A high-throughput method for detecting corrosion resistance of metals

Abstract

The present application relates to the field of corrosion electrochemistry, and discloses a high-throughput detection method for metal corrosion resistance. The present application discloses a distributed multi-channel electrochemical workstation, which comprises an independent multi-channel direct-current test electrochemical workstation and an independent multi-channel alternating-current test electrochemical workstation; and a high-throughput detection method for metal corrosion resistance, which comprises using the distributed multi-channel electrochemical workstation to detect the metal corrosion resistance. The distributed multi-channel electrochemical workstation provided by the present application can effectively avoid the galvanic corrosion phenomenon caused by the wire bundle electrode electrochemical corrosion experiment, and solve the problems of high cost and large space occupation of the traditional independent parallel high-throughput electrochemical corrosion experiment. The high-throughput detection method for metal corrosion resistance provided by the present application can ensure the detection efficiency and greatly reduce the test cost, and can be applied to the high-throughput electrochemical corrosion experiment test of different metal materials.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electrochemical corrosion technology, in particular to a high-throughput detection method for metal corrosion resistance. BACKGROUND

[0002] In marine environment, metal materials are prone to electrochemical corrosion reaction due to surface wetting or direct immersion under the influence of salt mist, humidity, temperature and other factors, which seriously affects the working performance and service life of marine engineering equipment. The research object of existing corrosion characterization technology is usually a single sample and a single solution system, which takes a long time to test and cannot meet the needs of new material development and characterization.

[0003] High-throughput experiment refers to an experimental method that can complete the preparation or characterization of a large number of samples in a short time, the key of which is to prepare or characterize multiple samples in parallel, so as to complete the comprehensive processing of experimental data of multiple materials at the same time. At present, the high-throughput corrosion resistance characterization methods of multiple materials mainly include wire beam electrode high-throughput experiment (WBEHE) and independent parallel high-throughput experiment (IPHE).

[0004] Wire beam electrode technology refers to preparing an array of microelectrodes with different compositions of samples, and obtaining the local corrosion distribution characteristics and non-uniform electrochemical dissolution process of the surface of different composition metals by cyclic scanning the potential and current distribution of the surface of the wire beam electrode. Wire beam electrode technology is widely used in high-throughput corrosion resistance screening, but the size of the wire beam electrode is small (1-3mm), the preparation is complicated and the measurement precision is high. At the same time, due to the use of a set of solution system, the test results of the wire beam electrode cannot effectively avoid the problem of galvanic corrosion, which further causes certain errors in the screening results.

[0005] Independent parallel experiment refers to increasing the number of channels of the electrochemical workstation, and setting each working electrode as an independent environmental parameter condition and electrochemical test condition, which can realize high-throughput in-situ electrochemical test of different metal materials. However, the traditional independent parallel high-throughput experiment requires a large number of electrochemical workstations, occupies a large space, and has high cost. SUMMARY

[0006] The present application aims to at least solve one of the above technical problems in the prior art. To this end, one of the objects of the present application is to provide a distributed multi-channel electrochemical workstation; and the second object of the present application is to provide a high-throughput detection method for metal corrosion resistance.

[0007] To achieve the above object, the technical scheme adopted by the present application is:

[0008] The first aspect of the present application provides a distributed multi-channel electrochemical workstation, which comprises an independent multi-channel direct current test electrochemical workstation and an independent multi-channel alternating current test electrochemical workstation.

[0009] Preferably, the number of channels of the multi-channel direct current test electrochemical workstation and the multi-channel alternating current test electrochemical workstation is determined by an enumeration method or an intelligent optimization algorithm;

[0010] The objective function expression for determining the number of channels is Z = αT + βC;

[0011] The objective function satisfies the following constraint conditions:

[0012] (1) T DC = m * t DC / x;

[0013] (2) T AC = m * t AC / y;

[0014] (3) T = max(T DC , T AC );

[0015] (4) C = p * x + q * y;

[0016] In the formula, m is the number of working electrodes to be measured, i.e.

