AgNWS aqueous solution to obtain a mixed solution;
(2)将步骤(1)中的所述混合溶液转移到聚四氟乙烯反应釜中并放入烘箱中,在设定的温度和时间下反应结束后得到黑色混合溶液,使用去离子水和无水乙醇对所述黑色混合溶液多次离心洗涤去除杂物得到Ag-rGO溶液;(2) the described mixed solution in the step (1) is transferred in the polytetrafluoroethylene reactor and put into the baking oven, after the reaction finishes at the set temperature and time, obtain the black mixed solution, use deionized water and The black mixed solution was centrifuged and washed with absolute ethanol for several times to remove impurities to obtain an Ag-rGO solution;
(3)将步骤(2)中的所述Ag-rGO溶液超声粉碎得到均匀分散至去离子水中的Ag-rGO复合溶液,将所述均匀分散至去离子水中的Ag-rGO复合溶液滴至滤纸,再将所述滤纸抽滤干燥得到Ag-rGO滤纸;(3) ultrasonically pulverizing the Ag-rGO solution in step (2) to obtain an Ag-rGO composite solution uniformly dispersed in deionized water, and dropping the Ag-rGO composite solution uniformly dispersed in deionized water onto filter paper , and then the filter paper is filtered and dried to obtain Ag-rGO filter paper;
(4)将步骤(3)中的所述Ag-rGO滤纸放入热压机的压槽里使Ag-rGO和所述滤纸能够更好的复合,待热压后的所述Ag-rGO滤纸干燥后剪至理想形状,将铜线使用银胶粘至剪至理想形状后的所述Ag-rGO滤纸的两端并放入烘箱中干燥,最后在干燥后的所述Ag-rGO滤纸的表面涂抹一层PDMS,再至烘箱中干燥便得到一个Ag-rGO滤纸柔性传感器。(4) Put the Ag-rGO filter paper in step (3) into the pressing groove of the hot press so that Ag-rGO and the filter paper can be better compounded, and the Ag-rGO filter paper after hot pressing Cut to an ideal shape after drying, glue copper wires to both ends of the Ag-rGO filter paper cut to the desired shape with silver glue and put it in an oven to dry, and finally put the surface of the dried Ag-rGO filter paper on the surface A layer of PDMS was applied and dried in an oven to obtain an Ag-rGO filter paper flexible sensor.
(5)在所述Ag-rGO滤纸柔性传感器的一面贴上双面胶或者其它粘性物质使其和检测物表面贴合。(5) A double-sided tape or other viscous substance is attached to one side of the Ag-rGO filter paper flexible sensor to make it adhere to the surface of the detection object.
作为优选,步骤(1)中的所述AgNWS水溶液浓度为4-10mg/ml。Preferably, the AgNWS aqueous solution concentration in step (1) is 4-10 mg/ml.
作为优选,步骤(1)中的所述抗坏血酸(AA)与所述氧化石墨烯溶液中的氧化石墨烯的质量比为3:1。Preferably, the mass ratio of the ascorbic acid (AA) in the step (1) to the graphene oxide in the graphene oxide solution is 3:1.
作为优选,步骤(1)中的所述氧化石墨烯溶液的浓度为2-10mg/ml。Preferably, the concentration of the graphene oxide solution in step (1) is 2-10 mg/ml.
作为优选,步骤(1)中的所述AgNWS水溶液中的AgNWS与所述氧化石墨烯水溶液中的氧化石墨烯的质量比为1-2.5。Preferably, in step (1), the mass ratio of AgNWS in the AgNWS aqueous solution to the graphene oxide in the graphene oxide aqueous solution is 1-2.5.
作为优选,步骤(2)中烘箱的反应设定温度为120℃-140℃,时间为3-5h。Preferably, in step (2), the reaction setting temperature of the oven is 120°C-140°C, and the time is 3-5h.
作为优选,步骤(3)中超声粉碎间隔为3:2,周期为30s,循环90次。Preferably, in step (3), the ultrasonic pulverization interval is 3:2, the period is 30s, and the cycle is 90 times.
