WO2018018689A1 - 一种超亲水仿生基质含水量传感器及其制备方法 - Google Patents

一种超亲水仿生基质含水量传感器及其制备方法 Download PDF

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WO2018018689A1
WO2018018689A1 PCT/CN2016/096843 CN2016096843W WO2018018689A1 WO 2018018689 A1 WO2018018689 A1 WO 2018018689A1 CN 2016096843 W CN2016096843 W CN 2016096843W WO 2018018689 A1 WO2018018689 A1 WO 2018018689A1
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layer
hydrophilic
nano
substrate
micro
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French (fr)
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张西良
耿妙妙
徐坤
印学号
李萍萍
赵麟
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江苏大学
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/048—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance for determining moisture content of the material

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  • the invention belongs to the application field of a novel matrix water content sensor, in particular to a super-hydrophilic biomimetic substrate water content sensor and a preparation method thereof, which are used for real-time measurement of water content of a certain amount of water content soil and cultivation substrate.
  • the soil and the cultivation substrate are a mixed component of minerals and organic matter, mainly solid particles, but there are certain gases and liquids in the gaps of the solid particles, which are heterogeneous systems. Its complex composition and heterogeneous mixed state make the soil matrix exhibit many different physicochemical properties. In addition, due to the looseness of the soil and the matrix itself, the poor contact is not good, resulting in poor detection of the parameters, resulting in poor adaptability to its parameter detection, low detection sensitivity, large error, poor stability, etc. In-situ measurements bring difficulty.
  • the traditional soil water content detection methods include drying method, neutron scattering method, electric resistance method and capacitance method.
  • the drying method is a standard method for obtaining soil water content, and is also a theoretical standard value of water content, and has good adaptability to matrix parameter detection.
  • it is not possible to detect in real time on site and requires a lot of manpower and material resources, and can not get the soil sensation in time.
  • the neutron scattering method does not require soil sampling, and the adaptability to the matrix parameter detection is good, but there are disadvantages such as high cost and radiation.
  • the electric resistance method utilizes the correspondence between the resistance value and the water content of the humidity sensitive resistor, and has the advantages of low cost, simpleness and rapidity, but has hysteresis and poor sensitivity and accuracy, especially the adaptability of the matrix parameter detection. difference.
  • the capacitance method is to use the measured soil material as a part of the capacitor dielectric, and combine the relationship between the soil water content and the total dielectric constant to obtain the soil water content value.
  • Commonly used capacitive sensors are parallel plate and cylindrical, and their structure is simple and easy to implement, but the sensitivity is not high, and there are nonlinear problems caused by edge effects.
  • the above method for detecting soil water content is used for in-situ detection of substrate water content. Since the matrix itself is relatively loose and insufficient in compactness, it often causes poor detection, resulting in low detection sensitivity, large error, poor stability, etc. Problems and deficiencies.
  • CA contact angle
  • a contact angle of >150° with water droplets obtained by surface modification is generally referred to as a superhydrophobic surface, and a contact angle of ⁇ 5° is referred to as a superhydrophilic surface.
  • researchers have studied the super-hydrophilicity of different materials and considered that the super-hydrophilicity is related to the electron-hole pairs of the materials and the coarseness of the surface of the materials.
  • the preparation of super-hydrophilic surfaces can be carried out in two ways, one is photo-induced super-hydrophilic; the other is to construct a rough structure on the surface of the hydrophilic material.
  • Second test for soil water content The various approaches are suitable.
  • the various textured surfaces have different interfacial effects.
  • the surface texture is improved by suitable texture surface, so that the water content sensor can quickly adsorb water molecules, reduce response time and improve accuracy.
  • the object of the present invention is to solve the problem of in situ measurement of soil water content in soil culture substrate, and propose a super-hydrophilic biomimetic substrate water content sensor and a preparation method thereof for realizing water content in a heterogeneous system such as soil and cultivation substrate.
  • the invention combines the resistance logarithm and the relative humidity of the graphene oxide film into a linear characteristic, and the sensor is formed by the graphene oxide film to reflect the water content in the detected substrate, and the super-hydrophilic structure and graphene oxide on the surface of the sensor sensitive layer.
  • the hydrophilic nature of the oxygen-containing functional groups in the thin layer of sensitive materials can greatly enhance the contact effect between the sensor and the water molecules in the tested matrix, and significantly improve the sensitivity and stability of the sensor to water, thereby effectively overcoming the looseness of the matrix itself.
  • the problems caused by poor contact detection, low sensitivity, large error, and poor stability are brought about.