[0017] x is the number of channels of the multi-channel direct current test electrochemical workstation;

[0018] y is the number of channels of the multi-channel alternating current test electrochemical workstation;

[0019] t DC is the time consumption of direct current test for each working electrode, min;

[0020] t AC is the time consumption of alternating current test for each working electrode, min;

[0021] T DC is the total amount of direct current test time for m working electrodes, min;

[0022] T AC is the total amount of alternating current test time for m working electrodes, min;

[0023] T is the total time of electrochemical experiment test for m working electrodes, min;

[0024] p is the cost of each channel of the multi-channel direct current test electrochemical workstation, ten thousand yuan;

[0025] q is the cost of each channel of the multi-channel alternating current test electrochemical workstation, ten thousand yuan;

[0026] C is the total cost of the electrochemical workstation, ten thousand yuan;

[0027] Z is the weighted sum; and a and β are weight coefficients.

[0028] Preferably, according to the working area, the distributed multi-channel electrochemical workstation comprises a waiting area I, a direct current test waiting area, a direct current test area, an alternating current test waiting area and an alternating current test area connected in sequence.

[0029] Preferably, the waiting area I is used for loading the working electrode into an electrolytic cell and adding an electrolyte solution.

[0030] Preferably, the direct current test waiting area is used for storing the working electrode to be tested through the waiting area I and the working electrode after completing the alternating current test.

[0031] Preferably, the direct current test area is used for direct current test of the working electrode.

[0032] Preferably, the alternating current test area is used for alternating current test of the working electrode.

[0033] Preferably, the alternating current test waiting area is used for storing the working electrode after completing the direct current test.

[0034] The second aspect of the present application provides a high-throughput detection method for metal corrosion resistance, comprising the following steps: using the distributed multi-channel electrochemical workstation of the first aspect of the present application to detect the metal corrosion resistance.

[0035] Preferably, in the distributed multi-channel electrochemical workstation, the multi-channel direct current test electrochemical workstation performs linear polarization method test.

[0036] Preferably, in the distributed multi-channel electrochemical workstation, the multi-channel alternating current test electrochemical workstation performs alternating current impedance method test.

[0037] Preferably, the parameter setting of the multi-channel direct current test electrochemical workstation includes test potential, scan rate and direct current test time consumption of each working electrode.

[0038] Preferably, the test potential is ±20mV vs OC; further preferably, the test potential is ±10mV vs OC.

[0039] Preferably, the scan rate is 0.1-0.5mV / s; further preferably, the scan rate is 0.1-0.3mV / s.

[0040] Preferably, the direct current test of each working electrode takes 2-5 minutes; further preferably, the direct current test of each working electrode takes 2-3 minutes.

[0041] Preferably, the parameter settings of the multi-channel alternating current test electrochemical workstation include a sweep range, an amplitude, and a time consumption of each working electrode alternating current test.

[0042] Preferably, the sweep range is 0.01-100000 Hz.

[0043] Preferably, the amplitude is 8-12 mV; further preferably, the amplitude is 9-10 mV.

[0044] Preferably, the time consumption of each working electrode alternating current test is 15-20 minutes; further preferably, the time consumption of each working electrode alternating current test is 16-18 minutes.

[0045] Preferably, the method specifically comprises the following steps: grouping the working electrodes to be tested, and synchronously feeding the working electrodes of different groups into different workstations for testing according to the maximum capacity of the multi-channel direct current test electrochemical workstation and the multi-channel alternating current test electrochemical workstation.

[0046] Preferably, the expression of the grouping of the working electrodes to be tested is as follows:

[0047] n = min(x, y);

[0048] f = ROUNDUP[m / min(x, y)];

[0049] In the formula, n is the number of working electrodes in each group, units of;

[0050] f is the number of groups, units of;

[0051] ROUNDUP represents an upward rounding function;

[0052] m is the number of working electrodes to be tested, units of;

[0053] x is the number of channels of the multi-channel direct current test electrochemical workstation;

[0054] y is the number of channels of the multi-channel alternating current test electrochemical workstation.