作为优选,步骤(2)中离心机的转速为5000-8000rad/min,时间为5-10min。Preferably, in step (2), the rotating speed of the centrifuge is 5000-8000 rad/min, and the time is 5-10 min.
作为优选,步骤(4)热压机温度为130-180℃,时间为700-1000s。Preferably, the temperature of the hot press in step (4) is 130-180°C, and the time is 700-1000s.
作为优选,步骤(4)中烘箱温度为110-130℃,直至其干燥。Preferably, in step (4), the oven temperature is 110-130° C. until it is dry.
有益效果beneficial effect
与现有技术相比,本发明的优点在于:Compared with the prior art, the advantages of the present invention are:
1.将AgNWS与氧化石墨烯复合,通过AgNWS来提高还原氧化石墨烯的导电性,改变还原氧化石墨烯片层间的接触方式,增加导通路径,从而提高传感器的灵敏度,Ag-rGO滤纸柔性传感器的适用范围广,具有应变检测能力;灵敏度高;以多次的疲劳测试后仍能保持良好的性能,既能测试小变形的脉搏振动,又能检测大变形的屈肘运动,且能用于唇部运动测试,实现唇语识别的能力;1. Composite AgNWS and graphene oxide, improve the conductivity of reduced graphene oxide through AgNWS, change the contact mode between the reduced graphene oxide sheets, increase the conduction path, thereby improving the sensitivity of the sensor, Ag-rGO filter paper is flexible The sensor has a wide range of applications and has the ability to detect strain; it has high sensitivity; it can still maintain good performance after repeated fatigue tests. In the lip movement test, the ability to realize lip language recognition;
2.反应采用一步溶剂水热法制备Ag-rGO复合溶液且直接将其抽滤在滤纸上,以滤纸为载体,操作简单,成本低廉,成功率极高,产量稳定,纯度高,得到的材料形貌结构可控,便于大规模生产;2. The reaction adopts a one-step solvent hydrothermal method to prepare the Ag-rGO composite solution and directly filter it on the filter paper. The filter paper is used as the carrier. The operation is simple, the cost is low, the success rate is extremely high, the yield is stable, and the purity is high. The obtained material The morphology and structure are controllable, which is convenient for mass production;
3.在Ag-rGO滤纸上滴涂具有微圆柱阵列的聚二甲基硅氧烷(PDMS)薄膜,烘干后将Ag-rGO滤纸薄膜互相嵌合,构筑柔性互锁结构传感器,该传感器对拉伸、压力、弯曲、剪切力均有响应,能区分人体运动,与双层平面传感器和单层微柱阵列传感器相比,能实现更加细致的多峰检测,对未来的医疗诊断和健康监测具有重要意义。3. A polydimethylsiloxane (PDMS) film with micro-cylindrical arrays was drop-coated on the Ag-rGO filter paper. After drying, the Ag-rGO filter paper films were embedded with each other to construct a flexible interlocking structure sensor. It responds to stretching, pressure, bending, and shearing forces, and can distinguish human motion. Compared with double-layer planar sensors and single-layer micro-pillar array sensors, it can achieve more detailed multi-peak detection, which is useful for future medical diagnosis and health. Monitoring is important.
4.采取了热压工艺,经过热压后的Ag-rGO薄膜和滤纸能够更好的复合,使得Ag嵌入到滤纸中,在Ag-rGO滤纸柔性传感器工作时产生的微弱电流使Ag转变为游离态,Ag离子有抗菌效果且经查证,Ag和rGO组合抗菌效果更优;4. The hot-pressing process is adopted, and the Ag-rGO film and filter paper can be better combined after hot-pressing, so that Ag is embedded in the filter paper, and the weak current generated when the Ag-rGO filter paper flexible sensor works makes Ag into a free state. , Ag ions have antibacterial effect and it has been verified that the antibacterial effect of Ag and rGO combination is better;
5.在滤纸一侧可以粘贴双面胶或者任何粘性物质使Ag-rGO滤纸柔性传感器可以应用到不同的场景。5. Double-sided tape or any sticky substance can be pasted on one side of the filter paper, so that the flexible sensor of Ag-rGO filter paper can be applied to different scenarios.