  • the technical scheme of the present invention is: a super-hydrophilic biomimetic substrate water content sensor comprising a substrate, a micro-nano texture layer, a sensitive layer and an electrode lead;
  • the front surface of the substrate is provided with a rectangular groove, and the two sides of the rectangular groove are respectively provided with a long groove, and the rectangular groove is sequentially provided with a micro-nano texture layer and a sensitive layer, and electrode leads are respectively attached to the long groove;
  • the micro-nano texture layer includes an epoxy resin layer and a hydrophilic nano-SiO 2 layer, and the epoxy resin layer is located under the hydrophilic nano-SiO 2 layer; the hydrophilic nano-silica The surface of the layer is subjected to microtexture processing;
  • the sensitive layer is a thin layer of graphene oxide attached to the surface of the hydrophilic nano-silica layer.
  • the electrode lead includes a nickel transition layer and a silver layer, and the nickel transition layer is located under the silver layer.
  • the substrate is an alumina ceramic material.
  • the surface of the hydrophilic nano-silica layer is micro-textured to form a cylindrical pit having a pore depth of 40 nm to 80 nm and a pore diameter of 1 ⁇ m to 2 ⁇ m.
  • the cylindrical pit has a pore depth of 50 nm and a pore diameter of 1 ⁇ m.
  • the thin layer of the graphene oxide has a thickness of 20 nm.
  • the nickel transition layer has a thickness of 80 nm; and the silver layer has a thickness of about 3 ⁇ m.
  • the substrate has a thickness of 1.5 mm or more; and the rectangular groove and the two long grooves have a depth of 3.1 ⁇ m.
  • the pads are formed on the electrode leads.
  • a method for preparing the superhydrophilic biomimetic substrate water content sensor comprises the following steps:
  • the substrate moisture content sensor substrate of the present invention selects an alumina ceramic material and is grooved on the surface, and is provided with a micro-nano texture layer, a sensitive layer and electrode leads, which has low cost, easy preparation, good stability and corrosion resistance. Anti-wear, impact resistance, high strength and so on.
  • the sensitive material of the matrix water content sensor of the present invention is a thin layer of graphene oxide, has a large number of covalently bonded oxygen-containing functional groups, exhibits good hydrophilicity, improves detection sensitivity, and shortens sensor detection response time. .
  • the surface of the matrix water content sensor of the present invention is a micro-textured groove or pit structure, so that the contact surface of the sensor surface with the surface of the water droplet is less than 5°, has super hydrophilic property, and has a certain water content in the soil and cultivation. In the environment such as matrix, it can quickly adsorb water molecules, realize rapid measurement and reduce response time; and the nano-scale super-hydrophilic micro-textured surface also has self-cleaning biomimetic effect.
  • FIG. 1 is a front elevational view showing the structure of a superhydrophilic biomimetic matrix water content sensor according to an embodiment of the present invention
  • Figure 2 is a front elevational view of the base
  • Figure 3 is a cross-sectional view of the sensor in the A-A direction
  • Figure 4 is a cross-sectional view of the sensor in the B-B direction.
  • the super-hydrophilic biomimetic substrate water content sensor comprising a substrate 1, a micro-nano texture layer 2, a sensitive layer 3 and an electrode
  • the lead 4 is formed on the electrode lead 4, and the resistance signal is taken out through the electrode lead 4 and the pad 5 to facilitate connection with the subsequent detection processing circuit and experimental test.
  • the front surface of the substrate 1 is provided with a rectangular groove 11, and the two sides of the rectangular groove 11 are respectively provided with long grooves 12.
  • the substrate 1 is an alumina ceramic material having a thickness of 1.5 mm or more, a square shape and a side length of about 1 cm
  • the rectangular groove 11 has a depth of about 3.1 um, a length L 1 of about 0.6 cm, and a width W 1 .
  • the long trough 12 has a depth of about 3.1 um, a length L 2 of about 0.8 cm, and a width of about W 2 of about 0.1 cm.
  • the substrate 1 is made of alumina ceramic material, and a rectangular groove 11 and a long groove 12 are formed on the front surface, and the micro-nano texture layer 2 and the sensitive layer 3 are attached to the rectangular groove 11, and the two long grooves 12 are respectively provided with electrodes
  • the lead wire 4 has the advantages of low cost, easy preparation, good stability, corrosion resistance, abrasion resistance, impact resistance, high strength, and the like, and is suitable for inserting into the soil and the cultivation substrate.
  • the micro/nano texture layer 2 includes an epoxy resin layer 21 and a hydrophilic nano-SiO 2 layer 22, and the epoxy resin layer 21 is located on the hydrophilic nano-silicon dioxide. Below the layer 22. The surface of the hydrophilic nano-SiO 2 layer 22 is subjected to a microtexture processing.
