CN113768496B - Device for monitoring motion state of biological body surface or bionic body inner surface - Google Patents
Device for monitoring motion state of biological body surface or bionic body inner surface Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/103—Measuring devices for testing the shape, pattern, colour, size or movement of the body or parts thereof, for diagnostic purposes
- A61B5/11—Measuring movement of the entire body or parts thereof, e.g. head or hand tremor or mobility of a limb
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/01—Measuring temperature of body parts ; Diagnostic temperature sensing, e.g. for malignant or inflamed tissue
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/68—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient
- A61B5/6801—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be attached to or worn on the body surface
- A61B5/6802—Sensor mounted on worn items
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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Abstract
Description
技术领域technical field
本发明属于电子材料制备及其器件加工技术领域,特别是涉及一种监测生物体表或仿生体内表面运动状态的装置。The invention belongs to the technical field of electronic material preparation and device processing, and in particular relates to a device for monitoring the movement state of a biological surface or a bionic internal surface.
背景技术Background technique
当前,柔性技术被视为下一代智能硬件的主流交互形态之一,柔性设备也以指数级的规模快速增长。柔性设备的快速发展引起了人们对许多应用的极大兴趣,如健康监控设备、电子皮肤和可植入设备。同时,健康中国理念的深入人心也对检测装置的便捷性要求越来越高,能够实时监测生物体表及内部的运动状态,有助于迅速、全面掌握生物体的机能特征,这对于提高健康质量是十分有必要的。其中,电连接体的质量对生物体运动状态的实时监测至关重要。柔性电连接体的弹性、可弯曲性和可拉伸性,可以很好的适应生物体表皮与组织的拉伸与弯曲,使其制备的装置可实时、精准地测量生物体表面的运动状态。同时,采用3D打印制备的仿生体,通过选取与生物体理化性能相近的丙烯酸树脂材料,可模仿生物体的理化性质,达到真实模拟生物体特征的目的,并通过在其内表面制备装置,模拟生物内体的运动状态并实现实时监测,为深入研究生物体内的运动状态提供一种有效的手段。At present, flexible technology is regarded as one of the mainstream interactive forms of next-generation intelligent hardware, and flexible devices are also growing rapidly on an exponential scale. The rapid development of flexible devices has aroused great interest in many applications, such as health monitoring devices, electronic skin, and implantable devices. At the same time, the popularization of the concept of healthy China also requires more and more convenient detection devices, which can monitor the movement status of the surface and interior of organisms in real time, which is helpful to quickly and comprehensively grasp the functional characteristics of organisms, which is very important for improving health. Quality is very necessary. Among them, the quality of electrical connectors is crucial to the real-time monitoring of the movement status of organisms. The elasticity, bendability and stretchability of the flexible electrical connector can well adapt to the stretching and bending of the epidermis and tissue of the organism, so that the device prepared by it can measure the motion state of the surface of the organism in real time and accurately. At the same time, the bionic body prepared by 3D printing can imitate the physical and chemical properties of the biological body by selecting acrylic resin materials with similar physical and chemical properties to the biological body, and achieve the purpose of truly simulating the characteristics of the biological body. Real-time monitoring of the movement state of the biological endosome provides an effective means for in-depth research on the movement state of the living body.
液态金属本身具有很好的导电性,并且在常温下处于液体状态,因而可以作为柔性导电材料,并通过打印的方式制作柔性电连接体。液态金属制备的电连接体有着能够快速制造,环境友好,可用于制作柔性可弯曲,可拉伸电连接体等诸多优点。然而,液态金属制备的电连接体需要使用一定的封装技术,将导线与外界环境相隔离,避免液态金属导线的氧化或物理性破坏。目前液态金属制备电连接体通常使用PDMS或硅胶等材料,将未固化的PDMS或硅胶材料填充到液态金属制备的电连接体表面,利用高温或者自然固化,使得封装材料凝固,并起到保护电连接体的作用。这种方法需要等待较长时间,且由于使用自然固化方法,封装厚度以及均匀度都很难得到保证。同时,液态金属对制备载体的选择性高,这也进一步限制了其应用推广。Liquid metal itself has good electrical conductivity and is in a liquid state at room temperature, so it can be used as a flexible conductive material and a flexible electrical connector can be made by printing. The electrical connector made of liquid metal has many advantages such as being able to be rapidly manufactured, being environmentally friendly, and can be used to make a flexible, bendable, and stretchable electrical connector. However, the electrical connector made of liquid metal needs to use a certain packaging technology to isolate the wire from the external environment and avoid oxidation or physical damage to the liquid metal wire. At present, materials such as PDMS or silica gel are usually used to prepare electrical connectors from liquid metals. Fill uncured PDMS or silica gel materials into the surface of electrical connectors prepared from liquid metals, and use high temperature or natural curing to solidify the packaging materials and protect the electrical connectors. The role of connectors. This method needs to wait for a long time, and because of the natural curing method, it is difficult to guarantee the thickness and uniformity of the package. At the same time, liquid metal has a high selectivity for preparing carriers, which further limits its application and promotion.