[0055] Compared with the prior art, the present application has the following beneficial effects:

[0056] 1) The distributed multi-channel electrochemical workstation provided by the application splits the direct current test function and the alternating current test function compared with the traditional multi-channel electrochemical workstation, forms a multi-channel direct current test electrochemical workstation and a multi-channel alternating current test electrochemical workstation, and the working electrode alternately performs direct current test and alternating current test, which can effectively avoid the galvanic corrosion phenomenon caused by the electrochemical corrosion experiment of the wire electrode, and solve the problems of high cost and large occupied space of the traditional independent parallel high-throughput electrochemical corrosion experiment;

[0057] 2) The high-throughput detection method of the metal corrosion resistance provided by the application can ensure the detection efficiency and greatly reduce the test cost, and can be applied to high-throughput electrochemical corrosion experiment test of different metal materials. BRIEF DESCRIPTION OF DRAWINGS

[0058] Figure 1 It is a schematic diagram of a traditional multi-channel electrochemical workstation;

[0059] Figure 2 It is a schematic diagram of the distributed multi-channel electrochemical workstation in Example 1;

[0060] Figure 3 It is a schematic diagram of the working state of each region of the distributed multi-channel electrochemical workstation in Example 1 at 0-2.5 min;

[0061] Figure 4 It is a schematic diagram of the working state of each region of the distributed multi-channel electrochemical workstation in Example 1 at 2.5-5 min;

[0062] Figure 5 It is the linear polarization data of the direct current test in Example 1;

[0063] Figure 6 It is the alternating current impedance data of the alternating current test in Example 1. DETAILED DESCRIPTION

[0064] The content of the application will be further described in detail through specific examples. The raw materials, reagents or devices used in the examples and comparative examples can be obtained from conventional commercial channels or can be obtained by the prior art method, unless otherwise specified. Unless otherwise specified, the test or test method is a conventional method in the art.

[0065] In the following examples and comparative examples, the working electrode to be tested is a carbon steel working electrode, the number is 96, and the working electrode is treated by resin packaging, polishing and polishing, and ultrasonic cleaning. The exposed surface is 1cm*1cm; the test conditions are as follows: 3.5% NaCl solution, saturated calomel reference electrode, platinum sheet counter electrode.

[0066] Example 1

[0067] The embodiment detects the corrosion resistance of the carbon steel working electrode in high flux, Figure 1 It is a schematic diagram of a traditional multi-channel electrochemical workstation, each channel has direct current test and alternating current test functions, and is independent of each other and does not interfere with each other. Figure 2 It is a schematic diagram of a distributed multi-channel electrochemical workstation in Example 1, which includes a multi-channel direct current test electrochemical workstation ( Figure 2 (a)) and a multi-channel alternating current test electrochemical workstation ( Figure 2 (b)) which are independent of each other.

[0068] In the distributed multi-channel electrochemical workstation, the multi-channel direct current test electrochemical workstation performs linear polarization method test, sets the test potential to ±20mV vs OC, the scanning rate is 0.1667mV / s, and the test time is 2.5min per working electrode; the multi-channel alternating current test electrochemical workstation performs alternating current impedance method test, sets the frequency scanning range to 100000Hz to 0.01Hz, the amplitude to 10mV, and the test time to 17min per working electrode.

[0069] The cost of the multi-channel direct current test electrochemical workstation is 20,000 yuan per channel, the cost of the multi-channel alternating current test electrochemical workstation is 20,000 yuan per channel, and the objective function expression of the number of channels is Z=αT+βC, and the constraint conditions are:

[0070] (1) The total amount of direct current test time (min): T DC =96*2.5 / x;

[0071] (2) The total amount of alternating current test time (min): T AC =96*17 / y;

[0072] (3) The total electrochemical test time (min): T=max(T DC , T AC );

[0073] (4) The total cost of the electrochemical workstation (10,000 yuan): C=2*x+2*y;

[0074] Set the weight coefficient α=β=1, that is, consider the cost and efficiency comprehensively, then the objective function is Z=T+C, and the optimal number of multi-channel direct current test electrochemical workstation channels x=4 and the optimal number of multi-channel alternating current test electrochemical workstation channels y=24 are obtained by enumeration method.