  • the epoxy layer 21 functions to enhance the connection between the hydrophilic nano-SiO 2 layer 22 and the substrate 1 alumina ceramic material; the hydrophilic nano-SiO 2 layer 22 is micro-textured to The surface of the sensitive layer 3 provides a super-hydrophilic structure, and the hydrophilic nano-silica 22 is a hydrophilic insulating material, which can improve the hydrophilic property of the sensor without affecting the resistance value reflecting the water content.
  • the epoxy resin layer 21 has a thickness of about 80 nm
  • the hydrophilic nano-silica layer 22 has a thickness of about 3 ⁇ m
  • the surface of the hydrophilic nano-SiO 2 layer 22 is micro-textured to form a cylindrical pit.
  • the pore depth is 40 nm to 80 nm
  • the pore diameter is 1 ⁇ m to 2 ⁇ m.
  • the cylindrical pit has a pore depth of 50 nm and a pore diameter of 1 ⁇ m.
  • the material of the sensitive layer 3 is a thin layer 31 of graphene oxide attached to the surface of the hydrophilic nano-silicon dioxide layer 22.
  • the thin layer 31 of graphene oxide has a thickness of about 20 nm.
  • the two-dimensional layered graphene oxide thin layer 31 has a large number of oxygen-containing functional groups, is favorable for binding with water molecules, has hydrophilicity, and improves sensor sensitivity; and the surface of the hydrophilic nano-silicon dioxide layer 22 is micro-woven.
  • the structure treatment is combined with the thin layer 31 of graphene oxide to make the contact surface of the sensor surface with water droplets less than 5°, and has super hydrophilic property.
  • the electrode lead 4 includes a nickel transition layer 41 and a silver layer 42, and the nickel transition layer 41 is located below the silver layer 42.
  • the thickness of the nickel transition layer is about 80 nm, which serves to enhance the connection between the silver layer and the base alumina ceramic material; preferably, the thickness of the silver layer is about 3 ⁇ m, which is used to extract the detection resistance signal.
  • the invention also provides a method for preparing the superhydrophilic biomimetic substrate water content sensor, comprising the following steps:
  • the substrate 1 is prepared, and the substrate 1 is made of an alumina ceramic material having a thickness of 1.5 mm or more.
  • the substrate 1 has a square shape with a side length of about 1 cm, and has a rectangular opening 11 having a depth of about 3.1 ⁇ m at the front surface and a length L 1 of about 0.6 cm. a width W 1 of about 0.4 cm, and a depth of about 3.1 ⁇ m long groove 12 on each side of the rectangular groove 11, a length L 2 of about 0.8 cm, a width W 2 of about 0.1 cm;
  • the micro-nano texture layer 2 is prepared, and the epoxy resin is coated in a rectangular groove 11 having a length of about 0.8 cm and a width of 0.4 cm by spin coating to obtain an epoxy resin layer 21 having a thickness of about 80 nm;
  • Hydrophilic nano-silica is prepared, and hydrophilic nano-silica is deposited on the surface of the epoxy resin layer by a sol-gel method to obtain a hydrophilic nano-silica layer 22 having a thickness of about 3 ⁇ m, and then passed through The femtosecond laser performs micro-texture processing on the surface of the hydrophilic nano-silica layer 22 to process cylindrical pits of a nanometer scale with a pore depth of about 50 nm and a pore diameter of about 1 ⁇ m;
  • an electrode lead 4 depositing a nickel transition layer 41 having a thickness of 80 nm in a rectangular groove (12) having a length of about 0.8 cm and a width of about 0.1 cm by DC magnetron sputtering; and then depositing silver by magnetron sputtering Deposited on the surface of the nickel transition layer 41 to obtain a silver layer 42 having a thickness of about 3 ⁇ m;
  • the sensitive layer 3 is prepared, and the sensitive material graphene oxide is prepared by the Hummers method; then the prepared graphene oxide is subjected to vacuum low-temperature heat treatment to increase its conductivity, and then the hydrophilic nano-structure having a hydrophilic structure is prepared by spin coating.
  • the surface of the silicon dioxide layer 22, and a portion of the surface of the silver layer 42 adjacent to the hydrophilic nano-silica layer 22, that is, a uniformly distributed graphite oxide is coated in a rectangular region having a length of about 0.8 cm and a width of about 0.1 cm.
  • the thin layer 31 of olefin has a thickness of about 20 nm.
  • the electrode lead 4 may be deposited in the step S3 in one of electrochemical deposition, physical vapor deposition, and chemical vapor deposition, such as magnetron sputtering, laser confocal sputtering, pulsed laser sputtering, and the like.
  • the super-hydrophilic biomimetic substrate water content sensor of the invention has the advantages of super hydrophilicity, self-cleaning, etc., has high sensitivity and good stability for detecting water molecules, and is suitable for in situ measurement of water content of the cultivated soil substrate.

