CN110018215B - Fick diffusion law-based miniature chloride ion sensor and method thereof - Google Patents
Fick diffusion law-based miniature chloride ion sensor and method thereof Download PDFInfo
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Abstract
本发明公开了一种基于Fick扩散定律的微型氯离子传感器及其方法,采用本发明所述方法制备的氯离子传感器为薄片式、全固态的微型氯离子传感器,具有体积小、结构稳定性好、可靠性高、密封性好的优点,可以安放在仪器设备的任何测试部位,受外界因素影响小,尤其适用于高盐高湿微液膜环境下飞行器腐蚀状况的实时监测。本发明能够弥补之前被动式测量信号弱、稳定性差、寿命短、响应时间长等多种缺点,并且测量微液膜状态下的氯离子浓度,能够应用于飞行器盐雾腐蚀与防护,提高飞行器使用寿命。
The invention discloses a micro chloride ion sensor based on Fick's diffusion law and a method thereof. The chloride ion sensor prepared by the method of the invention is a thin-sheet, all-solid-state micro chloride ion sensor, which has small size and good structural stability. It has the advantages of high reliability and good sealing. It can be placed in any testing part of the instrument and equipment, and is less affected by external factors. It is especially suitable for real-time monitoring of aircraft corrosion conditions in high-salt and high-humidity micro-liquid film environments. This invention can make up for the shortcomings of previous passive measurement methods such as weak signal, poor stability, short life, and long response time. It can also measure the chloride ion concentration in the micro-liquid film state, and can be applied to aircraft salt spray corrosion and protection, and improve the service life of aircraft. .
Description
技术领域Technical field
本发明涉及氯离子传感器领域,尤其涉及一种基于Fick扩散定律的微型氯离子传感器及其方法。The invention relates to the field of chloride ion sensors, and in particular to a miniature chloride ion sensor based on Fick's diffusion law and a method thereof.
背景技术Background technique
腐蚀是飞行器结构损伤的主要形式之一,占全部结构损伤的20%。飞行器结构腐蚀是构件在大气腐蚀微液膜环境下通过化学或电化学作用而发生的积累性化学损失和破坏。在腐蚀发生初期,腐蚀部位很难探测到,当其萌生后若不加以控制将比其它损伤发展更快、更严重。飞行器的腐蚀损伤直接影响着飞行器的出勤率,更严重影响着飞行员的人生安全。因此,必须采取积极防护措施,提早预估飞行器腐蚀程度,以降低飞行器维修成本及避免悲剧的发生。Corrosion is one of the main forms of aircraft structural damage, accounting for 20% of all structural damage. Aircraft structural corrosion is the cumulative chemical loss and damage of components through chemical or electrochemical effects in an atmospheric corrosive micro-liquid film environment. In the early stages of corrosion, it is difficult to detect the corrosion site. If it is not controlled after its initiation, it will develop faster and more seriously than other damages. Corrosion damage to aircraft directly affects the aircraft's availability, and more seriously affects the pilot's life safety. Therefore, active protective measures must be taken to predict the degree of aircraft corrosion in advance to reduce aircraft maintenance costs and avoid tragedies.
我国东部沿海地区不管是民用还是军用飞机,由于长期在高盐雾、高湿度等恶劣、复杂环境下执行飞行任务,飞行器表面甚至驾驶舱内部无时无刻不在遭受着各种各样的腐蚀。这些腐蚀在发生初期人的肉眼一般观察不到,等到发现时飞行器表面已经遭受了严重腐蚀,这将大大缩减飞行器的服役寿命,并将严重威胁飞行员的人生安全。Whether it is a civilian or military aircraft in the eastern coastal areas of my country, due to long-term flight missions in harsh and complex environments such as high salt spray and high humidity, the surface of the aircraft and even the interior of the cockpit are subject to various corrosions all the time. These corrosions are generally invisible to the naked eye in the early stages of occurrence. By the time they are discovered, the surface of the aircraft has already suffered severe corrosion, which will greatly reduce the service life of the aircraft and seriously threaten the safety of pilots.