发明内容Contents of the invention
基于背景技术所述存在的技术问题,本发明的目的是提供了一种监测生物体表或仿生体内表面运动状态的装置,采用高粘度高分子聚合物溶胶在生物体表面或仿生体内表面涂覆、干燥后获得高分子聚合物固化膜,然后使用改性石墨烯掺杂的液态金属复合材料在其表面制备电连接体,并贴装运动状态监测、供能及控制模块。该装置制备简单、安全性高,使用的改性石墨烯掺杂的液态金属复合材料具有良好的载体适应性,可在高分子聚合物固化膜表面制备出均匀、稳定的电连接体,且不需要额外的表面封装处理、适用范围广。同时,制备的电连接体具有高导电性和柔性,可满足生物体表或仿生体内表面运动状态监测的应用需求。具体技术方案如下:Based on the existing technical problems described in the background technology, the object of the present invention is to provide a device for monitoring the movement state of the surface of a living body or the surface of a bionic interior, which is coated with a high-viscosity polymer sol on the surface of a living body or the surface of a bionic interior. 1. Obtain a polymer cured film after drying, and then use the modified graphene-doped liquid metal composite material to prepare an electrical connector on its surface, and mount the motion state monitoring, energy supply and control modules. The device is simple to prepare and has high safety. The modified graphene-doped liquid metal composite material used has good carrier adaptability, and can prepare uniform and stable electrical connectors on the surface of the polymer cured film without Requires additional surface encapsulation treatment and has a wide range of applications. At the same time, the prepared electrical connector has high conductivity and flexibility, which can meet the application requirements of monitoring the movement state of the surface of the biological body or the surface of the bionic body. The specific technical scheme is as follows:
一种监测生物体表或仿生体内表面运动状态的装置,其制备方法包括以下步骤:A device for monitoring the movement state of the surface of a biological body or the surface of a bionic body, the preparation method of which comprises the following steps:
(1)将高粘度的高分子聚合物溶胶A涂覆在生物体的表面或仿生体的内表面,然后使用红外干燥或低温干燥的方式进行固化,获得紧贴生物体表面或仿生体内表面的高分子聚合物固化膜,红外干燥的功率为10-50W,红外干燥时间为3-5min;低温干燥的温度为40-60℃,低温干燥时间为5-10min;(1) Coat the high-viscosity polymer sol A on the surface of the living body or the inner surface of the bionic body, and then use infrared drying or low-temperature drying to cure it to obtain a sol that is close to the surface of the living body or the inner surface of the bionic body. Polymer cured film, infrared drying power is 10-50W, infrared drying time is 3-5min; low-temperature drying temperature is 40-60℃, low-temperature drying time is 5-10min;
(2)使用改性石墨烯掺杂的液态金属复合材料B在高分子聚合物固化膜表面制备电连接体,制备的电连接体为半固态,可均匀附着于高分子聚合物固化膜表面,无需额外增加封装工艺;所述改性石墨烯掺杂的液态金属复合材料B制备电连接体的方法包括挤出、电流体动力学直写、毛笔绘制中的一种或几种;(2) Use the liquid metal composite material B doped with modified graphene to prepare an electrical connector on the surface of the polymer cured film. The prepared electrical connector is semi-solid and can be evenly attached to the surface of the polymer cured film. There is no need to add an additional packaging process; the method for preparing an electrical connector from the modified graphene-doped liquid metal composite material B includes one or more of extrusion, electrohydrodynamic direct writing, and brush drawing;
(3)在电连接体表面贴装运动状态监测、供能、信号传输、及控制模块,获得用于生物体表或仿生体内表面运动状态监测的装置。(3) Mount motion state monitoring, energy supply, signal transmission, and control modules on the surface of the electrical connector to obtain a device for monitoring motion state on the surface of a biological body or the surface of a bionic body.
所述的高分子聚合物溶胶包括PVP水溶胶、PVP-PEG水溶胶、PVP-PLA水溶胶、PVP-PEG-PLA水溶胶中的一种或几种,所述高分子聚合物溶胶的粘度为1,000-4,000cp。所选高分子聚合物溶胶材料,对生物具有良好的相容性和低毒性,且来源丰富,因而不需要担心生物安全问题。Described high molecular polymer sol comprises one or more in PVP hydrosol, PVP-PEG hydrosol, PVP-PLA hydrosol, PVP-PEG-PLA hydrosol, and the viscosity of described high molecular polymer sol is 1,000-4,000cp. The selected polymer sol material has good biocompatibility and low toxicity, and is rich in sources, so there is no need to worry about biosafety issues.
所述的仿生体采用光固化3D打印丙烯酸复合树脂的方式制备,所述丙烯酸复合树脂由二丙烯酸(1,4-丁二醇)酯、二(乙二醇)二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、甲基丙烯酸2-羟乙基酯、甲基丙烯酸羟丙酯中的两种或两种以上的树脂混合而成。所选的仿生体材料采用光固化处理后具有良好的弹性、韧性及可拉伸性,因而可作为生物体结构和功能的仿生材料。The bionic body is prepared by light-curing 3D printing acrylic composite resin, and the acrylic composite resin is composed of (1,4-butylene glycol) diacrylate, di(ethylene glycol) dimethacrylate, 1, It is made by mixing two or more resins of 4-butanediol dimethacrylate, 2-hydroxyethyl methacrylate and hydroxypropyl methacrylate. The selected biomimetic body material has good elasticity, toughness and stretchability after photocuring, so it can be used as a biomimetic material for the structure and function of organisms.