[0075] That is, the total amount of direct current test time of 96 carbon steel working electrodes is 60min, the total amount of alternating current test time is 68min, the total electrochemical test time is 68min, and the total cost of the electrochemical workstation is 560,000 yuan.

[0076] The specific test process is: 96 carbon steel working electrodes are grouped, and the expression is:

[0077] n = min(4, 24), f = ROUNDUP [96 / (4, 24)], that is, 96 working electrodes are divided into 24 groups according to 4 each, and numbered a-x.

[0078] The distributed multi-channel electrochemical workstation is divided into five areas: direct current test area, alternating current test area, waiting area I, direct current test waiting area and alternating current test waiting area. The linear polarization test is carried out in the direct current test area, about 2.5 min / group, and 1 group is tested each time. The alternating current impedance test is carried out in the alternating current test area, about 17 min / group, and 6 groups are tested simultaneously each time; the waiting area I is used to load the working electrode into the electrolytic cell and add electrolyte solution, about 2.5 min / group, and 1 group is tested each time; the direct current test waiting area is used to store new working electrodes after the waiting area I and working electrodes after the alternating current test; the alternating current test waiting area is used to store working electrodes after the direct current test; the test numbers of each period and each area are shown in Table 1.

[0079] The specific test process is described as follows:

[0080] 0-2.5min: Working electrode group a performs direct current test, groups b-g perform alternating current test simultaneously, group i enters the waiting area I to load the cell and add electrolyte, and group h enters the direct current test waiting area to queue for direct current test, Figure 3 The working state of each area of the distributed multi-channel electrochemical workstation in Example 1 at 0-2.5min is shown in Figure 1;

[0081] 2.5-5min: Working electrode group h performs direct current test, groups b-g perform alternating current test simultaneously, group j enters the waiting area I to load the cell and add electrolyte, group i enters the direct current test waiting area to queue for direct current test, and group a enters the alternating current test waiting area to queue for alternating current test, Figure 4 The working state of each area of the distributed multi-channel electrochemical workstation in Example 1 at 2.5-5min is shown in Figure 2;

[0082] This cycle is repeated, and the corrosion resistance test of 96 carbon steel working electrodes is completed according to the test numbers of each period and each area in Table 1, and the test data is obtained, wherein, Figure 5 The linear polarization data of the direct current test in Example 1 is shown in Figure 3, Figure 6 The alternating current impedance data of the alternating current test in Example 1 is shown in Figure 4.

[0083] Table 1 Test numbers of each period and each area of the distributed multi-channel electrochemical workstation in Example 1

[0084]

[0085] Comparative Example 1

[0086] The corrosion resistance of 96 working electrodes was tested by using a 1-channel array electrode electrochemical scanning system through the wire beam electrode technology.

[0087] Comparative Example 2

[0088] The corrosion resistance of 96 working electrodes was tested by using a 96-channel full-function electrochemical workstation through the traditional independent parallel high-throughput experiment method.

[0089] Table 2 is a comparison of the three high-throughput electrochemical corrosion experiment methods in Example 1 and Comparative Examples 1 and 2. As shown in Table 2, the corrosion resistance of 96 working electrodes was tested by using the distributed multi-channel electrochemical workstation and the high-throughput detection method of metal corrosion resistance provided in the application in Example 1, and the direct current test and alternating current test were performed by using the independent multi-channel direct current test electrochemical workstation and the multi-channel alternating current test electrochemical workstation, the total test time was 68 min, the test flux was 84.7 / h, and the construction cost of the electrochemical workstation was 560,000 yuan; in Comparative Example 1, the traditional wire beam electrode technology was used, and a 1-channel array electrode electrochemical scanning system was used, the cost of the electrochemical workstation was low, only 40,000 yuan, but the total test time was 1634.5 min, the efficiency was low, and since a set of solution system was shared, the test results of the wire beam electrode could not effectively avoid the problem of galvanic corrosion; in Comparative Example 2, the traditional independent parallel high-throughput experiment method was used, and a 96-channel full-function electrochemical workstation was used, and the test could be completed in 19.5 min, but the cost of the electrochemical workstation was as high as 3,840,000 yuan, which was expensive, and the occupied area was large.