目前,我国对飞行器的腐蚀防护还只是以密封隔水和机体定期检查为主,传统检测方式效率较低、成本偏高,虽然也有报道通过超声、红外成像等技术来评估飞行器等的腐蚀状况,但这些方法都是在飞行器已经被腐蚀比较严重情况下才检测出腐蚀部位,效率低下且成本较高。目前国内对飞行器的腐蚀检查主要以酸碱度为主,由于氯离子对飞行器的腐蚀速率低于氢离子对飞行器的腐蚀速率,所以国内外对氯离子的腐蚀防护一直未开始研究,但是在沿海环境、海岛环境这种高盐、高湿、弱酸性环境中氯离子对飞行器的腐蚀速率几乎成倍增加,飞行器中迫切需要一种对氯离子浓度进行监测的传感器。At present, my country's corrosion protection for aircraft is mainly based on water sealing and regular inspection of the aircraft body. Traditional detection methods are inefficient and costly. Although there are also reports of using ultrasound, infrared imaging and other technologies to evaluate the corrosion status of aircraft, etc. However, these methods only detect the corroded parts when the aircraft has been severely corroded, which is inefficient and costly. At present, domestic corrosion inspections of aircraft are mainly based on pH. Since the corrosion rate of chlorine ions on aircraft is lower than the corrosion rate of hydrogen ions on aircraft, research on chloride ion corrosion protection has not been started at home and abroad. However, in coastal environments, In a high-salt, high-humidity, weakly acidic environment such as an island environment, the corrosion rate of chloride ions on aircraft almost doubles. There is an urgent need for a sensor to monitor chloride ion concentration in aircraft.
发明内容Contents of the invention
本发明所要解决的技术问题是针对背景技术中所涉及到的缺陷,提供一种基于Fick扩散定律的微型氯离子传感器及其方法。The technical problem to be solved by the present invention is to provide a miniature chloride ion sensor and method based on Fick's diffusion law in view of the defects involved in the background technology.
本发明为解决上述技术问题采用以下技术方案:The present invention adopts the following technical solutions to solve the above technical problems:
基于Fick扩散定律的微型氯离子传感器,包含聚酰亚胺薄片基板、辅助电极、感受电极、参比电极和对电极;A miniature chloride ion sensor based on Fick's diffusion law, including a polyimide sheet substrate, auxiliary electrode, sensing electrode, reference electrode and counter electrode;
所述辅助电极、感受电极、参比电极、对电极均设置在所述聚酰亚胺薄片基板上,均包含敏感元、导线、以及通过导线和敏感元相连的焊点;The auxiliary electrode, sensing electrode, reference electrode, and counter electrode are all arranged on the polyimide sheet substrate, and each includes a sensitive element, a wire, and a solder joint connected to the sensitive element through the wire;
所述感受电极的敏感元呈叉指状;所述辅助电极的敏感元呈矩形,其上设有用于放置感受电极敏感元的凹槽;所述感受电极的敏感元放置在辅助电极敏感元的凹槽内;The sensing element of the sensing electrode is interdigitated; the sensing element of the auxiliary electrode is rectangular, with a groove for placing the sensing element of the sensing electrode; the sensing element of the sensing electrode is placed on the sensitive element of the auxiliary electrode inside the groove;
所述参比电极、对电极的敏感元均呈长条状,分别设置在所述辅助电极敏感元两侧、和辅助电极敏感元两侧的边平行,且和感受单机敏感元的叉指长度方向垂直;The sensitive elements of the reference electrode and the counter electrode are all in the shape of long strips, which are respectively arranged on both sides of the auxiliary electrode sensitive element and parallel to the sides of the auxiliary electrode sensitive element, and are the same as the interdigital length of the sensing element of the stand-alone machine. Orientation vertical;
所述辅助电极的敏感元、感受电极的敏感元、参比电极的敏感元从下至上均包含Ti粘附层、Pt电极层和Au薄膜层;所述对电极的敏感元从下至上均包含Ti粘附层和Pt电极层;The sensitive elements of the auxiliary electrode, the sensitive element of the sensing electrode, and the sensitive elements of the reference electrode all include Ti adhesion layer, Pt electrode layer and Au film layer from bottom to top; the sensitive elements of the counter electrode all include from bottom to top. Ti adhesion layer and Pt electrode layer;
所述所述辅助电极的敏感元、感受电极的敏感元、参比电极的敏感元上镀有Ag薄膜层,且Ag薄膜层上镀有AgCl薄膜层;The sensitive element of the auxiliary electrode, the sensitive element of the sensing electrode, and the sensitive element of the reference electrode are plated with an Ag thin film layer, and the Ag thin film layer is plated with an AgCl thin film layer;
所述辅助电极、感受电极、参比电极、对电极之间均不接触。There is no contact between the auxiliary electrode, the sensing electrode, the reference electrode and the counter electrode.