所述改性石墨烯掺杂的液态金属复合材料B的制备过程为:将改性石墨烯、液体金属和酯类溶剂按照(0.001-0.03):(0.1-0.2):1的比例混合,并采用球磨的方式混匀后真空干燥,球磨转速为100-300rpm,球磨时间为6-24h,真空干燥的温度为120-180℃,真空干燥时间为4-6h。石墨烯是一类具有优异的电学、热学、力学等物理化学性能的二维碳纳米材料,但其片层之间具有很强的π-π相互作用以及高比表面能,导致其具有很强的化学惰性,易趋于聚集,限制其优异的性能的发挥。通过对石墨烯进行表面修饰,一方面可以提高石墨烯在酯类溶剂中的分散性,有利于石墨烯掺杂到液态金属中;另一方面可以增加石墨烯与液态金属之间的化学键和分子间作用力,进而获得可在高分子聚合物固化膜表面均匀、稳定附着的改性石墨烯掺杂的液态金属复合材料。The preparation process of the liquid metal composite material B doped with modified graphene is as follows: the modified graphene, liquid metal and ester solvent are mixed according to the ratio of (0.001-0.03): (0.1-0.2): 1, and The mixture is mixed by ball milling and then vacuum dried. The ball milling speed is 100-300rpm, the ball milling time is 6-24h, the vacuum drying temperature is 120-180°C, and the vacuum drying time is 4-6h. Graphene is a kind of two-dimensional carbon nanomaterials with excellent electrical, thermal, mechanical and other physical and chemical properties, but its sheets have strong π-π interactions and high specific surface energy, resulting in its strong Chemical inertness tends to aggregate, which limits its excellent performance. By surface modification of graphene, on the one hand, the dispersion of graphene in ester solvents can be improved, which is conducive to the doping of graphene into liquid metal; on the other hand, the chemical bonds and molecules between graphene and liquid metal can be increased. Interaction force, and then obtain the modified graphene-doped liquid metal composite material that can be uniformly and stably attached to the surface of the polymer cured film.
所述改性石墨烯包括卤族元素修饰还原氧化石墨烯、高活性氧含量修饰氧化石墨烯中的一种或几种。The modified graphene includes one or more of reduced graphene oxide modified with halogen elements and graphene oxide modified with high active oxygen content.
所述卤族元素修饰还原氧化石墨烯的制备过程为:将氧化石墨烯与浓度为1mol·L-1的卤素修饰液按照质量比(0.01-0.25):1混合后加热、离心、干燥,加热温度为60-90℃,加热时间为6-12h,所述的卤素修饰液中含有AlI3、AlBr3、FeI2、FeBr2中的一种或几种。The preparation process of the halogen element modified reduced graphene oxide is as follows: graphene oxide is mixed with a halogen modification solution with a concentration of 1 mol L -1 according to the mass ratio (0.01-0.25): 1, then heated, centrifuged, dried, heated The temperature is 60-90° C., the heating time is 6-12 hours, and the halogen modification solution contains one or more of AlI 3 , AlBr 3 , FeI 2 , and FeBr 2 .
所述高活性氧含量修饰氧化石墨烯的制备过程为:将氧化石墨烯放入H2SO4和HNO3等体积混合的氧化液中,真空条件下回流加热8-18h,加热温度为70-90℃,然后将二次氧化后的氧化石墨烯使用去离子水反复冲洗三次后,重复上述步骤三次,离心获得高活性氧含量修饰氧化石墨烯。The preparation process of the modified graphene oxide with high active oxygen content is as follows: put the graphene oxide into the oxidizing liquid mixed with equal volumes of H2SO4 and HNO3 , and heat under reflux for 8-18h under vacuum conditions, and the heating temperature is 70- 90°C, and then the graphene oxide after secondary oxidation was repeatedly washed with deionized water three times, the above steps were repeated three times, and centrifuged to obtain modified graphene oxide with high active oxygen content.
所述的液态金属为镓基液态金属,金属镓含量为65-95质量份、金属铟含量为5-25质量份,金属锡含量为0-25质量份,所述镓基液态金属的熔点为3-40℃。The liquid metal is a gallium-based liquid metal, the content of gallium metal is 65-95 parts by mass, the content of indium metal is 5-25 parts by mass, and the content of tin metal is 0-25 parts by mass. The melting point of the gallium-based liquid metal is 3-40°C.
所述的酯类溶剂包括甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸丁酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯中的一种或几种。The ester solvent includes one or more of methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.
所述的运动状态监测模块包括用于测量温度、压力、无机盐/糖类/酶/抗体等物质的监测模块中的一种或几种。The exercise state monitoring module includes one or more monitoring modules for measuring temperature, pressure, inorganic salts/sugars/enzymes/antibodies and other substances.
