CN108680493B - Method for measuring corrosion current density in galvanic corrosion of metal welding joint part - Google Patents
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Abstract
本发明公开金属焊接接头部位电偶腐蚀中腐蚀电流密度的测定方法，使用金属焊接接头部位电偶腐蚀的测定装置进行测定，计算机对采集的电流信号进行分析处理，输出电偶腐蚀电流，根据电偶腐蚀电流时间图可以确定焊接接头试样表面的阴阳极区域并判断焊接接头各部位的电偶腐蚀敏感性强弱，首先计算出腐蚀电流密度的大小，在计算出电偶腐蚀电流密度之后，知道阴极区与阳极区腐蚀速度的差值，通过该值得大小与正负以判断出阳极和阴极，以及二者腐蚀速度的差异，最后计算得到腐蚀电流密度。
The invention discloses a method for measuring the corrosion current density in the galvanic corrosion of metal welded joints. The measuring device for galvanic corrosion of metal welded joints is used to measure, the computer analyzes and processes the collected current signals, outputs the galvanic corrosion current, and according to the electrical The couple corrosion current time diagram can determine the cathode and anode areas on the surface of the welded joint sample and judge the galvanic corrosion sensitivity of each part of the welded joint. First, the corrosion current density is calculated. After calculating the galvanic corrosion current density, Knowing the difference between the corrosion rate of the cathode area and the anode area, the anode and the cathode, as well as the difference in the corrosion rate of the two, can be judged by the value and positive and negative, and finally the corrosion current density can be calculated.
Description
本发明申请是母案申请“金属焊接接头部位电偶腐蚀的测定装置与测定方法”的分案申请，母案申请的申请日为2016年4月29日，申请号为2016102867138。The present application is a divisional application of the parent application "Measuring Apparatus and Measuring Method for Galvanic Corrosion of Metal Welded Joints", the filing date of the parent application is April 29, 2016, and the application number is 2016102867138.
技术领域technical field
本发明属于电偶腐蚀的测定装置领域，尤其是金属焊接接头部位电偶腐蚀的测定装置与测定方法。The invention belongs to the field of measuring devices for galvanic corrosion, in particular to a measuring device and method for measuring galvanic corrosion of metal welded joints.
背景技术Background technique
电偶腐蚀,也称之为双金属腐蚀。当两种或两种以上不同金属或同种金属的不同组织(如焊缝)在导电介质中接触后，由于各自电极电位不同而构成腐蚀原电池。在电解质水膜下，形成腐蚀宏电池，会加速其中负电位金属的腐蚀。影响电偶腐蚀的因素有环境、介质导电性、阴阳极的面积比等。电偶腐蚀一般取决于异种金属之间的电位差。这里的电位指的是两种金属或同种金属的不同组织(如焊缝)分别在电解质溶液(腐蚀介质)中的实际电位，即该金属在溶液中的腐蚀电位。其中，通常来讲，电位高的作为阴极，电位低的作为阳极，特别是当阳极面积较小时会形成小阳极大阴极的电偶对，使腐蚀加剧。在其他条件不变的情况下，电位差越大，腐蚀速度可能越大。这里说的可能是由于电位是热力学数据，通过热力学数据无法确切的表述出腐蚀过程的快慢，甚至有时因为外界环境的差异还会出现相反的结论。因此，对动力学过程的数据，即电偶腐蚀电流的测量就变得尤为重要。通过测量得到的腐蚀电流能够计算出不同材料或不同组织之间腐蚀速度差异。从而判断设备在特定环境中的腐蚀行为。Galvanic corrosion, also known as bimetallic corrosion. When two or more different metals or different structures of the same metal (such as welds) are in contact in a conductive medium, a corrosion galvanic cell is formed due to the different potentials of their respective electrodes. Under the electrolyte water film, corrosion macro cells are formed, which will accelerate the corrosion of negative potential metals. Factors affecting galvanic corrosion include environment, dielectric conductivity, area ratio of cathode and anode, etc. Galvanic corrosion generally depends on the potential difference between dissimilar metals. The potential here refers to the actual potential of two metals or different structures of the same metal (such as welds) in the electrolyte solution (corrosion medium), that is, the corrosion potential of the metal in the solution. Among them, generally speaking, the high potential is used as the cathode, and the low potential is used as the anode, especially when the anode area is small, a galvanic pair of small anode and large cathode will be formed, which will aggravate the corrosion. Under the condition that other conditions remain unchanged, the greater the potential difference, the greater the corrosion rate may be. What is said here may be because the potential is thermodynamic data, and the speed of the corrosion process cannot be accurately expressed by thermodynamic data, and sometimes even the opposite conclusion will appear due to the difference in the external environment. Therefore, data on the kinetic process, that is, the measurement of galvanic corrosion current, becomes particularly important. The corrosion rate difference between different materials or different structures can be calculated by measuring the corrosion current. So as to judge the corrosion behavior of the equipment in a specific environment.