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Abstract

一种超亲水仿生基质含水量传感器及其制备方法，传感器包括基底（1）、微纳织构层（2）、敏感层（3）和电极引线（4），基底（1）为氧化铝陶瓷材料，微纳织构层（2）包括环氧树脂层（21）和亲水性纳米二氧化硅层（22），敏感层（3）为亲水材料氧化石墨烯薄层（31），电极引线（4）包括镍过渡层（41）和银层（42）。制备方法包括：制作基底（1），在基底（1）正面开槽（11）；制作微纳织构层（2），通过旋涂法获得环氧树脂层（21），通过气相法制备亲水性纳米二氧化硅，获得亲水性纳米二氧化硅层（22），在亲水性纳米二氧化硅层（22）表面微织构加工出圆柱凹坑；制作电极引线（4）；制作敏感层（3）得到氧化石墨烯薄层（31）。具有超亲水、自清洁等优点，对水分子检测灵敏度高、稳定性好。

Description

一种超亲水仿生基质含水量传感器及其制备方法 技术领域
本发明属于新型基质含水量传感器的应用领域，尤其涉及一种超亲水仿生基质含水量传感器及其制备方法，用于实现对一定量含水量土壤、栽培基质含水量的原位测量。
背景技术
土壤和栽培基质是矿物和有机物的混合组成部分，主要是固态颗粒，但是在固体颗粒间隙中存在着一定气体和液体，属于非均相体系。其复杂的组成，以及非均相混合态，使得土壤基质表现出迥然众多不同的物理化学特性。此外，由于部分土壤和基质本身比较松散、紧实度不够，引起的检测接触不良，导致了对其参数检测适应性差，检测灵敏度低、误差大、稳定性不好等问题，为土壤基质含水量的原位测量带来难度。
目前，传统的土壤含水量检测方法有烘干法、中子散射法、电阻法和电容法。烘干法是获取土壤含水量的标准做法，也是理论上的含水量标准值，且对基质参数检测适应性较好。但是不能够在现场实时检测且需要大量的人力和物力，不能及时获得土壤的墒情。与烘干法相比，中子散射法不需要进行土壤取样，同样对基质参数检测适应性较好，但是存在成本高昂、辐射等不足。电阻法是利用湿敏电阻的电阻值与含水量之间的对应关系，具有成本低、简单、快速的优点，但是存在着滞后性且灵敏度和准确度较差，尤其对基质参数检测适应性较差。电容法是将被测土壤物质作为电容器电介质的一部分，并结合土壤含水量和总的介电常数之间的对应关系，就可以得到土壤的含水量值。常用的电容传感器有平行极板式和圆柱式，其结构简单、易于实现，但是灵敏度不高，且存在边缘效应导致的非线性问题。
总之，以上的土壤含水量检测方法用于对基质含水量原位检测，由于基质本身比较松散、紧实度不够，往往引起检测接触不良，导致了检测灵敏度低、误差大、稳定性不好等问题和不足。
超亲水表面研究取得很大进展，并且在工业生产和实际生活中有广泛应用。表面浸润性是固体表面的一个重要特征，通常以接触角(contact angle，CA)表征液体对固体的浸润程度。通常把通过表面改性获得跟水滴接触角>150°称为超疏水性表面，接触角<5°称为超亲水表面。科研人员通过对不同材料的超亲水性研究，认为超亲水性与材料的电子空穴对及材料表面粗超度有关。一般来说制备超亲水表面可以通过两种途径，一是光引发超亲水；另一种是在亲水材料表面构造粗糙结构。对土壤含水量检测采用第二 种途径比较合适，各类织构表面具有不同的界面效应，通过合适的织构表面提高表面亲水性，使含水量传感器能够快速吸附水分子，减少响应时间，提高准确度。
随着对氧化石墨烯材料研究的不断深入，发现了二维层状结构的氧化石墨烯含有大量的含氧官能团，如羧基、羟基等，具有着极强的亲水特性。相关研究表明，氧化石墨烯的电阻会随温度升高显著减少，较高氧化程度的氧化石墨烯薄膜的电阻对数与相对湿度呈线性变化，具有良好的湿敏特性，因而也被逐步广泛的应用于气湿敏新型传感器的研制中。
发明内容
本发明的目的是针对土壤栽培基质含水量原位测量难题，提出一种超亲水仿生基质含水量传感器及其制备方法，用于实现对土壤、栽培基质等非均相体系的含水量原位测量，本发明综合应用氧化石墨烯薄膜的电阻对数与相对湿度呈线性特性，通过氧化石墨烯薄膜制作传感器反映被检测基质中含水量，以及传感器敏感层表面的超亲水结构和氧化石墨烯敏感材料薄层中含氧官能团的亲水特性，可以极大的增强传感器与被检测基质中水分子的接触效果，显著提升传感器的对水的灵敏度和稳定性，从而有效的克服由于基质本身松散带来的检测接触不良、灵敏度低、误差大、稳定性不好等问题。
本发明的技术方案是：一种超亲水仿生基质含水量传感器，包括基底、微纳织构层、敏感层和电极引线；
所述基底的正面开有长方形槽，所述长方形槽两侧分别开有长槽，所述长方形槽上依次附微纳织构层和敏感层，在所述长槽上分别附电极引线；