本发明的有益效果是:通过设计并制备了一种监测生物体表或仿生体内表面运动状态的装置。该装置制备简单、安全性高,改性石墨烯掺杂的液态金属复合材料具有良好的载体适应性,可在高分子聚合物固化膜表面制备出均匀、稳定的电连接体,且不需要额外的表面封装处理、适用范围广。同时,制备的电连接体具有高导电性、柔性、可靠性以及适用范围,可满足生物体表或仿生体内表面运动状态监测的应用需求。The beneficial effects of the present invention are: a device for monitoring the movement state of the surface of a living body or the surface of a bionic body is designed and prepared. The device is simple to prepare and has high safety. The modified graphene-doped liquid metal composite material has good carrier adaptability, and can prepare uniform and stable electrical connectors on the surface of the polymer cured film without additional Surface packaging treatment, wide application range. At the same time, the prepared electrical connector has high conductivity, flexibility, reliability and scope of application, which can meet the application requirements of monitoring the movement state of the surface of a biological body or the surface of a bionic body.
附图说明Description of drawings
图1为本发明实施例1中使用的改性石墨烯掺杂的液态金属复合材料的SEM图;Fig. 1 is the SEM figure of the liquid metal composite material doped with modified graphene used in the embodiment of the present invention 1;
图2为本发明实施例1中改性石墨烯掺杂的液态金属复合材料在PVP固化膜表面制备的电连接体的相干干涉图;Fig. 2 is the coherent interferogram of the electrical connector prepared on the surface of the PVP cured film by the liquid metal composite material doped with modified graphene in Example 1 of the present invention;
图3为本发明对比例2中不使用改性石墨烯掺杂的液态金属在PVP固化膜表面制备的电连接体的相干干涉图。3 is a coherent interference diagram of an electrical connector prepared on the surface of a PVP cured film without using modified graphene-doped liquid metal in Comparative Example 2 of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例和附图,对本发明的技术方案进行清楚、完整的描述,显然,所描述的内容仅仅是本发明的一部分,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式,都属于本发明保护的范围。The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention and the accompanying drawings. Obviously, the described content is only a part of the present invention, and those of ordinary skill in the art can make it without any creative work. All other obtained implementation modes belong to the protection scope of the present invention.
为了解决现有技术中液态金属直接制备的电连接体均匀性差,对载体的选择性高,适用范围狭窄,以及采用液态金属制备电连接体的工艺繁复、安全性差等问题。本发明设计并制备了一种用于生物体表或仿生体内表面运动状态监测的装置,采用高粘度高分子聚合物溶胶在生物体表面或仿生体内表面涂覆、干燥后获得高分子聚合物固化膜,然后使用改性石墨烯掺杂的液态金属复合材料在其表面制备电连接体,并贴装运动状态监测、供能及控制模块。该方法制备简单、安全性高,改性石墨烯掺杂的液态金属复合材料具有良好的载体适应性,可在高分子聚合物固化膜表面制备出均匀、稳定的电连接体,且不需要额外的表面封装处理。同时,制备的电连接体具有高导电性和柔性,可满足生物体表或仿生体内表面运动状态监测的应用需求。In order to solve the problems of poor uniformity of electrical connectors directly prepared by liquid metal, high selectivity to carriers, narrow application range, complicated process and poor safety of electrical connectors prepared by liquid metal in the prior art. The present invention designs and prepares a device for monitoring the movement state of the surface of a biological body or a bionic internal surface, and uses a high-viscosity high-molecular polymer sol to coat and dry the surface of a biological body or a bionic internal surface to obtain a solidified polymer Then use the modified graphene-doped liquid metal composite material to prepare electrical connectors on its surface, and mount the motion status monitoring, energy supply and control modules. The method is simple to prepare and has high safety. The modified graphene-doped liquid metal composite material has good carrier adaptability, and can prepare uniform and stable electrical connectors on the surface of the polymer cured film without additional Surface encapsulation treatment. At the same time, the prepared electrical connector has high conductivity and flexibility, which can meet the application requirements of monitoring the movement state of the surface of the biological body or the surface of the bionic body.
实施例1Example 1
本发明提供的一种监测生物体表或仿生体内表面运动状态的装置,其制备方法包括以下步骤:The present invention provides a device for monitoring the movement state of the surface of a living body or the surface of a bionic body, and its preparation method comprises the following steps:
(1)将PVP水溶胶涂覆在生物体的表面或仿生体的内表面,然后使用红外干燥的方式进行固化,获得紧贴生物体表面或仿生体内表面的高分子聚合物固化膜,红外干燥的功率为50W,红外干燥时间为5min;(1) Coat the PVP water sol on the surface of the organism or the inner surface of the bionic body, and then use infrared drying to cure it to obtain a cured polymer film that is close to the surface of the organism or the inner surface of the bionic body, and then dry it by infrared The power is 50W, and the infrared drying time is 5min;
(2)使用改性石墨烯掺杂的液态金属复合材料B(如图1所示)在高分子聚合物固化膜表面制备电连接体(如图2所示),制备的电连接体为半固态,可均匀附着于高分子聚合物固化膜表面;电连接体通过挤出的方法制备,获得的电连接体的电阻为2Ω;(2) Use the modified graphene-doped liquid metal composite material B (as shown in Figure 1) to prepare an electrical connector (as shown in Figure 2) on the surface of the polymer cured film, and the prepared electrical connector is half Solid state, can evenly adhere to the surface of the polymer cured film; the electrical connector is prepared by extrusion, and the resistance of the obtained electrical connector is 2Ω;
(3)在电连接体表面贴装运动状态监测、供能、信号传输、及控制模块,获得监测生物体表或仿生体内表面运动状态的装置。(3) Mount motion state monitoring, energy supply, signal transmission, and control modules on the surface of the electrical connector to obtain a device for monitoring the motion state of the surface of the biological body or the surface of the bionic body.