焊接是工程制造中的重要工艺环节，许多零部件都是通过焊接连接在一起。由于焊接过程中不可避免对焊接接头的组织产生影响，所以即使两个连接部件和焊材都是同种材料，焊接接头也会因为组织不均匀在腐蚀环境中发生电偶腐蚀。研究金属焊接接头部位腐蚀的方法主要有：盐雾试验，浸泡实验法(全浸、间浸等)和电化学实验法(电位测量、电偶电流测量、极化测量、电化学阻抗测量等)。前者只能得到失重数据和表面腐蚀形貌，无法得到腐蚀电流数据，耗时长。电化学方法虽然能得到电化学信息，但大多局限于分别研究单一区域，对实验室制备的工作电极也有加工复杂耗时等缺点，更无法实现在线无损检测。Welding is an important process link in engineering manufacturing, and many components are connected together by welding. Since the welding process inevitably affects the structure of the welded joint, even if the two connecting parts and the welding material are of the same material, the welded joint will suffer from galvanic corrosion in a corrosive environment due to uneven structure. The main methods for studying the corrosion of metal welded joints are: salt spray test, immersion test method (full immersion, inter-immersion, etc.) and electrochemical test method (potential measurement, galvanic current measurement, polarization measurement, electrochemical impedance measurement, etc.) . The former can only obtain weight loss data and surface corrosion morphology, but cannot obtain corrosion current data, which takes a long time. Although electrochemical methods can obtain electrochemical information, most of them are limited to the study of a single area, and the working electrodes prepared in the laboratory also have disadvantages such as complicated and time-consuming processing, and can not achieve on-line non-destructive testing.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术的不足，提供了金属焊接接头部位电偶腐蚀的测定装置与测定方法，在线检测出金属焊接接头表面各区域之间的腐蚀电偶电流，从而判断阳极区和阴极区，得到金属焊接接头表面各区域的电偶腐蚀程度，从而判断出其电偶腐蚀敏感性。The purpose of the present invention is to overcome the deficiencies of the prior art, and to provide a measuring device and a measuring method for galvanic corrosion of metal welded joints, so as to detect the corrosion galvanic current between various areas on the surface of metal welded joints online, thereby judging the difference between the anode area and the galvanic area. Cathode area, get the galvanic corrosion degree of each area on the surface of metal welded joint, so as to judge its galvanic corrosion susceptibility.
为了解决上述技术问题，本发明是通过以下技术方案实现的：In order to solve the above-mentioned technical problems, the present invention is achieved through the following technical solutions:
金属焊接接头部位电偶腐蚀的测定装置，包括测试探头，离子通道，电化学测量装置和计算机，其中：Apparatus for the determination of galvanic corrosion at metal welded joints, including test probes, ion channels, electrochemical measurement apparatus and computer, wherein:
电化学测量装置和计算机相连，电化学测量装置将采集的电化学信号传递给计算机，计算机以对采集的电流信号进行分析处理，输出测试时间内的电偶腐蚀电流的数值；The electrochemical measurement device is connected to the computer, and the electrochemical measurement device transmits the collected electrochemical signal to the computer, and the computer analyzes and processes the collected current signal, and outputs the value of the galvanic corrosion current within the test time;
电化学测量装置的工作端和接地端分别连接两块待测焊接试样，用以采集信号；测试探头包括第一测试探头和第二测试探头，两者结构相同且分别固定在两块待测焊接试样上，由探头上盖、探头主体、探头下管和磁性固定栓组成，探头上盖下端与探头主体相连并在两者的连接处设置密封圈，探头主体的下端面中央设置探头下管，探头主体的下端面的四角对称设置磁性固定栓，在磁性固定栓的末端设置磁石，用于吸附在焊接测试区域；在探头下管的下端面设置试样接触圆环；在探头上盖上且沿探头上盖的轴向设置贯穿探头上盖的离子通道连接孔，在探头主体和探头下端的内部设置空腔，在探头上盖、探头主体和探头下端连接成一体后，离子通道连接孔和空腔同轴连接成一体的溶液储存腔；The working end and the grounding end of the electrochemical measurement device are respectively connected to two welding samples to be tested for signal acquisition; the test probe includes a first test probe and a second test probe, both of which have the same structure and are respectively fixed on the two test probes. The welding sample is composed of the probe upper cover, the probe main body, the probe lower tube and the magnetic fixing bolt. The lower end of the probe upper cover is connected with the probe main body and a sealing ring is arranged at the connection between the two. The four corners of the lower end face of the probe body are symmetrically arranged with magnetic fixing bolts, and a magnet is arranged at the end of the magnetic fixing bolt to be adsorbed in the welding test area; a sample contact ring is arranged on the lower end face of the lower tube of the probe; An ion channel connection hole is arranged on the top of the probe and along the axial direction of the probe upper cover, and a cavity is arranged inside the probe body and the lower end of the probe. After the probe upper cover, the probe body and the lower end of the probe are connected into one, the ion channel is connected The hole and the cavity are coaxially connected to form a solution storage cavity;
离子通道的一端设置在第一测试探头的探头上盖的离子通道连接孔中，其另一端设置在第二测试探头的探头上盖的离子通道连接孔中，以连通两个测试探头的溶液储存腔。One end of the ion channel is set in the ion channel connection hole of the probe upper cover of the first test probe, and the other end of the ion channel is set in the ion channel connection hole of the probe upper cover of the second test probe, so as to connect the solution storage of the two test probes cavity.
在上述技术方案中，在溶液储存腔中设置金属焊接接头实际工作环境下的溶液，以模拟待测试部位的工作环境。In the above technical solution, the solution under the actual working environment of the metal welded joint is set in the solution storage cavity to simulate the working environment of the part to be tested.