所述微纳织构层包括环氧树脂层和亲水性纳米二氧化硅层、且所述环氧树脂层位于亲水性纳米二氧化硅层的下面；所述亲水性纳米二氧化硅层表面进行微织构加工处理；
所述敏感层为氧化石墨烯薄层，所述氧化石墨烯薄层附在亲水性纳米二氧化硅层的表面。
上述方案中，所述电极引线包括镍过渡层和银层，且镍过渡层位于银层的下面。
上述方案中，所述基底为氧化铝陶瓷材料。
上述方案中，所述亲水性纳米二氧化硅层表面进行微织构加工出圆柱凹坑，所述圆柱凹坑的孔深为40nm～80nm，孔径为1μm～2μm。
进一步的，所述圆柱凹坑的孔深为50nm，孔径为1μm。
上述方案中，所述氧化石墨烯薄层的厚度为20nm。
上述方案中，所述镍过渡层厚度为80nm；所述银层厚度约3μm。
上述方案中，所述基底的厚度为1.5mm以上；所述长方形槽和两条长槽的深度为3.1μm。
上述方案中，所述电极引线上制作焊盘。
一种制备所述超亲水仿生基质含水量传感器的方法，包括以下步骤：
S1、制作基底，选用氧化铝陶瓷作为基底材料，且在正面开长方形槽，在长方形槽两侧分别开有长槽；
S2、制作微纳织构层，通过旋涂法将环氧树脂涂在长方形槽内，获得环氧树脂层，然后通过气相法制备亲水性纳米二氧化硅，并通过溶胶-凝胶法将亲水性纳米二氧化硅沉积在环氧树脂层表面，获得亲水性纳米二氧化硅层，再通过飞秒激光对亲水性纳米二氧化硅层表面进行微织构加工处理，加工出尺度为纳米级的圆柱凹坑；
S3、制作电极引线，通过直流磁控溅射法在长槽内沉积镍过渡层，然后通过磁控溅射法，将银沉积在镍过渡层表面，获得银层；
S4、制作敏感层，通过Hummers法制备敏感材料氧化石墨烯，然后对制备的氧化石墨烯进行真空低温热处理，增大其导电性，再通过旋涂法在亲水性纳米二氧化硅层表面，以及与亲水性纳米二氧化硅层相邻的部分银层表面，涂得均匀分布的氧化石墨烯薄层。
本发明采用上述技术解决方案所能达到的有益效果是：
1.本发明的基质含水量传感器基底选择氧化铝陶瓷材料，并在表面开槽，附上微纳织构层、敏感层和电极引线，具有成本低、制备容易、稳定性好、抗腐蚀、抗磨损、抗冲击、强度高等优点。
2.本发明的基质含水量传感器的敏感材料为氧化石墨烯薄层，具有大量共价键结合的含氧官能团，表现出良好的亲水性，提高了检测的灵敏度，缩短了传感器检测响应时间。
3.本发明的基质含水量传感器表面为微织构化的凹槽或凹坑结构，使传感器表面与水滴表面接触角小于5°，具有超亲水特性，在有一定含水量的土壤和栽培基质等环境下能够快速吸附水分子，实现快速测量，减少响应时间；而且纳米级超亲水微织构表面还具有自清洁仿生作用。
附图说明
图1是本发明一实施方式的超亲水仿生基质含水量传感器结构正面主视图；
图2是基底正面主视图；
图3是传感器在A-A方向的剖视图；
图4是传感器在B-B方向的剖视图。
其中，1、基底；2、微纳织构层；3、敏感层；4、电极引线；5、焊盘；11、长方形槽；12、长槽；21、环氧树脂层；22、亲水性纳米二氧化硅层；31、氧化石墨烯薄层；41、镍过渡层；42、银层。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步详细说明，但本发明的保护范围并不限于此。
图1所示为本发明所述超亲水仿生基质含水量传感器的一种实施方式，所述超亲水仿生基质含水量传感器，包括基底1、微纳织构层2、敏感层3和电极引线4；在电极引线4上制作焊盘5，并通过电极引线4和焊盘5引出电阻信号，方便与后续检测处理电路连接及实验测试。
如图2所示，所述基底1的正面开有长方形槽11，所述长方形槽11两侧分别开有长槽12。优选的，所述基底1为厚度为1.5mm以上的氧化铝陶瓷材料，形状为正方形，边长约为1cm，所述长方形槽11深度约3.1um，长L1约0.6cm，宽度W1约0.4cm，所述长槽12深度约3.1um，长L2约0.8cm，宽约W2约0.1cm。，所述基底1选择氧化铝陶瓷材料制，且在正面上制作长方形槽11和长槽12，长方形槽11上附微纳织构层2和敏感层3，2条长槽12上分别附电极引线4，具有成本低、制备容易、稳定性好、抗腐蚀、抗磨损、抗冲击、强度高等优点，适合插入土壤及栽培基质。
如图3和图4所示，所述微纳织构层2包括环氧树脂层21和亲水性纳米二氧化硅层22、且所述环氧树脂层21位于亲水性纳米二氧化硅层22的下面。所述亲水性纳米二氧化硅层22表面进行微织构加工处理。所述环氧树脂层21作用是增强亲水性纳米二氧化硅层22与基底1氧化铝陶瓷材料之间的连接；所述亲水性纳米二氧化硅层22作用是经过微织构加工为敏感层3表面提供超亲水结构，且亲水性纳米二氧化硅22是一种亲水性绝缘材料，可提高传感器亲水特性，同时不会影响反映水含量的电阻值。