PVP水溶胶的粘度为4,000cp。The viscosity of PVP hydrosol is 4,000 cp.
所述的仿生体采用光固化3D打印丙烯酸复合树脂的方式制备,所述丙烯酸复合树脂由二丙烯酸(1,4-丁二醇)酯、二(乙二醇)二甲基丙烯酸酯混合而成。The bionic body is prepared by light-curing 3D printing acrylic composite resin, and the acrylic composite resin is made by mixing (1,4-butylene glycol) diacrylate and di(ethylene glycol) dimethacrylate .
所述改性石墨烯掺杂的液态金属复合材料B的制备过程为:将改性石墨烯、液体金属和酯类溶剂按照0.03:0.1:1的比例混合,并采用球磨的方式混匀后真空干燥,球磨转速为100rpm,球磨时间为6h,真空干燥的温度为180℃,真空干燥时间为6h。The preparation process of the modified graphene-doped liquid metal composite material B is as follows: the modified graphene, liquid metal and ester solvent are mixed according to the ratio of 0.03:0.1:1, and the mixture is mixed by ball milling and vacuum For drying, the ball milling speed is 100 rpm, the ball milling time is 6 hours, the vacuum drying temperature is 180° C., and the vacuum drying time is 6 hours.
所述改性石墨烯为卤族元素修饰还原氧化石墨烯。The modified graphene is reduced graphene oxide modified with halogen elements.
所述卤族元素修饰还原氧化石墨烯的制备过程为:将氧化石墨烯与浓度为1mol·L-1的卤素修饰液按照质量比0.01:1混合后加热、离心、干燥,加热温度为60℃,加热时间为12h,所述的卤素修饰液中含有AlI3和AlBr3。The preparation process of the halogen element modified reduced graphene oxide is as follows: graphene oxide is mixed with a halogen modification solution with a concentration of 1 mol·L -1 according to the mass ratio of 0.01:1, then heated, centrifuged, and dried at a heating temperature of 60°C , the heating time is 12h, and the halogen modification solution contains AlI 3 and AlBr 3 .
所述的液态金属为镓基液态金属,金属镓含量为70质量份、金属铟含量为5质量份,金属锡含量为25质量份。The liquid metal is gallium-based liquid metal, the content of gallium metal is 70 parts by mass, the content of metal indium is 5 parts by mass, and the content of metal tin is 25 parts by mass.
所述的酯类溶剂为甲酸甲酯和乙酸甲酯按照质量比1:1混合。The ester solvent is a mixture of methyl formate and methyl acetate in a mass ratio of 1:1.
所述的运动状态监测模块包括用于测量温度、压力、无机盐/糖类/酶/抗体等物质的监测模块中的一种或几种。The exercise state monitoring module includes one or more monitoring modules for measuring temperature, pressure, inorganic salts/sugars/enzymes/antibodies and other substances.
实施例2Example 2
本发明提供的一种监测生物体表或仿生体内表面运动状态的装置,其制备方法包括以下步骤:The present invention provides a device for monitoring the movement state of the surface of a living body or the surface of a bionic body, and its preparation method comprises the following steps:
(1)将PVP-PEG-PLA水溶胶涂覆在生物体的表面或仿生体的内表面,然后使用低温干燥的方式进行固化,获得紧贴生物体表面或仿生体内表面的高分子聚合物固化膜;低温干燥的温度为60℃,低温干燥时间为10min;(1) Coating the PVP-PEG-PLA hydrosol on the surface of the organism or the inner surface of the bionic body, and then curing it by low-temperature drying to obtain a solidified polymer that is close to the surface of the organism or the inner surface of the bionic body Film; the low temperature drying temperature is 60°C, and the low temperature drying time is 10 minutes;
(2)使用改性石墨烯掺杂的液态金属复合材料B在高分子聚合物固化膜表面制备电连接体,制备的电连接体为半固态,可均匀附着于高分子聚合物固化膜表面;电连接体通过电流体动力学直写的方法制备,获得的电连接体的电阻为1Ω;(2) Using liquid metal composite material B doped with modified graphene to prepare an electrical connector on the surface of the polymer cured film, the prepared electrical connector is semi-solid and can evenly adhere to the surface of the polymer cured film; The electrical connector is prepared by electrohydrodynamic direct writing, and the resistance of the obtained electrical connector is 1Ω;
(3)在电连接体表面贴装运动状态监测、供能、信号传输、及控制模块,获得监测生物体表或仿生体内表面运动状态的装置。(3) Mount motion state monitoring, energy supply, signal transmission, and control modules on the surface of the electrical connector to obtain a device for monitoring the motion state of the surface of the biological body or the surface of the bionic body.
PVP-PEG-PLA水溶胶的粘度为1,000cp。The viscosity of the PVP-PEG-PLA hydrosol is 1,000 cp.