作为本发明基于Fick扩散定律的微型氯离子传感器进一步的优化方案,所述感受电极的敏感元的叉指数为3,叉指宽度为5μm,叉指间距为1mm,叉指长度为3mm;所述感受电极的导线线宽为70μm,所述感受电极的焊点为1*1.5mm的长方形;As a further optimization solution of the present invention's miniature chloride ion sensor based on Fick's diffusion law, the interdigital index of the sensing element of the sensing electrode is 3, the interdigital width is 5μm, the interdigital spacing is 1mm, and the interdigital length is 3mm; The wire width of the sensing electrode is 70 μm, and the solder joint of the sensing electrode is a rectangle of 1*1.5mm;
所述辅助电极的敏感元为8*4mm的长方形;辅助电极敏感元和感受电极敏感元的距离为5μm;所述辅助电极的的导线线宽为70μm,所述辅助电极焊点为1*1.5mm的长方形;The sensitive element of the auxiliary electrode is a rectangle of 8*4mm; the distance between the sensitive element of the auxiliary electrode and the sensitive element of the sensing electrode is 5μm; the wire width of the auxiliary electrode is 70μm, and the soldering point of the auxiliary electrode is 1*1.5 mm rectangle;
所述参比电极的敏感元为70*3000μm的长方形;参比电极敏感元和辅助电极敏感元之间的距离为70μm;所述参比电极导线线宽为70μm,所述参比电极焊点为1*1.5mm的长方形;The sensitive element of the reference electrode is a rectangle of 70*3000 μm; the distance between the sensitive element of the reference electrode and the sensitive element of the auxiliary electrode is 70 μm; the line width of the reference electrode wire is 70 μm, and the soldering point of the reference electrode It is a rectangle of 1*1.5mm;
所述对电极的敏感元为70*3000μm的长方形;所述对电极敏感元和辅助电极敏感元之间的距离为70μm;所述对电极导线线宽为70μm,所述对电极焊点为1*1.5mm的长方形。The sensitive element of the counter electrode is a rectangle of 70*3000 μm; the distance between the sensitive element of the counter electrode and the sensitive element of the auxiliary electrode is 70 μm; the line width of the counter electrode wire is 70 μm, and the soldering point of the counter electrode is 1 *1.5mm rectangle.
作为本发明基于Fick扩散定律的微型氯离子传感器进一步的优化方案,还包含第一至第四连接头;As a further optimization solution of the present invention's miniature chloride ion sensor based on Fick's diffusion law, it also includes first to fourth connectors;
所述第一至第四连接头的一端分别和辅助电极、感受电极、参比电极、Pt对电极的焊点相连,另一端均用于和外界相连;One end of the first to fourth connectors is connected to the solder joints of the auxiliary electrode, the sensing electrode, the reference electrode, and the Pt counter electrode respectively, and the other ends are used to connect to the outside world;
所述辅助电极、感受电极、参比电极、Pt对电极的导线和焊点上均设有绝缘层。Insulating layers are provided on the wires and solder joints of the auxiliary electrode, sensing electrode, reference electrode, and Pt counter electrode.
本发还公开了一种用该基于Fick扩散定律的微型氯离子传感器的测量方法,包含以下步骤:The present invention also discloses a measurement method using the miniature chloride ion sensor based on Fick's diffusion law, which includes the following steps:
步骤1),设置电流源、函数发生器和电位测量装置,其中,电流源的控制端接函数发生器、通过函数发生器产生恒定脉冲恒电流,电流源的正极接对电极的焊点,电流源的负极接辅助电极的焊点;电位测量装置的正极接感受电极的焊点,电位测量装置的负极接参比电极的焊点;Step 1), set up a current source, a function generator and a potential measuring device. The control terminal of the current source is connected to the function generator, and a constant pulse constant current is generated through the function generator. The positive electrode of the current source is connected to the solder joint of the counter electrode, and the current The negative electrode of the source is connected to the solder joint of the auxiliary electrode; the positive electrode of the potential measuring device is connected to the solder joint of the receiving electrode, and the negative electrode of the potential measuring device is connected to the solder joint of the reference electrode;
步骤2),通过电位测量装置测量得到微型氯离子传感器中感受电极的电位曲线;Step 2), measure the potential curve of the sensing electrode in the miniature chloride ion sensor through a potential measuring device;
步骤3),对电位曲线求导,得到电位曲线的导数曲线,令导数曲线峰值对应的时间为过渡时间τ;Step 3): Derive the potential curve to obtain the derivative curve of the potential curve, and let the time corresponding to the peak value of the derivative curve be the transition time τ;
步骤4),根据以下公式计算出微型氯离子传感器测得的氯离子浓度C* O:Step 4), calculate the chloride ion concentration C * O measured by the micro chloride ion sensor according to the following formula:
式中,DO是氯离子扩散系数,A是辅助电极的表面积,F是法拉第系数,I是电流源施加的电流。In the formula, DO is the chloride ion diffusion coefficient, A is the surface area of the auxiliary electrode, F is the Faraday coefficient, and I is the current applied by the current source.