在上述技术方案中，离子通道能够导通离子且无法导通电子，选用塑料管道并在其中填充能够导通离子且无法导通电子的材料，例如海绵、溶液，凝胶，优选填充饱和氯化钾凝胶的硅胶管作为离子通道。In the above technical solution, the ion channel can conduct ions but cannot conduct electrons. Plastic pipes are selected and filled with materials that can conduct ions but cannot conduct electrons, such as sponges, solutions, gels, preferably filled with saturated chloride Silicone tubes of potassium gel serve as ion channels.
在上述技术方案中，测试探头整体上选用绝缘材料制备，例如聚四氟乙烯。In the above technical solution, the test probe is made of insulating material as a whole, such as polytetrafluoroethylene.
在上述技术方案中，第一测试探头设置在待测试样品的母材区、热影响区或者焊合区(即焊缝区)；第二测试探头设置在待测试样品的母材区、热影响区或者焊合区(即焊缝区)，这样一来，两个探头之间配合可分别测定焊缝区、热影响区；热影响区、母材；焊缝区、母材之间的，不同的热影响区之间的电偶腐蚀电流。In the above technical solution, the first test probe is arranged in the base metal area, the heat-affected zone or the welding zone (ie the weld zone) of the sample to be tested; the second test probe is arranged in the base metal area of the sample to be tested, the heat affected zone In this way, the cooperation between the two probes can measure the weld zone, the heat-affected zone; the heat-affected zone, the base metal; the weld zone and the base metal, respectively. Galvanic corrosion current between different heat-affected zones.
在进行使用时，按照下述步骤进行：When using it, follow the steps below:
步骤1，利用磁石和磁性固定栓将测试探头固定在待测样品的表面并紧密贴合，在结合处使用绝缘材料(例如环氧树脂胶、白硅胶、502)进行防漏液处理，此时试样接触圆环与待测样品的表面紧密贴合
在步骤1中，若待测样品表面不平整，粗糙，或者属于无磁性的材料，使用白硅胶或环氧树脂对测试探头直接给予固定。In
步骤2，向溶液储存腔中加入预先配置的溶液，以模拟待测样品的不同工作状态，待测样品在试样接触圆环中的部分即为样品的测试面积，在这一区域上浸泡预先配置的模拟溶液；再利用离子通道连通两个测试探头的溶液储存腔中的溶液。Step 2: Add a preconfigured solution to the solution storage cavity to simulate different working states of the sample to be tested. The part of the sample to be tested in the sample contact ring is the test area of the sample, and soaking in this area is pre-dip. The configured simulated solution; the solution in the solution storage cavity of the two test probes is connected by ion channel.
步骤3，将待测样品分别与电化学测量装置的工作端和接地端相连，开启电化学测量装置进行测试，同时以计算机对信号予以记录。Step 3: Connect the sample to be tested to the working end and the grounding end of the electrochemical measuring device respectively, turn on the electrochemical measuring device for testing, and simultaneously record the signal with a computer.
在上述技术方案中，第一测试探头设置在待测试样品的母材区、热影响区或者焊合区(即焊缝区)，且设置第一测试探头的待测试样品与电化学测量装置的工作端相连；第二测试探头设置在待测试样品的母材区、热影响区或者焊合区(即焊缝区)，且设置第二测试探头的待测试样品与电化学测量装置的接地端相连；这样一来，两个探头之间配合可分别测定焊缝区、热影响区；热影响区、母材；焊缝区、母材之间的，不同的热影响区之间的电偶腐蚀电流。通过此方法测得的电偶腐蚀电流为导通状态下第一测试探头所覆盖区域组织相对于第二测试探头所覆盖区域组织的腐蚀电流的差值，即I＝I1-I2。In the above technical solution, the first test probe is arranged in the base metal area, the heat-affected zone or the welding area (that is, the weld area) of the sample to be tested, and the first test probe is arranged between the sample to be tested and the electrochemical measurement device. The working ends are connected; the second test probe is arranged in the base metal area, the heat affected zone or the welding area (that is, the weld area) of the sample to be tested, and the sample to be tested of the second test probe is arranged with the grounding end of the electrochemical measuring device In this way, the cooperation between the two probes can respectively measure the weld zone, the heat affected zone; the heat affected zone and the base metal; corrosion current. The galvanic corrosion current measured by this method is the difference between the corrosion current of the tissue in the area covered by the first test probe relative to the tissue in the area covered by the second test probe in the conducting state, ie I=I 1 -I 2 .
在上述技术方案中，在开始测量之前，设置第一测试探头的待测试样品与电化学测量装置的工作端相连并形成导通状态，设置第二测试探头的待测试样品与电化学测量装置的接地端处于断开状态，在开始测试时以得到连通瞬间的暂态脉冲电流。In the above technical solution, before starting the measurement, the sample to be tested on which the first test probe is set is connected to the working end of the electrochemical measuring device to form a conducting state, and the sample to be tested on which the second test probe is set is connected to the working end of the electrochemical measuring device. The ground terminal is disconnected, and the transient pulse current at the moment of connection is obtained when the test is started.