所述环氧树脂层21厚度约为80nm，亲水性纳米二氧化硅层22厚度约为3μm，亲水性纳米二氧化硅层22表面微织构加工出圆柱凹坑，所述圆柱凹坑的孔深为40nm～80nm，孔径为1μm～2μm。优选的，所述圆柱凹坑的孔深为50nm，孔径为1μm。
所述敏感层3的材料为氧化石墨烯薄层31，所述氧化石墨烯薄层31附在亲水性纳米二氧化硅层22的表面。优选的，所述氧化石墨烯薄层31的厚度约为20nm。其二维层状结构的氧化石墨烯薄层31具有大量的含氧官能团，有利于与水分子的结合，具有亲水性，提高了传感器灵敏度；亲水性纳米二氧化硅层22表面微织构处理与氧化石墨烯薄层31结合，使传感器表面与水滴接触角小于5°，具有超亲水特性。
所述电极引线4包括镍过渡层41和银层42，且镍过渡层41位于银层42的下面。优选的，所述镍过渡层厚度约为80nm，作用是增强银层与基地氧化铝陶瓷材料之间的连接；优选的，所述银层厚度约为3μm，作用是引出检测电阻信号。
本发明还提供一种制备所述超亲水仿生基质含水量传感器的方法，包括以下步骤：
S1、制作基底1，基底1选用厚1.5mm以上氧化铝陶瓷材料制作，基底1形状为正方形，边长约为1cm，且在正面开深度约3.1μm长方形槽11，长L1约0.6cm，宽度W1约0.4cm，以及在长方形槽11两侧分别开深度约3.1μm长槽12，长L2约0.8cm，宽W2约0.1cm；
S2、制作微纳织构层2，通过旋涂法将环氧树脂涂在长约0.8cm，宽度0.4cm的长方形槽11内，获得厚度约为80nm的环氧树脂层21；然后通过气相法制备亲水性纳米二氧化硅，并通过溶胶-凝胶法将亲水性纳米二氧化硅沉积在环氧树脂层表面，获得厚度约为3μm的亲水性纳米二氧化硅层22，再通过飞秒激光对亲水性纳米二氧化硅层22表面进行微织构加工处理，加工出尺度为纳米级的圆柱凹坑，孔深约50nm，孔径约1μm；
S3、制作电极引线4，通过直流磁控溅射法在长约0.8cm，宽约0.1cm的长方形槽(12)内沉积厚度80nm的镍过渡层41；然后通过磁控溅射法，将银沉积在镍过渡层41表面，获得厚度约为3μm的银层42；
S4、制作敏感层3，通过Hummers法制备敏感材料氧化石墨烯；然后对制备的氧化石墨烯进行真空低温热处理，增大其导电性，再通过旋涂法在具有亲水结构的亲水性纳米二氧化硅层22表面，以及与亲水性纳米二氧化硅层22相邻的部分银层42表面，即在长约0.8cm，宽约0.1cm的长方形区域内上涂得均匀分布的氧化石墨烯薄层31，厚度约20nm。
所述步骤S3中电极引线4的沉积方式可以是电化学沉积，物理气相沉积，化学气相沉积中的一种，如磁控溅射，激光共聚焦溅射，脉冲激光溅射等。
本发明所述超亲水仿生基质含水量传感器具有超亲水、自清洁等优点，对水分子检测灵敏度高、稳定性好，适合栽培土壤基质的含水量原位测量。
应当理解，虽然本说明书是按照各个实施例描述的，但并非每个实施例仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
上文所列出的一系列的详细说明仅仅是针对本发明的可行性实施例的具体说明，它们并非用以限制本发明的保护范围，凡未脱离本发明技艺精神所作的等效实施例或变更均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种超亲水仿生基质含水量传感器，其特征在于，包括基底(1)、微纳织构层(2)、敏感层(3)和电极引线(4)；
    所述基底(1)的正面开有长方形槽(11)，所述长方形槽(11)两侧分别开有长槽(12)，所述长方形槽(11)上依次附微纳织构层(2)和敏感层(3)，在所述长槽(12)上分别附电极引线(4)；
    所述微纳织构层(2)包括环氧树脂层(21)和亲水性纳米二氧化硅层(22)、且所述环氧树脂层(21)位于亲水性纳米二氧化硅层(22)的下面；所述亲水性纳米二氧化硅层(22)表面进行微织构加工处理；
    所述敏感层(3)为氧化石墨烯薄层(31)，所述氧化石墨烯薄层(31)附在亲水性纳米二氧化硅层(22)的表面。
  2. 根据权利要求1所述的超亲水仿生基质含水量传感器，其特征在于，所述电极引线(4)包括镍过渡层(41)和银层(42)，且镍过渡层(41)位于银层(42)的下面。
  3. 根据权利要求1所述的超亲水仿生基质含水量传感器，其特征在于，所述基底(1)为氧化铝陶瓷材料。
  4. 根据权利要求1所述的超亲水仿生基质含水量传感器，其特征在于，所述亲水性纳米二氧化硅层(22)表面进行微织构加工出圆柱凹坑，所述圆柱凹坑的孔深为40nm～80nm，孔径为1μm～2μm。
  5. 根据权利要求4所述的超亲水仿生基质含水量传感器，其特征在于，所述圆柱凹坑的孔深为50nm，孔径为1μm。
  6. 根据权利要求1所述的超亲水仿生基质含水量传感器，其特征在于，所述氧化石墨烯薄层(31)的厚度为20nm。