本发明还公开了一种该基于Fick扩散定律的微型氯离子传感器的制备方法,包含以下步骤:The invention also discloses a preparation method of the miniature chloride ion sensor based on Fick's diffusion law, which includes the following steps:
步骤A),采用磁控溅射法在聚酰亚胺薄片基板上依次溅射Ti粘附层、Pt电极层;Step A), using the magnetron sputtering method to sequentially sputter the Ti adhesion layer and the Pt electrode layer on the polyimide sheet substrate;
步骤B),采用基于光刻技术在溅射过Ti粘附层、Pt电极层后的聚酰亚胺薄片基板上面进行线路图形转移,形成参比电极、感受电极、辅助电极、对电极在Ti粘附层和Pt电极层上的图案;Step B), use photolithography technology to transfer the circuit pattern on the polyimide sheet substrate after sputtering the Ti adhesion layer and the Pt electrode layer to form the reference electrode, the sensing electrode, the auxiliary electrode, and the counter electrode on the Ti Patterns on the adhesion layer and Pt electrode layer;
步骤C),采用电镀的方法在参比电极、感受电极、辅助电极的图案的Pt电极层上进行电镀Au,形成Au薄膜层;Step C), electroplating Au on the Pt electrode layer of the pattern of the reference electrode, sensing electrode, and auxiliary electrode using an electroplating method to form an Au thin film layer;
步骤D),采用电镀的方法在参比电极、感受电极、辅助电极的Au薄膜层上进行电镀Ag,形成Ag薄膜层;Step D), electroplating Ag on the Au thin film layers of the reference electrode, sensing electrode, and auxiliary electrode using an electroplating method to form an Ag thin film layer;
步骤E),采用电镀的方法在参比电极、感受电极、辅助电极的Ag薄膜层上进行电镀AgCl,形成AgCl薄膜层。Step E), electroplating AgCl on the Ag thin film layers of the reference electrode, the sensing electrode, and the auxiliary electrode by electroplating to form an AgCl thin film layer.
本发明采用以上技术方案与现有技术相比,具有以下技术效果:Compared with the existing technology, the present invention adopts the above technical solution and has the following technical effects:
本发明稳定性高、灵敏性好、能够在弱酸性盐雾环境中对氯离子进行实时监测,解决了目前大气监测以传统监测站点为主、站点少、覆盖面积少、数据更新实时性差、不能够真实反应出人们身边接触的真实空气质量信息的问题。The invention has high stability, good sensitivity, and can perform real-time monitoring of chloride ions in a weakly acidic salt spray environment. It solves the problem that the current atmospheric monitoring is mainly based on traditional monitoring sites, with few sites, small coverage area, poor real-time data update, and inconsistency. It can truly reflect the real air quality information that people are exposed to around them.
附图说明Description of the drawings
图1为本发明提供的微型氯离子传感器的整体结构示意图。Figure 1 is a schematic diagram of the overall structure of the micro chloride ion sensor provided by the present invention.
图2为图1中A处的局部放大图;Figure 2 is a partial enlarged view of point A in Figure 1;
图3为本发明提供的微型氯离子传感器溅射、光刻方案图;Figure 3 is a diagram of the sputtering and photolithography scheme of the micro chloride ion sensor provided by the present invention;
图4为本发明提供的氯离子传感器测试电路连接图;Figure 4 is a connection diagram of the chloride ion sensor test circuit provided by the present invention;
图5为本发明提供的微型氯离子传感器脉冲电流函数图;Figure 5 is a pulse current function diagram of the micro chloride ion sensor provided by the present invention;
图6为本发明提供的微型氯离子传感器Nernst理论电位曲线图;Figure 6 is a Nernst theoretical potential curve diagram of the miniature chloride ion sensor provided by the present invention;
图7为本发明实施例微型氯离子传感器分别在0.1、0.3、0.5、0.7、1mol/L氯离子浓度微液膜条件下电位值与时间经过信号处理后得到的关系曲线图;Figure 7 is a graph showing the relationship between potential value and time obtained after signal processing of the micro-chloride ion sensor according to the embodiment of the present invention under micro-liquid membrane conditions with chloride ion concentrations of 0.1, 0.3, 0.5, 0.7 and 1 mol/L respectively;
图8为本发明实施例微型氯离子传感器分别在0.1、0.3、0.5、0.7、1mol/L氯离子浓度微液膜条件下测试结果导数图;Figure 8 is a derivative diagram of the test results of the micro-chloride ion sensor according to the embodiment of the present invention under micro-liquid membrane conditions with chloride ion concentrations of 0.1, 0.3, 0.5, 0.7, and 1 mol/L;
图9为本发明实施例微型氯离子传感器分别在0.1、0.3、0.5、0.7、1mol/L氯离子浓度微液膜条件进行十次测试得到的过渡时间标定曲线与理论方程对比图。Figure 9 is a comparison diagram of the transition time calibration curve and the theoretical equation obtained by conducting ten tests on the micro-liquid membrane conditions of chloride ion concentrations of 0.1, 0.3, 0.5, 0.7, and 1 mol/L according to the embodiment of the present invention.