在上述技术方案中，由计算机记录电化学测量装置采集的信号，在设置第二测试探头的待测试样品与电化学测量装置的接地端导通瞬间，由于电位差异所导致的瞬间暂态脉冲电流，之后继续读取电偶腐蚀电流信号，待电偶腐蚀电流稳定之后，继续采集一段时间后停止采集(例如200—1000s)。并将所得数据拷贝至TXT文档中或其他格式的记录文件中。计算机对采集的电流信号进行分析处理，输出电偶腐蚀电流，根据电偶腐蚀电流时间图可以确定焊接接头试样表面的阴阳极区域并判断焊接接头各部位的电偶腐蚀敏感性强弱。In the above technical solution, the signal collected by the electrochemical measurement device is recorded by the computer, and at the moment when the sample to be tested where the second test probe is set and the ground end of the electrochemical measurement device are turned on, the instantaneous transient pulse current caused by the potential difference , and then continue to read the galvanic corrosion current signal. After the galvanic corrosion current is stabilized, continue to collect for a period of time and then stop collecting (for example, 200-1000s). And copy the obtained data to a TXT file or a record file in other formats. The computer analyzes and processes the collected current signal and outputs the galvanic corrosion current. According to the galvanic corrosion current time diagram, the cathode and anode areas on the surface of the welded joint sample can be determined and the galvanic corrosion sensitivity of each part of the welded joint can be judged.
与现有技术相比，本发明的有益效果是：该装置可以检测出金属焊接接头表面各区域之间的腐蚀电偶电流，从而判断阳极区和阴极区，得到金属焊接接头表面各区域的电偶腐蚀程度，从而判断出其电偶腐蚀敏感性。Compared with the prior art, the beneficial effects of the present invention are: the device can detect the corrosion galvanic current between each area on the surface of the metal welded joint, so as to determine the anode area and the cathode area, and obtain the electrical current of each area on the surface of the metal welded joint. The degree of galvanic corrosion can be judged to determine its susceptibility to galvanic corrosion.
附图说明Description of drawings
图1为本发明的测试探头结构示意图；1 is a schematic structural diagram of a test probe of the present invention;
图2为本发明的热影响区对母材区的电偶腐蚀电流实验接线示意图；Fig. 2 is the schematic diagram of the wiring diagram of the galvanic corrosion current experiment of the base metal zone of the heat affected zone of the present invention;
图3为本发明的接线原理图示意；3 is a schematic diagram of a wiring schematic diagram of the present invention;
图4为本发明技术方案进行性能测试的热影响区对母材区的电偶腐蚀电流图；Fig. 4 is the galvanic corrosion current diagram of the base metal zone of the heat-affected zone in the performance test of the technical solution of the present invention;
图5为本发明技术方案进行性能测试的热影响区对焊合区的电偶腐蚀电流图；Fig. 5 is the galvanic corrosion current diagram of the heat-affected zone to the welding zone in the performance test of the technical solution of the present invention;
图6为本发明技术方案进行性能测试的母材区对焊合区的电偶腐蚀电流图。FIG. 6 is a diagram of the galvanic corrosion current of the base metal area to the welding area in the performance test of the technical solution of the present invention.
其中1为离子通道连接孔，2为探头上盖，3为密封圈，4为探头主体，5为溶液储存腔，6为探头下管，7为磁性固定栓，8为试样接触圆环，9为磁石，10为工作端，11为接地端，12为焊合区，13为热影响区，14为母材区，15为第一测试探头，16为第二测试探头，17为第一测试探头的工作圆环，18为第二测试探头的工作圆环，19为离子通道，20为电化学测量装置，21为计算机。1 is the ion channel connection hole, 2 is the probe upper cover, 3 is the sealing ring, 4 is the probe body, 5 is the solution storage cavity, 6 is the probe lower tube, 7 is the magnetic fixing bolt, 8 is the sample contact ring, 9 is the magnet, 10 is the working end, 11 is the grounding end, 12 is the welding zone, 13 is the heat-affected zone, 14 is the base metal zone, 15 is the first test probe, 16 is the second test probe, and 17 is the first test probe The working ring of the test probe, 18 is the working ring of the second test probe, 19 is the ion channel, 20 is the electrochemical measurement device, and 21 is the computer.
具体实施方式Detailed ways
下面结合附图与具体的实施方式对本发明作进一步详细描述：The present invention is described in further detail below in conjunction with the accompanying drawings and specific embodiments:
如附图1—3所示，本发明的金属焊接接头部位电偶腐蚀的测定装置，包括测试探头，离子通道，电化学测量装置和计算机，其中：As shown in the accompanying drawings 1-3, the measuring device for galvanic corrosion of metal welded joints of the present invention includes a test probe, an ion channel, an electrochemical measurement device and a computer, wherein:
电化学测量装置和计算机相连，电化学测量装置将采集的电化学信号传递给计算机，计算机以对采集的电流信号进行分析处理，输出测试时间内的电偶腐蚀电流的数值；The electrochemical measurement device is connected to the computer, and the electrochemical measurement device transmits the collected electrochemical signal to the computer, and the computer analyzes and processes the collected current signal, and outputs the value of the galvanic corrosion current within the test time;
电化学测量装置的工作端和接地端分别连接两块待测焊接试样，用以采集信号；测试探头包括第一测试探头和第二测试探头，两者结构相同且分别固定在两块待测焊接试样上，由探头上盖、探头主体、探头下管和磁性固定栓组成，探头上盖下端与探头主体相连并在两者的连接处设置密封圈，探头主体的下端面中央设置探头下管，探头主体的下端面的四角对称设置磁性固定栓，在磁性固定栓的末端设置磁石，用于吸附在焊接测试区域；在探头下管的下端面设置试样接触圆环；在探头上盖上且沿探头上盖的轴向设置贯穿探头上盖的离子通道连接孔，在探头主体和探头下端的内部设置空腔，在探头上盖、探头主体和探头下端连接成一体后，离子通道连接孔和空腔同轴连接成一体的溶液储存腔；The working end and the grounding end of the electrochemical measurement device are respectively connected to two welding samples to be tested for signal acquisition; the test probe includes a first test probe and a second test probe, both of which have the same structure and are respectively fixed on the two test probes. The welding sample is composed of the probe upper cover, the probe main body, the probe lower tube and the magnetic fixing bolt. The lower end of the probe upper cover is connected with the probe main body and a sealing ring is arranged at the connection between the two. The four corners of the lower end face of the probe body are symmetrically arranged with magnetic fixing bolts, and a magnet is arranged at the end of the magnetic fixing bolt to be adsorbed in the welding test area; a sample contact ring is arranged on the lower end face of the lower tube of the probe; An ion channel connection hole is arranged on the top of the probe and along the axial direction of the probe upper cover, and a cavity is arranged inside the probe body and the lower end of the probe. After the probe upper cover, the probe body and the lower end of the probe are connected into one, the ion channel is connected The hole and the cavity are coaxially connected to form a solution storage cavity;
离子通道的一端设置在第一测试探头的探头上盖的离子通道连接孔中，其另一端设置在第二测试探头的探头上盖的离子通道连接孔中，以连通两个测试探头的溶液储存腔(及溶液)。One end of the ion channel is set in the ion channel connection hole of the probe upper cover of the first test probe, and the other end of the ion channel is set in the ion channel connection hole of the probe upper cover of the second test probe, so as to connect the solution storage of the two test probes cavity (and solution).