所述的仿生体采用光固化3D打印丙烯酸复合树脂的方式制备,所述丙烯酸复合树脂由1,4-丁二醇二甲基丙烯酸酯、甲基丙烯酸2-羟乙基酯、甲基丙烯酸羟丙酯混合而成。The bionic body is prepared by photocuring 3D printing acrylic composite resin, and the acrylic composite resin is composed of 1,4-butanediol dimethacrylate, 2-hydroxyethyl methacrylate, methacrylate hydroxyl Propyl esters are mixed.
所述改性石墨烯掺杂的液态金属复合材料B的制备过程为:将改性石墨烯、液体金属和酯类溶剂按照0.001:0.2:1的比例混合,并采用球磨的方式混匀后真空干燥,球磨转速为300rpm,球磨时间为24h,真空干燥的温度为120℃,真空干燥时间为4h。The preparation process of the modified graphene-doped liquid metal composite material B is as follows: the modified graphene, liquid metal and ester solvent are mixed according to the ratio of 0.001:0.2:1, and the mixture is mixed by ball milling and vacuum For drying, the ball milling speed is 300 rpm, the ball milling time is 24 hours, the vacuum drying temperature is 120° C., and the vacuum drying time is 4 hours.
所述改性石墨烯为高活性氧含量修饰氧化石墨烯。The modified graphene is graphene oxide modified with high active oxygen content.
所述高活性氧含量修饰氧化石墨烯的制备过程为:将氧化石墨烯放入H2SO4和HNO3等体积混合的氧化液中,真空条件下回流加热18h,加热温度为70℃,然后将二次氧化后的氧化石墨烯使用去离子水反复冲洗三次后,重复上述步骤三次,离心获得高活性氧含量修饰氧化石墨烯。The preparation process of the modified graphene oxide with high active oxygen content is as follows: put the graphene oxide into an oxidizing solution mixed with equal volumes of H2SO4 and HNO3 , heat under reflux for 18 hours under vacuum conditions , and the heating temperature is 70 °C, and then After the secondary oxidized graphene oxide was repeatedly washed with deionized water three times, the above steps were repeated three times, and centrifuged to obtain modified graphene oxide with high active oxygen content.
所述的液态金属为镓基液态金属,金属镓含量为80质量份、金属铟含量为10质量份,金属锡含量为10质量份。The liquid metal is a gallium-based liquid metal, the content of gallium metal is 80 parts by mass, the content of metal indium is 10 parts by mass, and the content of metal tin is 10 parts by mass.
所述的酯类溶剂为甲酸乙酯、乙酸乙酯按照质量比1:3混合。The ester solvent is a mixture of ethyl formate and ethyl acetate in a mass ratio of 1:3.
所述的运动状态监测模块包括用于测量温度、压力、无机盐/糖类/酶/抗体等物质的监测模块中的一种或几种。The exercise state monitoring module includes one or more monitoring modules for measuring temperature, pressure, inorganic salts/sugars/enzymes/antibodies and other substances.
实施例3Example 3
本发明提供的一种监测生物体表或仿生体内表面运动状态的装置,其制备方法包括以下步骤:The present invention provides a device for monitoring the movement state of the surface of a living body or the surface of a bionic body, and its preparation method comprises the following steps:
(1)将PVP-PLA水溶胶涂覆在生物体的表面或仿生体的内表面,然后使用红外干燥的方式进行固化,获得紧贴生物体表面或仿生体内表面的高分子聚合物固化膜,红外干燥的功率为10W,红外干燥时间为3min;(1) Coating PVP-PLA hydrosol on the surface of the organism or the inner surface of the bionic body, and then curing by infrared drying to obtain a cured polymer film that is close to the surface of the organism or the inner surface of the bionic body, The power of infrared drying is 10W, and the infrared drying time is 3min;
(2)使用改性石墨烯掺杂的液态金属复合材料B在高分子聚合物固化膜表面制备电连接体,制备的电连接体为半固态,可均匀附着于高分子聚合物固化膜表面;电连接体通过毛笔绘制的方法制备,获得的电连接体的电阻为2Ω;(2) Using liquid metal composite material B doped with modified graphene to prepare an electrical connector on the surface of the polymer cured film, the prepared electrical connector is semi-solid and can evenly adhere to the surface of the polymer cured film; The electrical connector is prepared by drawing with a brush, and the resistance of the obtained electrical connector is 2Ω;
(3)在电连接体表面贴装运动状态监测、供能、信号传输、及控制模块,获得监测生物体表或仿生体内表面运动状态的装置。(3) Mount motion state monitoring, energy supply, signal transmission, and control modules on the surface of the electrical connector to obtain a device for monitoring the motion state of the surface of the biological body or the surface of the bionic body.
PVP-PLA水溶胶的粘度为2,000cp。The viscosity of the PVP-PLA hydrosol is 2,000 cp.
所述的仿生体采用光固化3D打印丙烯酸复合树脂的方式制备,所述丙烯酸复合树脂由二(乙二醇)二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯混合而成。The bionic body is prepared by light-curing 3D printing acrylic composite resin, and the acrylic composite resin is mixed with di(ethylene glycol) dimethacrylate and 1,4-butanediol dimethacrylate .