图中,1-对电极的敏感元,2-对电极的导线,3-对电极的焊点,4-辅助电极的敏感元,5-辅助电极的导线,6-辅助电极的焊点,7-感受电极的敏感元,8-感受电极的导线,9-感受电极的焊点,10-参比电极的敏感元,11-参比电极的导线,12-参比电极的焊点,13-聚酰亚胺薄片基板。In the figure, 1 - the sensitive element of the counter electrode, 2 - the wire of the counter electrode, 3 - the solder joint of the counter electrode, 4 - the sensitive element of the auxiliary electrode, 5 - the wire of the auxiliary electrode, 6 - the solder joint of the auxiliary electrode, 7 - The sensitive element of the sensing electrode, 8 - The wire of the sensing electrode, 9 - The solder joint of the sensing electrode, 10 - The sensitive element of the reference electrode, 11 - The wire of the reference electrode, 12 - The solder joint of the reference electrode, 13 - Polyimide sheet substrate.
具体实施方式Detailed ways
下面结合附图对本发明的技术方案做进一步的详细说明:The technical solution of the present invention will be further described in detail below in conjunction with the accompanying drawings:
本发明可以以许多不同的形式实现,而不应当认为限于这里所述的实施例。相反,提供这些实施例以便使本公开透彻且完整,并且将向本领域技术人员充分表达本发明的范围。在附图中,为了清楚起见放大了组件。The invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, components are exaggerated for clarity.
如图1所示,本发明公开了一种基于Fick扩散定律的微型氯离子传感器,包含聚酰亚胺薄片基板、辅助电极、感受电极、参比电极和对电极;As shown in Figure 1, the present invention discloses a miniature chloride ion sensor based on Fick's diffusion law, which includes a polyimide sheet substrate, an auxiliary electrode, a sensing electrode, a reference electrode and a counter electrode;
所述辅助电极、感受电极、参比电极、对电极均设置在所述聚酰亚胺薄片基板上,均包含敏感元、导线、以及通过导线和敏感元相连的焊点;The auxiliary electrode, sensing electrode, reference electrode, and counter electrode are all arranged on the polyimide sheet substrate, and each includes a sensitive element, a wire, and a solder joint connected to the sensitive element through the wire;
如图2所示,所述感受电极的敏感元呈叉指状;所述辅助电极的敏感元呈矩形,其上设有用于放置感受电极敏感元的凹槽;所述感受电极的敏感元放置在辅助电极敏感元的凹槽内;As shown in Figure 2, the sensing element of the sensing electrode is interdigitated; the sensing element of the auxiliary electrode is rectangular, with a groove for placing the sensing electrode sensing element; the sensing element of the sensing electrode is placed In the groove of the auxiliary electrode sensitive element;
所述参比电极、对电极的敏感元均呈长条状,分别设置在所述辅助电极敏感元两侧、和辅助电极敏感元两侧的边平行,且和感受单机敏感元的叉指长度方向垂直;The sensitive elements of the reference electrode and the counter electrode are all in the shape of long strips, which are respectively arranged on both sides of the auxiliary electrode sensitive element and parallel to the sides of the auxiliary electrode sensitive element, and are the same as the interdigital length of the sensing element of the stand-alone machine. Orientation vertical;
所述辅助电极的敏感元、感受电极的敏感元、参比电极的敏感元从下至上均包含Ti粘附层、Pt电极层和Au薄膜层;所述对电极的敏感元从下至上均包含Ti粘附层和Pt电极层;The sensitive elements of the auxiliary electrode, the sensitive element of the sensing electrode, and the sensitive elements of the reference electrode all include Ti adhesion layer, Pt electrode layer and Au film layer from bottom to top; the sensitive elements of the counter electrode all include from bottom to top. Ti adhesion layer and Pt electrode layer;
所述所述辅助电极的敏感元、感受电极的敏感元、参比电极的敏感元上镀有Ag薄膜层,且Ag薄膜层上镀有AgCl薄膜层;The sensitive element of the auxiliary electrode, the sensitive element of the sensing electrode, and the sensitive element of the reference electrode are plated with an Ag thin film layer, and the Ag thin film layer is plated with an AgCl thin film layer;
所述辅助电极、感受电极、参比电极、对电极之间均不接触。There is no contact between the auxiliary electrode, the sensing electrode, the reference electrode and the counter electrode.