在上述技术方案中，在溶液储存腔中设置金属焊接接头实际工作环境下的溶液，以模拟待测试部位的工作环境。In the above technical solution, the solution under the actual working environment of the metal welded joint is set in the solution storage cavity to simulate the working environment of the part to be tested.
在上述技术方案中，离子通道能够导通离子且无法导通电子，选用塑料管道并在其中填充能够导通离子且无法导通电子的材料，例如海绵、溶液，凝胶，优选填充饱和氯化钾凝胶的硅胶管作为离子通道。In the above technical solution, the ion channel can conduct ions but cannot conduct electrons. Plastic pipes are selected and filled with materials that can conduct ions but cannot conduct electrons, such as sponges, solutions, gels, preferably filled with saturated chloride Silicone tubes of potassium gel serve as ion channels.
在上述技术方案中，测试探头整体上选用绝缘材料制备，例如聚四氟乙烯。In the above technical solution, the test probe is made of insulating material as a whole, such as polytetrafluoroethylene.
在上述技术方案中，第一测试探头设置在待测试样品的母材区、热影响区或者焊合区(即焊缝区)；第二测试探头设置在待测试样品的母材区、热影响区或者焊合区(即焊缝区)，这样一来，两个探头之间配合可分别测定焊缝区、热影响区；热影响区、母材；焊缝区、母材之间的，不同的热影响区之间的电偶腐蚀电流。In the above technical solution, the first test probe is arranged in the base metal area, the heat-affected zone or the welding zone (ie the weld zone) of the sample to be tested; the second test probe is arranged in the base metal area of the sample to be tested, the heat affected zone In this way, the cooperation between the two probes can measure the weld zone, the heat-affected zone; the heat-affected zone, the base metal; the weld zone and the base metal, respectively. Galvanic corrosion current between different heat-affected zones.
在进行使用时，按照下述步骤进行：When using it, follow the steps below:
步骤1，利用磁石和磁性固定栓将测试探头固定在待测样品的表面并紧密贴合，在结合处使用绝缘材料(例如环氧树脂胶、白硅胶、502)进行防漏液处理，此时试样接触圆环与待测样品的表面紧密贴合
在步骤1中，若待测样品表面不平整，粗糙，或者属于无磁性的材料，使用白硅胶或环氧树脂对测试探头直接给予固定。In
步骤2，向溶液储存腔中加入预先配置的溶液，以模拟待测样品的不同工作状态，待测样品在试样接触圆环中的部分即为样品的测试面积，在这一区域上浸泡预先配置的模拟溶液；再利用离子通道连通两个测试探头的溶液储存腔中的溶液。Step 2: Add a preconfigured solution to the solution storage cavity to simulate different working states of the sample to be tested. The part of the sample to be tested in the sample contact ring is the test area of the sample, and soaking in this area is pre-dip. The configured simulated solution; the solution in the solution storage cavity of the two test probes is connected by ion channel.
步骤3，将待测样品分别与电化学测量装置的工作端和接地端相连，开启电化学测量装置进行测试，同时以计算机对信号予以记录。Step 3: Connect the sample to be tested to the working end and the grounding end of the electrochemical measuring device respectively, turn on the electrochemical measuring device for testing, and simultaneously record the signal with a computer.