所述改性石墨烯掺杂的液态金属复合材料B的制备过程为:将改性石墨烯、液体金属和酯类溶剂按照0.001:0.1:1的比例混合,并采用球磨的方式混匀后真空干燥,球磨转速为150rpm,球磨时间为12h,真空干燥的温度为140℃,真空干燥时间为5h。The preparation process of the modified graphene-doped liquid metal composite material B is as follows: the modified graphene, liquid metal and ester solvent are mixed according to the ratio of 0.001:0.1:1, and the mixture is mixed by ball milling and vacuum For drying, the ball milling speed is 150 rpm, the ball milling time is 12 hours, the vacuum drying temperature is 140° C., and the vacuum drying time is 5 hours.
所述改性石墨烯为卤族元素修饰还原氧化石墨烯。The modified graphene is reduced graphene oxide modified with halogen elements.
所述卤族元素修饰还原氧化石墨烯的制备过程为:将氧化石墨烯与浓度为1mol·L-1的卤素修饰液按照质量比0.2:1混合后加热、离心、干燥,加热温度为90℃,加热时间为6h,所述的卤素修饰液中含有AlI3和FeI2。The preparation process of the halogen element modified reduced graphene oxide is as follows: graphene oxide is mixed with a halogen modification solution with a concentration of 1 mol·L -1 according to the mass ratio of 0.2:1, then heated, centrifuged, and dried at a heating temperature of 90°C , the heating time is 6h, and the halogen modification solution contains AlI 3 and FeI 2 .
所述的液态金属为镓基液态金属,金属镓含量为95质量份、金属铟含量为5质量份。The liquid metal is gallium-based liquid metal, the content of gallium metal is 95 parts by mass, and the content of metal indium is 5 parts by mass.
所述的酯类溶剂为甲酸丁酯和乙酸丙酯按照质量比1:10混合。The ester solvent is a mixture of butyl formate and propyl acetate in a mass ratio of 1:10.
所述的运动状态监测模块包括用于测量温度、压力、无机盐/糖类/酶/抗体等物质的监测模块中的一种或几种。The exercise state monitoring module includes one or more monitoring modules for measuring temperature, pressure, inorganic salts/sugars/enzymes/antibodies and other substances.
实施例4Example 4
本发明提供的一种监测生物体表或仿生体内表面运动状态的装置,其制备方法包括以下步骤:The present invention provides a device for monitoring the movement state of the surface of a living body or the surface of a bionic body, and its preparation method comprises the following steps:
(1)将PVP-PEG水溶胶涂覆在生物体的表面或仿生体的内表面,然后使用低温干燥的方式进行固化,获得紧贴生物体表面或仿生体内表面的高分子聚合物固化膜,低温干燥的温度为40℃,低温干燥时间为5min;(1) Coating the PVP-PEG hydrosol on the surface of the organism or the inner surface of the bionic body, and then curing it by low-temperature drying to obtain a cured polymer film that is close to the surface of the organism or the inner surface of the bionic body, The low-temperature drying temperature is 40°C, and the low-temperature drying time is 5 minutes;
(2)使用改性石墨烯掺杂的液态金属复合材料B在高分子聚合物固化膜表面制备电连接体,制备的电连接体为半固态,可均匀附着于高分子聚合物固化膜表面;电连接体通过电流体动力学直写的方法制备,获得的电连接体的电阻为1.5Ω;(2) Using liquid metal composite material B doped with modified graphene to prepare an electrical connector on the surface of the polymer cured film, the prepared electrical connector is semi-solid and can evenly adhere to the surface of the polymer cured film; The electrical connector is prepared by electrohydrodynamic direct writing, and the resistance of the obtained electrical connector is 1.5Ω;
(3)在电连接体表面贴装运动状态监测、供能、信号传输、及控制模块,获得监测生物体表或仿生体内表面运动状态的装置。(3) Mount motion state monitoring, energy supply, signal transmission, and control modules on the surface of the electrical connector to obtain a device for monitoring the motion state of the surface of the biological body or the surface of the bionic body.
PVP-PEG水溶胶的粘度为3,000cp。The viscosity of the PVP-PEG hydrosol is 3,000 cp.
所述的仿生体采用光固化3D打印丙烯酸复合树脂的方式制备,所述丙烯酸复合树脂由二丙烯酸(1,4-丁二醇)酯、1,4-丁二醇二甲基丙烯酸酯、甲基丙烯酸羟丙酯混合而成。The bionic body is prepared by light-curing 3D printing acrylic composite resin, and the acrylic composite resin is composed of (1,4-butanediol) diacrylate, 1,4-butanediol dimethacrylate, methyl A mixture of hydroxypropyl acrylate.
所述改性石墨烯掺杂的液态金属复合材料B的制备过程为:将改性石墨烯、液体金属和酯类溶剂按照0.03:0.2:1的比例混合,并采用球磨的方式混匀后真空干燥,球磨转速为220rpm,球磨时间为18h,真空干燥的温度为160℃,真空干燥时间为4.5h。The preparation process of the modified graphene-doped liquid metal composite material B is as follows: the modified graphene, liquid metal and ester solvent are mixed according to the ratio of 0.03:0.2:1, and the mixture is mixed by ball milling and vacuum For drying, the ball milling speed is 220 rpm, the ball milling time is 18 hours, the vacuum drying temperature is 160° C., and the vacuum drying time is 4.5 hours.