作为本发明基于Fick扩散定律的微型氯离子传感器进一步的优化方案,所述感受电极的敏感元的叉指数为3,叉指宽度为5μm,叉指间距为1mm,叉指长度为3mm;所述感受电极的导线线宽为70μm,所述感受电极的焊点为1*1.5mm的长方形;As a further optimization solution of the present invention's miniature chloride ion sensor based on Fick's diffusion law, the interdigital index of the sensing element of the sensing electrode is 3, the interdigital width is 5μm, the interdigital spacing is 1mm, and the interdigital length is 3mm; The wire width of the sensing electrode is 70 μm, and the solder joint of the sensing electrode is a rectangle of 1*1.5mm;
所述辅助电极的敏感元为8*4mm的长方形;辅助电极敏感元和感受电极敏感元的距离为5μm;所述辅助电极的的导线线宽为70μm,所述辅助电极焊点为1*1.5mm的长方形;The sensitive element of the auxiliary electrode is a rectangle of 8*4mm; the distance between the sensitive element of the auxiliary electrode and the sensitive element of the sensing electrode is 5μm; the wire width of the auxiliary electrode is 70μm, and the soldering point of the auxiliary electrode is 1*1.5 mm rectangle;
所述参比电极的敏感元为70*3000μm的长方形;参比电极敏感元和辅助电极敏感元之间的距离为70μm;所述参比电极导线线宽为70μm,所述参比电极焊点为1*1.5mm的长方形;The sensitive element of the reference electrode is a rectangle of 70*3000 μm; the distance between the sensitive element of the reference electrode and the sensitive element of the auxiliary electrode is 70 μm; the line width of the reference electrode wire is 70 μm, and the soldering point of the reference electrode It is a rectangle of 1*1.5mm;
所述对电极的敏感元为70*3000μm的长方形;所述对电极敏感元和辅助电极敏感元之间的距离为70μm;所述对电极导线线宽为70μm,所述对电极焊点为1*1.5mm的长方形。The sensitive element of the counter electrode is a rectangle of 70*3000 μm; the distance between the sensitive element of the counter electrode and the sensitive element of the auxiliary electrode is 70 μm; the line width of the counter electrode wire is 70 μm, and the soldering point of the counter electrode is 1 *1.5mm rectangle.
作为本发明基于Fick扩散定律的微型氯离子传感器进一步的优化方案,还包含第一至第四连接头;As a further optimization solution of the present invention's miniature chloride ion sensor based on Fick's diffusion law, it also includes first to fourth connectors;
所述第一至第四连接头的一端分别和辅助电极、感受电极、参比电极、Pt对电极的焊点相连,另一端均用于和外界相连;One end of the first to fourth connectors is connected to the solder joints of the auxiliary electrode, the sensing electrode, the reference electrode, and the Pt counter electrode respectively, and the other ends are used to connect to the outside world;
所述辅助电极、感受电极、参比电极、Pt对电极的导线和焊点上均设有绝缘层。Insulating layers are provided on the wires and solder joints of the auxiliary electrode, sensing electrode, reference electrode, and Pt counter electrode.
本发明还公开了一种该基于Fick扩散定律的微型氯离子传感器的制备方法,包含以下步骤:The invention also discloses a preparation method of the miniature chloride ion sensor based on Fick's diffusion law, which includes the following steps:
步骤A),采用磁控溅射法在聚酰亚胺薄片基板上依次溅射Ti粘附层、Pt电极层;Step A), using the magnetron sputtering method to sequentially sputter the Ti adhesion layer and the Pt electrode layer on the polyimide sheet substrate;
步骤B),采用基于光刻技术在溅射过Ti粘附层、Pt电极层后的聚酰亚胺薄片基板上面进行线路图形转移,形成参比电极、感受电极、辅助电极、对电极在Ti粘附层和Pt电极层上的图案;Step B), use photolithography technology to transfer the circuit pattern on the polyimide sheet substrate after sputtering the Ti adhesion layer and the Pt electrode layer to form the reference electrode, the sensing electrode, the auxiliary electrode, and the counter electrode on the Ti Patterns on the adhesion layer and Pt electrode layer;
步骤C),采用电镀的方法在参比电极、感受电极、辅助电极的图案的Pt电极层上进行电镀Au,形成Au薄膜层;Step C), electroplating Au on the Pt electrode layer of the pattern of the reference electrode, sensing electrode, and auxiliary electrode using an electroplating method to form an Au thin film layer;
步骤D),采用电镀的方法在参比电极、感受电极、辅助电极的Au薄膜层上进行电镀Ag,形成Ag薄膜层;Step D), electroplating Ag on the Au thin film layers of the reference electrode, sensing electrode, and auxiliary electrode using an electroplating method to form an Ag thin film layer;
步骤E),采用电镀的方法在参比电极、感受电极、辅助电极的Ag薄膜层上进行电镀AgCl,形成AgCl薄膜层。Step E), electroplating AgCl on the Ag thin film layers of the reference electrode, the sensing electrode, and the auxiliary electrode by electroplating to form an AgCl thin film layer.