  7. 根据权利要求2所述的超亲水仿生基质含水量传感器，其特征在于，所述镍过渡层(41)厚度为80nm；所述银层(42)厚度约3μm。
  8. 根据权利要求3所述的超亲水仿生基质含水量传感器，其特征在于，所述基底(1)的厚度为1.5mm以上；所述长方形槽(11)和两条长槽(12)的深度为3.1μm。
  9. 根据权利要求1所述的超亲水仿生基质含水量传感器，其特征在于，所述电极引线(4)上制作焊盘(5)。
  10. 一种制备权利要求1所述超亲水仿生基质含水量传感器的方法，其特征在于，包 括以下步骤：
    S1、制作基底(1)，选用氧化铝陶瓷作为基底(1)材料，且在正面开长方形槽(11)，在长方形槽两侧分别开有长槽(12)；
    S2、制作微纳织构层(2)，通过旋涂法将环氧树脂涂在长方形槽(11)内，获得环氧树脂层(21)，然后通过气相法制备亲水性纳米二氧化硅，并通过溶胶-凝胶法将亲水性纳米二氧化硅沉积在环氧树脂层(21)表面，获得亲水性纳米二氧化硅层(22)，再通过飞秒激光对亲水性纳米二氧化硅层(22)表面进行微织构加工处理，加工出尺度为纳米级的圆柱凹坑；
    S3、制作电极引线(4)，通过直流磁控溅射法在长槽(12)内沉积镍过渡层(41)，然后通过磁控溅射法，将银沉积在镍过渡层(41)表面，获得银层(42)；
    S4、制作敏感层(3)，通过Hummers法制备敏感材料氧化石墨烯，然后对制备的氧化石墨烯进行真空低温热处理，增大其导电性，再通过旋涂法在亲水性纳米二氧化硅层(22)表面，以及与亲水性纳米二氧化硅层(22)相邻的部分银层(42)表面，涂得均匀分布的氧化石墨烯薄层(31)。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110943265A (zh) * 2019-05-07 2020-03-31 吉林大学 耦合新型仿生热管的电池热管理装置制备及双向热流控制方法
CN111847376A (zh) * 2020-07-02 2020-10-30 上海集成电路研发中心有限公司 一种湿度传感器制备方法
CN112255286A (zh) * 2020-08-11 2021-01-22 江苏大学 一种集成仿生的栽培基质离子浓度在线检测装置及方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108693218B (zh) * 2018-03-23 2023-11-03 天津大学 一种可感知水工建筑物内部含水信息的智能骨料
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CN110514721B (zh) * 2019-07-24 2021-08-03 江苏大学 一种自储水自补水pH传感器
CN112704493B (zh) * 2021-01-05 2022-07-05 南方医科大学南方医院 一种具有长效超亲水性能的医疗传感器及其制备方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0775314B1 (de) * 1994-08-06 2004-07-14 Forschungszentrum Jülich Gmbh Chemische sensoren, insbesondere biosensoren auf siliciumbasis
JP2010500276A (ja) * 2006-08-09 2010-01-07 マサチューセッツ・インスティテュート・オブ・テクノロジー ナノ粒子被膜及び作製方法
CN102803127A (zh) * 2009-05-08 2012-11-28 加州大学评议会 超亲水纳米结构
JP2012246163A (ja) * 2011-05-26 2012-12-13 Canon Inc ナノ多孔質薄膜、およびその製造方法
CN103108705A (zh) * 2010-07-19 2013-05-15 哈佛大学校长及研究员协会 控制润湿特性的分层结构化表面
CN103364463A (zh) * 2013-06-20 2013-10-23 东南大学 一种基于还原氧化石墨烯的pH传感器及PH值检测方法
US20140106127A1 (en) * 2011-02-28 2014-04-17 Research Foundation Of The City University Of New York Polymer having optically transparent superhydrophobic surface