所述改性石墨烯为高活性氧含量修饰氧化石墨烯。The modified graphene is graphene oxide modified with high active oxygen content.
所述高活性氧含量修饰氧化石墨烯的制备过程为:将氧化石墨烯放入H2SO4和HNO3等体积混合的氧化液中,真空条件下回流加热8h,加热温度为90℃,然后将二次氧化后的氧化石墨烯使用去离子水反复冲洗三次后,重复上述步骤三次,离心获得高活性氧含量修饰氧化石墨烯。The preparation process of the modified graphene oxide with high active oxygen content is as follows: put the graphene oxide into an oxidizing solution mixed with equal volumes of H2SO4 and HNO3 , heat under reflux for 8 hours under vacuum conditions , and the heating temperature is 90 ° C, and then After the secondary oxidized graphene oxide was repeatedly washed with deionized water three times, the above steps were repeated three times, and centrifuged to obtain modified graphene oxide with high active oxygen content.
所述的液态金属为镓基液态金属,金属镓含量为65质量份、金属铟含量为25质量份。The liquid metal is gallium-based liquid metal, the content of gallium metal is 65 parts by mass, and the content of metal indium is 25 parts by mass.
所述的酯类溶剂为甲酸丙酯和乙酸丁酯按照质量比1:5混合。The ester solvent is a mixture of propyl formate and butyl acetate in a mass ratio of 1:5.
所述的运动状态监测模块包括用于测量温度、压力、无机盐/糖类/酶/抗体等物质的监测模块中的一种或几种。The exercise state monitoring module includes one or more monitoring modules for measuring temperature, pressure, inorganic salts/sugars/enzymes/antibodies and other substances.
对比例1Comparative example 1
将实施例1的技术方案改为:不使用高分子聚合物溶胶在生物体表或仿生体内表面涂覆高分子聚合物固化膜,而直接将改性石墨烯掺杂的液态金属复合材料制备在生物体表或仿生体内表面,液态金属中的少量金属元素会经由体表浸入到生物体内,造成一定的安全隐患。而且,改性石墨烯掺杂的液态金属复合材料无法直接在生物体表制备出均匀、连贯的高质量电连接体,会导致运动状态监测的可靠性降低。Change the technical scheme of Example 1 to: instead of using high molecular polymer sol to coat the high molecular polymer cured film on the surface of the biological body or the surface of the bionic body, the liquid metal composite material doped with modified graphene is directly prepared in the On the surface of a biological body or the surface of a bionic body, a small amount of metal elements in liquid metal will immerse into the biological body through the body surface, causing certain safety hazards. Moreover, the modified graphene-doped liquid metal composite cannot directly prepare uniform and coherent high-quality electrical connectors on the surface of organisms, which will reduce the reliability of motion state monitoring.
对比例2Comparative example 2
将实施例1的技术方案改为:不使用改性石墨烯掺杂的液态金属复合材料制备的电连接体,获得的电连接体的电阻为50Ω,且无法在高分子聚合物固化膜表面制备出的均匀、连续的高质量电连接体。图3为本发明对比例2中不使用改性石墨烯掺杂的液态金属在PVP固化膜表面制备的电连接体的相干干涉图。Change the technical scheme of Example 1 to: do not use the electrical connector prepared by the liquid metal composite material doped with modified graphene, the resistance of the obtained electrical connector is 50Ω, and it cannot be prepared on the surface of the polymer cured film Uniform, continuous high-quality electrical connections. 3 is a coherent interference diagram of an electrical connector prepared on the surface of a PVP cured film without using modified graphene-doped liquid metal in Comparative Example 2 of the present invention.
由以上内容可见,通过本发明实施例制备的监测生物体表或仿生体内表面运动状态的装置,制备过程简单、安全性高,改性石墨烯掺杂的液态金属复合材料具有良好的载体适应性,可在高分子聚合物固化膜表面制备出均匀、稳定的电连接体,且不需要额外的表面封装处理。同时,制备的电连接体具有高导电性和柔性,可满足监测生物体表或仿生体内表面运动状态的应用需求。It can be seen from the above that the device for monitoring the movement state of the surface of the living body or the surface of the bionic body prepared by the embodiment of the present invention has a simple preparation process and high safety, and the liquid metal composite material doped with modified graphene has good carrier adaptability , a uniform and stable electrical connection can be prepared on the surface of the polymer cured film, and no additional surface encapsulation treatment is required. At the same time, the prepared electrical connector has high conductivity and flexibility, which can meet the application requirements of monitoring the movement state of the surface of the biological body or the surface of the bionic body.
以上所述仅为本发明的较佳实施方式,并非用于限定本发明的保护范围。基于本发明中的实施例,熟悉本技术领域的人员还可据此做出多种变化,但任何与本发明等同或相类似的变化都属于本发明保护的范围。The above descriptions are only preferred implementation modes of the present invention, and are not intended to limit the protection scope of the present invention. Based on the embodiments of the present invention, those skilled in the art can make various changes accordingly, but any changes that are equivalent or similar to the present invention fall within the protection scope of the present invention.
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