所述聚酰亚胺薄片基板为15*10*1mm长方体基板。所述聚酰亚胺薄片基板所用材料为聚酰亚胺(Polyimide,PI),聚酰亚胺(PI)具有耐高温(达400℃)、优良的机械性能、高的耐辐照性能、良好的酸碱化学稳定性以及柔韧性等优点。使用聚酰亚胺作为氯离子传感器基板材料能够提高传感器使用温度范围,减小外界腐蚀环境对氯离子传感器影响,提高传感器在复杂环境下的稳定性和可靠性。此外聚酰亚胺是柔性材料,能够拓宽氯离子传感器应用领域和应用范围。The polyimide sheet substrate is a 15*10*1mm rectangular parallelepiped substrate. The material used for the polyimide sheet substrate is polyimide (PI). Polyimide (PI) has high temperature resistance (up to 400°C), excellent mechanical properties, high radiation resistance, and good Excellent acid and alkali chemical stability and flexibility. Using polyimide as the substrate material of the chloride ion sensor can increase the temperature range of the sensor, reduce the impact of the external corrosive environment on the chloride ion sensor, and improve the stability and reliability of the sensor in complex environments. In addition, polyimide is a flexible material that can broaden the application field and scope of chloride ion sensors.
图3为本发明提供的微型氯离子传感器溅射、光刻方案图。Figure 3 is a diagram of the sputtering and photolithography scheme of the micro chloride ion sensor provided by the present invention.
本发还公开了一种用该基于Fick扩散定律的微型氯离子传感器的测量方法,包含以下步骤:The present invention also discloses a measurement method using the miniature chloride ion sensor based on Fick's diffusion law, which includes the following steps:
步骤1),如图4所示,设置电流源、函数发生器和电位测量装置,其中,电流源的控制端接函数发生器、通过函数发生器产生恒定脉冲恒电流,电流源的正极接对电极的焊点,电流源的负极接辅助电极的焊点;电位测量装置的正极接感受电极的焊点,电位测量装置的负极接参比电极的焊点;Step 1), as shown in Figure 4, set up a current source, a function generator and a potential measuring device. The control terminal of the current source is connected to the function generator, and a constant pulse constant current is generated through the function generator. The positive electrode of the current source is connected to the The solder joint of the electrode, the negative electrode of the current source is connected to the solder joint of the auxiliary electrode; the positive electrode of the potential measuring device is connected to the solder joint of the receiving electrode, and the negative electrode of the potential measuring device is connected to the solder joint of the reference electrode;
步骤2),通过电位测量装置测量得到微型氯离子传感器中感受电极的电位曲线;Step 2), measure the potential curve of the sensing electrode in the miniature chloride ion sensor through a potential measuring device;
步骤3),对电位曲线求导,得到电位曲线的导数曲线,令导数曲线峰值对应的时间为过渡时间τ;Step 3): Derive the potential curve to obtain the derivative curve of the potential curve, and let the time corresponding to the peak value of the derivative curve be the transition time τ;
步骤4),根据以下公式计算出微型氯离子传感器测得的氯离子浓度C* O:Step 4), calculate the chloride ion concentration C * O measured by the micro chloride ion sensor according to the following formula:
式中,DO是氯离子扩散系数,A是辅助电极的表面积,F是法拉第系数,I是电流源施加的电流。In the formula, DO is the chloride ion diffusion coefficient, A is the surface area of the auxiliary electrode, F is the Faraday coefficient, and I is the current applied by the current source.