附图说明Description of drawings
图1为本发明中抽滤后滤纸的电镜图;Fig. 1 is the electron microscope picture of filter paper after suction filtration in the present invention;
图2为本发明中Ag-rGO滤纸柔性传感器的结构示意图;Figure 2 is a schematic structural diagram of the Ag-rGO filter paper flexible sensor in the present invention;
图3为本发明中Ag-rGO滤纸柔性传感器的截面图。Figure 3 is a cross-sectional view of the Ag-rGO filter paper flexible sensor in the present invention.
附图标记reference number
PDMS 1,滤纸2,Ag-rGO 3,双面胶或者其它粘性物质4。
具体实施方式Detailed ways
为更好地说明阐述本发明内容,下面结合附图和实施实例进行展开说明:In order to better illustrate and describe the content of the present invention, the following description will be carried out in conjunction with the accompanying drawings and implementation examples:
有图1-3所示,本发明公开了一种滤纸基具有抗菌功能的柔性传感器的制备方法,包括如下步骤:As shown in Figures 1-3, the present invention discloses a preparation method of a filter paper-based flexible sensor with antibacterial function, comprising the following steps:
(1)一步溶剂水热法制备Ag-rGO复合溶液:配制氧化石墨烯溶液和AgNWS水溶液,将抗坏血酸(AA)和氧化石墨烯溶液混合搅拌均匀后加入到AgNWS水溶液到得到混合溶液;(1) Ag-rGO composite solution is prepared by one-step solvent hydrothermal method: graphene oxide solution and AgNWS aqueous solution are prepared, ascorbic acid (AA) and graphene oxide solution are mixed and stirred evenly and then added to the AgNWS aqueous solution to obtain a mixed solution;
(2)将步骤(1)中的所述混合溶液转移到聚四氟乙烯反应釜中并放入烘箱中,在设定的温度和时间下反应结束后得到黑色混合溶液,使用去离子水和无水乙醇对所述黑色混合溶液多次离心洗涤去除杂物得到Ag-rGO溶液;(2) the described mixed solution in the step (1) is transferred in the polytetrafluoroethylene reactor and put into the baking oven, after the reaction finishes at the set temperature and time, obtain the black mixed solution, use deionized water and The black mixed solution was centrifuged and washed with absolute ethanol for several times to remove impurities to obtain an Ag-rGO solution;
(3)将步骤(2)中的所述Ag-rGO溶液超声粉碎得到均匀分散至去离子水中的Ag-rGO复合溶液,将所述均匀分散至去离子水中的Ag-rGO复合溶液滴至滤纸2,再将所述滤纸2抽滤干燥得到Ag-rGO滤纸;(3) ultrasonically pulverizing the Ag-rGO solution in step (2) to obtain an Ag-rGO composite solution uniformly dispersed in deionized water, and dropping the Ag-rGO composite solution uniformly dispersed in deionized water onto filter paper 2. The filter paper 2 is then filtered and dried to obtain Ag-rGO filter paper;
(4)将步骤(3)中的所述Ag-rGO滤纸放入热压机的压槽里使Ag-rGO 3和所述滤纸2能够更好的复合,待热压后的所述Ag-rGO滤纸干燥后剪至理想形状,将铜线使用银胶粘至剪至理想形状后的所述Ag-rGO滤纸的两端并放入烘箱中干燥,最后在干燥后的所述Ag-rGO滤纸的表面涂抹一层PDMS 1,再至烘箱中干燥便得到一个Ag-rGO滤纸柔性传感器。(4) Put the Ag-rGO filter paper in step (3) into the pressing groove of the hot press so that Ag-
(5)在所述Ag-rGO滤纸柔性传感器的一面贴上双面胶或者其它粘性物质4使其和检测物表面贴合。(5) A double-sided tape or other
作为优选,步骤(1)中的所述AgNWS水溶液浓度为4-10mg/ml。Preferably, the AgNWS aqueous solution concentration in step (1) is 4-10 mg/ml.
作为优选,步骤(1)中的所述抗坏血酸(AA)与所述氧化石墨烯溶液中的氧化石墨烯的质量比为3:1。Preferably, the mass ratio of the ascorbic acid (AA) in the step (1) to the graphene oxide in the graphene oxide solution is 3:1.