CN104458840A (zh) * 2014-11-12 2015-03-25 东莞市青麦田数码科技有限公司 基于氧化石墨烯的电化学传感器及其制备方法
CN104725075A (zh) * 2013-12-20 2015-06-24 中国科学院兰州化学物理研究所 一种仿生微纳结构超亲水硅表面的制备方法
CN105136860A (zh) * 2015-07-24 2015-12-09 浙江大学 基于氧化石墨烯/石墨烯/硅的湿度传感器及其制备方法
CN105531585A (zh) * 2013-07-16 2016-04-27 诺基亚技术有限公司 环境传感器和用于确定相对蒸汽压力的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103207217B (zh) * 2013-04-26 2015-04-22 江苏大学 一种非插入式栽培基质含水量传感器
CN103424147B (zh) * 2013-08-27 2015-12-02 江苏大学 无土栽培基质多参数检测仪
CN204359739U (zh) * 2015-01-29 2015-05-27 重庆墨希科技有限公司 一种石墨烯纳米墙电阻式湿度传感器

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0775314B1 (de) * 1994-08-06 2004-07-14 Forschungszentrum Jülich Gmbh Chemische sensoren, insbesondere biosensoren auf siliciumbasis
JP2010500276A (ja) * 2006-08-09 2010-01-07 マサチューセッツ・インスティテュート・オブ・テクノロジー ナノ粒子被膜及び作製方法
CN102803127A (zh) * 2009-05-08 2012-11-28 加州大学评议会 超亲水纳米结构
CN103108705A (zh) * 2010-07-19 2013-05-15 哈佛大学校长及研究员协会 控制润湿特性的分层结构化表面
US20140106127A1 (en) * 2011-02-28 2014-04-17 Research Foundation Of The City University Of New York Polymer having optically transparent superhydrophobic surface
JP2012246163A (ja) * 2011-05-26 2012-12-13 Canon Inc ナノ多孔質薄膜、およびその製造方法
CN103364463A (zh) * 2013-06-20 2013-10-23 东南大学 一种基于还原氧化石墨烯的pH传感器及PH值检测方法
CN105531585A (zh) * 2013-07-16 2016-04-27 诺基亚技术有限公司 环境传感器和用于确定相对蒸汽压力的方法
CN104725075A (zh) * 2013-12-20 2015-06-24 中国科学院兰州化学物理研究所 一种仿生微纳结构超亲水硅表面的制备方法
CN104458840A (zh) * 2014-11-12 2015-03-25 东莞市青麦田数码科技有限公司 基于氧化石墨烯的电化学传感器及其制备方法
CN105136860A (zh) * 2015-07-24 2015-12-09 浙江大学 基于氧化石墨烯/石墨烯/硅的湿度传感器及其制备方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110943265A (zh) * 2019-05-07 2020-03-31 吉林大学 耦合新型仿生热管的电池热管理装置制备及双向热流控制方法
CN110943265B (zh) * 2019-05-07 2024-04-26 吉林大学 耦合新型仿生热管的电池热管理装置制备及双向热流控制方法
CN111847376A (zh) * 2020-07-02 2020-10-30 上海集成电路研发中心有限公司 一种湿度传感器制备方法
CN112255286A (zh) * 2020-08-11 2021-01-22 江苏大学 一种集成仿生的栽培基质离子浓度在线检测装置及方法
CN112255286B (zh) * 2020-08-11 2022-10-28 江苏大学 一种集成仿生的栽培基质离子浓度在线检测装置及方法

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