图5为本发明提供的微型氯离子传感器脉冲电流函数图;参见图5,所述脉冲电流为直流信号,且随时间变化规律相同;脉冲电流为正时,传感器开始测量得到一个电位随时间变化的S型曲线,软件通过测试界面计算得到一个与之对应的过渡时间,脉冲电流为负时,传感器处于停滞状态,电位逐渐回到零值波动;Figure 5 is a pulse current function diagram of the micro chloride ion sensor provided by the present invention; see Figure 5, the pulse current is a DC signal, and the change pattern with time is the same; when the pulse current is positive, the sensor starts to measure a potential that changes with time S-shaped curve, the software calculates a corresponding transition time through the test interface. When the pulse current is negative, the sensor is in a stagnant state, and the potential gradually returns to zero value;
图6为本发明提供的微型氯离子传感器Nernst理论电位曲线图;参见图6,τ为氯离子浓度的过渡时间,理论上当t=τ时,电位为无穷大,图中显示为测量设备电位阈值;Figure 6 is a theoretical potential curve diagram of the micro chloride ion sensor Nernst provided by the present invention; referring to Figure 6, τ is the transition time of the chloride ion concentration. In theory, when t=τ, the potential is infinite, and the figure shows the potential threshold of the measuring equipment;
图7为本发明实施例微型氯离子传感器分别在0.1、0.3、0.5、0.7、1mol/L氯离子浓度微液膜条件下电位值与时间经过信号处理后得到的关系曲线图;参见图7,所述传感器在微液膜环境下测量得到的电位时间曲线为S型曲线,且随着浓度的升高,S型曲线逐渐后移,且浓度越高,其曲线越平滑,曲线的拐点(过渡时间)越清晰;Figure 7 is a graph showing the relationship between potential value and time obtained after signal processing of the micro-chloride ion sensor according to the embodiment of the present invention under micro-liquid membrane conditions with chloride ion concentrations of 0.1, 0.3, 0.5, 0.7 and 1 mol/L respectively; see Figure 7. The potential time curve measured by the sensor in a micro-liquid film environment is an S-shaped curve, and as the concentration increases, the S-shaped curve gradually moves backward, and the higher the concentration, the smoother the curve, and the inflection point (transition) of the curve time) the clearer;
图8为本发明实施例微型氯离子传感器分别在0.1、0.3、0.5、0.7、1mol/L氯离子浓度微液膜条件下测试结果导数图;参见图8,所述传感器分别在0.1、0.3、0.5、0.7、1mol/L氯离子浓度微液膜条件下测试结果导数曲线峰值很明显,可以通过自动寻峰函数求取导数曲线的峰值,峰值即为过渡时间值;Figure 8 is a derivative diagram of the test results of the micro chloride ion sensor according to the embodiment of the present invention under the conditions of micro-liquid membrane with chloride ion concentrations of 0.1, 0.3, 0.5, 0.7 and 1 mol/L respectively. Referring to Figure 8, the sensor is measured at 0.1, 0.3, 0.3, 0.7 and 1 mol/L respectively. The peak value of the derivative curve of the test results under micro-liquid membrane conditions with chloride ion concentrations of 0.5, 0.7, and 1 mol/L is very obvious. The peak value of the derivative curve can be obtained through the automatic peak-finding function, and the peak value is the transition time value;
图9为本发明实施例微型氯离子传感器分别在0.1、0.3、0.5、0.7、1mol/L氯离子浓度微液膜条件进行十次测试得到的过渡时间标定曲线与理论方程对比图;参见图9,所述传感器进行多次测量得到的过渡时间标定曲线与理论方程规律相同,且稳定性较好。Figure 9 is a comparison diagram between the transition time calibration curve and the theoretical equation obtained by conducting ten tests on the micro-liquid membrane conditions of 0.1, 0.3, 0.5, 0.7, and 1 mol/L chloride ion concentration of the micro-chloride ion sensor according to the embodiment of the present invention; see Figure 9 , the transition time calibration curve obtained by multiple measurements of the sensor is consistent with the theoretical equation and has good stability.
本技术领域技术人员可以理解的是,除非另外定义,这里使用的所有术语(包括技术术语和科学术语)具有与本发明所属领域中的普通技术人员的一般理解相同的意义。还应该理解的是,诸如通用字典中定义的那些术语应该被理解为具有与现有技术的上下文中的意义一致的意义,并且除非像这里一样定义,不会用理想化或过于正式的含义来解释。It can be understood by one of ordinary skill in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It should also be understood that terms such as those defined in general dictionaries are to be understood to have meanings consistent with their meaning in the context of the prior art, and are not to be taken in an idealized or overly formal sense unless defined as herein. explain.
以上所述的具体实施方式,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施方式而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The above-mentioned specific embodiments further describe the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above-mentioned are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.
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