在上述技术方案中，第一测试探头设置在待测试样品的母材区、热影响区或者焊合区(即焊缝区)，且设置第一测试探头的待测试样品与电化学测量装置的工作端相连；第二测试探头设置在待测试样品的母材区、热影响区或者焊合区(即焊缝区)，且设置第二测试探头的待测试样品与电化学测量装置的接地端相连；这样一来，两个探头之间配合可分别测定焊缝区、热影响区；热影响区、母材；焊缝区、母材之间的，不同的热影响区之间的电偶腐蚀电流。通过此方法测得的电偶腐蚀电流为导通状态下第一测试探头所覆盖区域组织相对于第二测试探头所覆盖区域组织的腐蚀电流的差值，即I＝I1-I2。In the above technical solution, the first test probe is arranged in the base metal area, the heat-affected zone or the welding area (that is, the weld area) of the sample to be tested, and the first test probe is arranged between the sample to be tested and the electrochemical measurement device. The working ends are connected; the second test probe is arranged in the base metal area, the heat affected zone or the welding area (that is, the weld area) of the sample to be tested, and the sample to be tested of the second test probe is arranged with the grounding end of the electrochemical measuring device In this way, the cooperation between the two probes can respectively measure the weld zone, the heat affected zone; the heat affected zone and the base metal; corrosion current. The galvanic corrosion current measured by this method is the difference between the corrosion current of the tissue in the area covered by the first test probe relative to the tissue in the area covered by the second test probe in the conducting state, ie I=I 1 -I 2 .
在上述技术方案中，在开始测量之前，设置第一测试探头的待测试样品与电化学测量装置的工作端相连并形成导通状态，设置第二测试探头的待测试样品与电化学测量装置的接地端处于断开状态，在开始测试时以得到连通瞬间的暂态脉冲电流。In the above technical solution, before starting the measurement, the sample to be tested on which the first test probe is set is connected to the working end of the electrochemical measuring device to form a conducting state, and the sample to be tested on which the second test probe is set is connected to the working end of the electrochemical measuring device. The ground terminal is disconnected, and the transient pulse current at the moment of connection is obtained when the test is started.
在上述技术方案中，由计算机记录电化学测量装置采集的信号，在设置第二测试探头的待测试样品与电化学测量装置的接地端导通瞬间，由于电位差异所导致的瞬间暂态脉冲电流，之后继续读取电偶腐蚀电流信号，待电偶腐蚀电流稳定之后，继续采集一段时间后停止采集(例如200—1000s)。并将所得数据拷贝至TXT文档中或其他格式的记录文件中。计算机对采集的电流信号进行分析处理，输出电偶腐蚀电流，根据电偶腐蚀电流时间图可以确定焊接接头试样表面的阴阳极区域并判断焊接接头各部位的电偶腐蚀敏感性强弱。In the above technical solution, the signal collected by the electrochemical measurement device is recorded by the computer, and at the moment when the sample to be tested where the second test probe is set and the ground end of the electrochemical measurement device are turned on, the instantaneous transient pulse current caused by the potential difference , and then continue to read the galvanic corrosion current signal. After the galvanic corrosion current is stabilized, continue to collect for a period of time and then stop collecting (for example, 200-1000s). And copy the obtained data to a TXT file or a record file in other formats. The computer analyzes and processes the collected current signal and outputs the galvanic corrosion current. According to the galvanic corrosion current time diagram, the cathode and anode areas on the surface of the welded joint sample can be determined and the galvanic corrosion sensitivity of each part of the welded joint can be judged.
电偶腐蚀电流数据的处理。在分析腐蚀电流之前，首先应计算出腐蚀电流密度的大小。腐蚀电流密度是腐蚀电流对腐蚀面积的乘积，其中，该面积为与电化学测量装置工作端相连的待测试样上测试探头的试样接触圆环中与(模拟)溶液相接触的待测试样面积(即试样接触圆环的面积)，而非对电极端的工作面积(与电化学测量装置接地端相连的待测试样上测试探头的试样接触圆环中与模拟溶液相接触的待测试样面积)。其腐蚀电流密度用如下公式计算：Processing of Galvanic Corrosion Current Data. Before analyzing the corrosion current, the magnitude of the corrosion current density should be calculated first. The corrosion current density is the product of the corrosion current to the corrosion area, wherein the area is the sample contact ring of the test probe on the test sample connected to the working end of the electrochemical measuring device, which is in contact with the (simulated) solution. The sample area (that is, the area where the sample contacts the ring), not the working area of the counter electrode end (the sample contact ring of the test probe on the sample to be tested connected to the ground terminal of the electrochemical measurement device is in phase with the simulated solution. contact area of the sample to be tested). Its corrosion current density is calculated by the following formula:
ID＝I/sI D = I/s
s＝πR2 s=πR 2
其中，ID为电偶腐蚀电流密度，I为电偶腐蚀电流，s为工作面积，R为测试探头工作圆环半径(试样接触圆环的半径)。Among them, I D is the galvanic corrosion current density, I is the galvanic corrosion current, s is the working area, and R is the working ring radius of the test probe (the radius of the sample contact ring).
当使用多探头进行测试时，其工作面积为与电化学工作装置的工作端所连接的测试探头的总工作面积(即每个试样接触圆环面积之和)。When using multiple probes for testing, the working area is the total working area of the test probes connected to the working end of the electrochemical working device (ie, the sum of the contact area of each sample).