作为优选,步骤(1)中的所述氧化石墨烯溶液的浓度为2-10mg/ml。Preferably, the concentration of the graphene oxide solution in step (1) is 2-10 mg/ml.
作为优选,步骤(1)中的所述AgNWS水溶液中的AgNWS与所述氧化石墨烯水溶液中的氧化石墨烯的质量比为1-2.5。Preferably, in step (1), the mass ratio of AgNWS in the AgNWS aqueous solution to the graphene oxide in the graphene oxide aqueous solution is 1-2.5.
作为优选,步骤(2)中烘箱的反应设定温度为120℃-140℃,时间为3-5h。Preferably, in step (2), the reaction setting temperature of the oven is 120°C-140°C, and the time is 3-5h.
作为优选,步骤(3)中超声粉碎间隔为3:2,周期为30s,循环90次。Preferably, in step (3), the ultrasonic pulverization interval is 3:2, the period is 30s, and the cycle is 90 times.
作为优选,步骤(2)中离心机的转速为5000-8000rad/min,时间为5-10min。Preferably, in step (2), the rotating speed of the centrifuge is 5000-8000 rad/min, and the time is 5-10 min.
作为优选,步骤(4)热压机温度为130-180℃,时间为700-1000s。Preferably, the temperature of the hot press in step (4) is 130-180°C, and the time is 700-1000s.
作为优选,步骤(4)中烘箱温度为110-130℃,直至其干燥。Preferably, in step (4), the oven temperature is 110-130° C. until it is dry.
具体地,配制氧化石墨烯溶液2mg/ml和AgNWS水溶液4mg/ml,将54mg抗坏血酸(AA)和10ml氧化石墨烯溶液混合搅拌均匀后加入到AgNWS水溶液(4mg/ml 5ml)到得到混合溶液,将混合溶液转移到聚四氟乙烯反应釜中并放入烘箱中120℃反应4h,反应结束后得到黑色混合溶液,使用去离子水和无水乙醇对黑色混合溶液多次离心洗涤去除杂物得到Ag-rGO3,转速为5000rad/min时间为5min,将离心洗涤后的溶液超声粉碎得到均匀分散至去离子水中的Ag-rGO复合溶液并将其抽滤在滤纸2上,转移至热压机上130℃800s,即得到干燥的Ag-rGO滤纸,将干燥的Ag-rGO滤纸剪至所需的理想形状并将铜线用银胶粘至两端,最后在其表面涂抹一层PDMS 1并放入烘箱,在120℃的直至其干燥,便得到了一个Ag-rGO滤纸柔性传感器,使用时可在Ag-rGO滤纸柔性传感器的滤纸面粘贴双面胶,以便适应于人体各个部分的贴附。Specifically, prepare graphene oxide solution 2mg/ml and AgNWS aqueous solution 4mg/ml, mix and stir 54mg ascorbic acid (AA) and 10ml graphene oxide solution and add to the AgNWS aqueous solution (4mg/ml 5ml) to obtain a mixed solution, the The mixed solution was transferred to a polytetrafluoroethylene reactor and placed in an oven for 4 hours at 120°C. After the reaction, a black mixed solution was obtained. The black mixed solution was centrifuged and washed several times with deionized water and absolute ethanol to remove impurities to obtain Ag. -rGO3, the rotation speed is 5000rad/min, the time is 5min, the solution after centrifugal washing is ultrasonically pulverized to obtain the Ag-rGO composite solution uniformly dispersed in deionized water, and it is suction filtered on filter paper 2, and transferred to a hot press at 130 ° C After 800s, the dry Ag-rGO filter paper is obtained. Cut the dry Ag-rGO filter paper to the desired desired shape and glue the copper wire to both ends with silver glue. Finally, apply a layer of
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明技术方案进行了详细的说明,本领域的技术人员应当理解,其依然可以对前述实施例所记载的技术方案进行修改,或者对其中部分技术特征进行同等替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神与范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the technical solutions of the present invention have been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they are still Modifications can be made to the technical solutions described in the foregoing embodiments, or some technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
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