电偶腐蚀行为与腐蚀不均衡性的确定。在计算出电偶腐蚀电流密度之后，我们只是知道了阴极区与阳极区腐蚀速度的差值，即ID＝I阳D-I阴D。虽然通过该值得大小与正负也可以判断出何者为阳极，何者为阴极，以及二者腐蚀速度的差异。但无法知道二者的腐蚀速度的绝对值。然而，通常来讲当两种自腐蚀电位不同的材料发生电偶腐蚀时，电位高的被阴极极化，腐蚀速度下降，电位低的被阳极极化，腐蚀速度上升。当二者的自腐蚀电位差异较大时，可以认为I阳D远大于I阴D，即ID≈I阳D。而当二者的自腐蚀电位差异较小时，应结合极化曲线等测试进行进一步的计算。Determination of Galvanic Corrosion Behavior and Corrosion Inhomogeneity. After calculating the galvanic corrosion current density, we only know the difference between the corrosion rates of the cathode region and the anode region, that is, I D =I positive D -I negative D . Although it is possible to judge which is the anode and which is the cathode through the value and the positive and negative values, and the difference in the corrosion rate of the two. However, the absolute value of the corrosion rate of the two cannot be known. However, in general, when two materials with different self-corrosion potentials undergo galvanic corrosion, the one with high potential is cathodically polarized, and the corrosion rate decreases, and the one with low potential is anodic polarized, and the corrosion rate increases. When the self-corrosion potentials of the two are quite different, it can be considered that I cation D is much larger than I cation D , that is, I D ≈ I cation D . When the difference between the two self-corrosion potentials is small, further calculations should be carried out in combination with tests such as polarization curves.
金属焊接接头腐蚀速度的确定。当二者的自腐蚀电位差异较大时，通过腐蚀电流密度可以计算出金属局部腐蚀的速度大小。Determination of corrosion rate of metal welded joints. When the self-corrosion potentials of the two are quite different, the local corrosion rate of the metal can be calculated by the corrosion current density.
其单位时间反应电量为Q＝tID The reaction charge per unit time is Q= tID
单位时间反应总质量为m＝QM/FnThe total mass of reaction per unit time is m=QM/Fn
其中t为时间，n为反应物与生成物的化合价之差，F＝96500为法拉第常数，M为反应原子摩尔质量。Where t is the time, n is the difference between the valences of the reactants and the products, F=96500 is the Faraday constant, and M is the molar mass of the reacting atoms.
因此腐蚀速度A＝m/tsSo the corrosion rate A=m/ts
其中A单位为g/m2h，s为电极反应面积(即计算腐蚀电流密度时采用的工作面积)。The unit of A is g/m 2 h, and s is the electrode reaction area (that is, the working area used when calculating the corrosion current density).
也可表示称腐蚀深度为B＝(24*365A)/1000dIt can also be expressed that the corrosion depth is B=(24*365A)/1000d
其中B单位为mm/年，d为材料的密度，单位为g/cm3 where B is in mm/year and d is the density of the material in g/ cm3
对上述公式，分别带入ID、I阳D和I阴D即可计算出不同区域的局部腐蚀速度的大小。For the above formula, the size of the local corrosion rate in different regions can be calculated by adding ID, IDD and IDD respectively.
第一焊接接头试样与第一测试探头的工作圆环中溶液的接触部分为工作电极，第二焊接接头试样与第二测试探头的工作圆环中溶液的接触部分为对电极；探头下管中工作圆环的直径选取应以不大于所测定组织的宽度为准，选取直径为5mm；工作圆环与金属试样之间应通过调节磁性固定栓保证紧密接触并做好防漏液工作；探头主体溶液储存腔内应加入焊接接头实验所需的溶液；离子导通管道粗细应与连接孔一致以防止溶液漏出；离子导通管道选择柔性材料(硅胶管)与探头主体内部溶液保持良好接触。The contact part of the first welded joint sample and the solution in the working ring of the first test probe is the working electrode, and the contact part of the second welded joint sample and the solution in the working ring of the second test probe is the counter electrode; The diameter of the working ring in the tube should be no larger than the width of the measured tissue, and the diameter should be 5mm; the magnetic fixing bolt should be adjusted between the working ring and the metal sample to ensure close contact and prevent leakage. ;The solution required for the welding joint experiment should be added to the solution storage cavity of the probe body; the thickness of the ion conduction pipeline should be consistent with the connection hole to prevent the solution from leaking; the ion conduction pipeline should be made of flexible material (silica gel tube) and keep good contact with the solution inside the probe body .
使用本发明的测试探头测试焊接接头不同组织之间的电偶腐蚀的电流的步骤如下：The steps of using the test probe of the present invention to test the current of galvanic corrosion between different tissues of the welded joint are as follows:
(1)将测试探头下管及磁性固定栓连接在探头主体上，并将第一测试探头与第二测试探头分别使用磁性固定栓使工作圆环吸附在第一焊接接头与第二焊接接头的不同组织上，本实施例分别测定了热影响区相对于母材区、热影响区相对于焊合区、母材区相对于焊合区的电偶腐蚀电流的大小。故在每组试验下第一测试探头与第二测试探头的工作圆环应吸附在相应的组织处。之后向探头主体的溶液储存腔内加入3.5wt％氯化钠水溶液(海水模拟液)。本实施例中的试样为T4003不锈钢，表面已经过打磨处理，在实验过程中没有发生溶液的漏出，故不需进一步的防漏液措施。注入溶液后再放入密封环并将探头上盖旋紧于探头主体上部，之后将内部含有饱和氯化钾凝胶的硅胶管插入柔性离子导通管道连接孔内，并保证与溶液密切接触，使两个探头间形成离子导通通道。(1) Connect the lower tube of the test probe and the magnetic fixing bolt to the main body of the probe, and use the magnetic fixing bolts for the first test probe and the second test probe respectively so that the working ring is adsorbed on the first welding joint and the second welding joint. For different structures, in this example, the magnitudes of the galvanic corrosion currents of the heat-affected zone relative to the base metal zone, the heat-affected zone relative to the welding zone, and the base metal zone relative to the welding zone were respectively measured. Therefore, under each group of tests, the working rings of the first test probe and the second test probe should be attached to the corresponding tissues. Then, 3.5wt% sodium chloride aqueous solution (seawater simulative solution) was added into the solution storage cavity of the probe body. The sample in this example is T4003 stainless steel, the surface has been polished, and no leakage of the solution occurred during the experiment, so no further anti-leakage measures are required. After injecting the solution, put in the sealing ring and tighten the probe cover to the upper part of the probe body, then insert the silicone tube containing saturated potassium chloride gel into the connection hole of the flexible ion conduction tube, and ensure that it is in close contact with the solution. An ion conduction channel is formed between the two probes.
(2)测试探头与电化学工做站的连接：本实验的连线图如图2所示，图2为热影响区对母材区的电偶腐蚀电流测试的接线图，对其他组织之间的电偶腐蚀电流测试，工作圆环所覆盖的组织应有所不同。值得注意的是：为了得到不同组织之间导通瞬态的腐蚀电流，应保证测试前电化学工作站工作端与第一焊接接头试样接触，并使电化学工作站接地端与第二焊接接头试样断开。当测试开始后，再将电化学工作站接地端与第二焊接接头试样相连接。(2) The connection between the test probe and the electrochemical work station: The connection diagram of this experiment is shown in Figure 2. Figure 2 is the connection diagram of the galvanic corrosion current test of the heat affected zone to the base metal area. Between galvanic corrosion current tests, the tissue covered by the working ring should be different. It is worth noting that: in order to obtain the transient corrosion current between different tissues, it should be ensured that the working end of the electrochemical workstation is in contact with the first welding joint sample before the test, and the grounding end of the electrochemical workstation and the second welding joint test should be ensured. disconnected. When the test is started, connect the ground terminal of the electrochemical workstation to the second welded joint sample.
(3)试验参数的设置：本实验采用上海正方电气有限公司生产的的ZF-100电化学工作站进行瞬态电偶电流测试，扫描频率为20Hz，扫描时间为15分钟。本实验对T4003不锈钢焊接接头试样不同组织之间的电偶腐蚀电流图如图4-图6所示。通过图4-6中稳态电偶腐蚀电流的大小可以得到该材料在该环境下不同组织平均腐蚀速率的差异。(3) Setting of test parameters: In this experiment, ZF-100 electrochemical workstation produced by Shanghai Zhengfang Electric Co., Ltd. was used for transient galvanic current test. The scanning frequency was 20 Hz and the scanning time was 15 minutes. In this experiment, the galvanic corrosion current diagrams between different microstructures of T4003 stainless steel welded joint samples are shown in Figure 4-Figure 6. The difference of the average corrosion rate of the material in different tissues in this environment can be obtained from the magnitude of the steady-state galvanic corrosion current in Figures 4-6.
通过测定计算，不同区域间的稳态电偶腐蚀电流的平均值的计算结果如下表所示：Through measurement and calculation, the calculation results of the average value of the steady-state galvanic corrosion current between different regions are shown in the following table:
在该电偶腐蚀电流测试中，若得到的电流为正值，则代表工作电极的腐蚀速度大于对电极，即为第一测试探头工作圆环所覆盖的区域的腐蚀速度更快。而越大的电偶腐蚀电流的值代表腐蚀速度的差异越大。由此，我们可以得出三种组织之间腐蚀速度的关系是：热影响区＞母材区＞焊合区。In the galvanic corrosion current test, if the obtained current is a positive value, it means that the corrosion rate of the working electrode is higher than that of the counter electrode, that is, the corrosion rate of the area covered by the working ring of the first test probe is faster. The larger the value of the galvanic corrosion current represents the greater the difference in corrosion rate. From this, we can conclude that the relationship between the corrosion rates of the three structures is: heat-affected zone>base metal zone>welding zone.
测试初期，连通电化学工作站接地端与第二焊接接头的瞬间得到的瞬态电偶腐蚀电流的方向与大小可以判断二者的电位关系与差值。在本实验中，三次测试得到的瞬态电偶腐蚀电流为正值，则可以判断三种组织之间腐蚀电位的关系是：热影响区＜母材区＜焊合区。通过以上关系可知，T4003不锈钢焊接接头不同组织之间耐蚀性的关系为：热影响区＜母材区＜焊合区。In the early stage of the test, the direction and magnitude of the transient galvanic corrosion current obtained at the moment of connecting the grounding end of the electrochemical workstation and the second welding joint can determine the potential relationship and difference between the two. In this experiment, the transient galvanic corrosion current obtained from the three tests is a positive value, and it can be judged that the relationship between the corrosion potentials of the three structures is: heat-affected zone < base metal zone < welding zone. It can be seen from the above relationship that the relationship between the corrosion resistance of different structures of T4003 stainless steel welded joints is: heat-affected zone < base metal zone < welding zone.
以上对本发明进行了详细说明，但所述内容仅为本发明的较佳实施例，不能被认为用于限定本发明的实施范围。凡依本发明申请范围所作的均等变化与改进等，均应仍归属于本发明的专利涵盖范围之内。The present invention has been described in detail above, but the above contents are only preferred embodiments of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made according to the scope of the application of the present invention should still belong to the scope of the patent of the present invention.
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| CN115343211A (en) * | 2022-07-25 | 2022-11-15 | 湖南华菱涟源钢铁有限公司 | Method for detecting corrosion sensitivity of welding joint |
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