[0090] Table 2 is a comparison of the three high-throughput electrochemical corrosion experiment methods in Example 1 and Comparative Examples 1 and 2. As shown in Table 2, the corrosion resistance of 96 working electrodes was tested by using the distributed multi-channel electrochemical workstation and the high-throughput detection method of metal corrosion resistance provided in the application in Example 1, and the direct current test and alternating current test were performed by using the independent multi-channel direct current test electrochemical workstation and the multi-channel alternating current test electrochemical workstation, the total test time was 68 min, the test flux was 84.7 / h, and the construction cost of the electrochemical workstation was 560,000 yuan; in Comparative Example 1, the traditional wire beam electrode technology was used, and a 1-channel array electrode electrochemical scanning system was used, the cost of the electrochemical workstation was low, only 40,000 yuan, but the total test time was 1634.5 min, the efficiency was low, and since a set of solution system was shared, the test results of the wire beam electrode could not effectively avoid the problem of galvanic corrosion; in Comparative Example 2, the traditional independent parallel high-throughput experiment method was used, and a 96-channel full-function electrochemical workstation was used, and the test could be completed in 19.5 min, but the cost of the electrochemical workstation was as high as 3,840,000 yuan, which was expensive, and the occupied area was large.

[0091]

[0092] The distributed multi-channel electrochemical workstation and the high-throughput detection method of metal corrosion resistance provided in the application greatly shorten the detection time compared with the traditional wire beam electrode technology, overcome the problem of galvanic corrosion, and the cost investment is within an acceptable range; compared with the traditional independent parallel high-throughput experiment method, the cost and space of the electrochemical workstation are greatly reduced, and the increase in detection time is also within an acceptable range. That is, in terms of detection efficiency and cost, the practicality of the distributed multi-channel electrochemical workstation and the high-throughput detection method of metal corrosion resistance provided in the application is much higher than that of the traditional wire beam electrode technology and the independent parallel high-throughput experiment method, and it can be applied to high-throughput electrochemical corrosion experiment testing of different metal materials, and better meet the needs of new material development and characterization.

Claims

1. A distributed multi-channel electrochemical work station, characterized by, The distributed multi-channel electrochemical workstation comprises an independent multi-channel direct current test electrochemical workstation and an independent multi-channel alternating current test electrochemical workstation; According to the working area, the distributed multi-channel electrochemical workstation comprises a waiting area I, a direct current test waiting area, a direct current test area, an alternating current test waiting area and an alternating current test area connected in sequence; The number of channels of the multi-channel direct current test electrochemical workstation and the multi-channel alternating current test electrochemical workstation is determined by an enumeration method or an intelligent optimization algorithm; The objective function expression for determining the number of channels is: Z = αT + βC ; The objective function satisfies the following constraint conditions: In the formula: m is the number of working electrodes to be measured, pieces; x Number of channels for multi-channel DC test electrochemical workstations; y Number of channels for multi-channel AC test electrochemical workstations; t DC Time taken for each working electrode direct current test, min; t AC Time taken for each working electrode AC test, min; T DC for m total amount of direct current test time for one working electrode, min; T AC for m total amount of alternating current test time for one working electrode, min; T For m Total time of electrochemical experiment test for one working electrode, min; p The cost of each channel of the multi-channel direct current test electrochemical workstation is 10,000 yuan; q For multi-channel alternating current test electrochemical workstation, each channel cost 10,000 yuan; C Total cost of electrochemical workstation, 10,000 yuan; Z is a weighted sum; α、β is a weight coefficient.

2. A method for high-throughput detection of corrosion resistance of metals, characterized in that, The method comprises the following steps: using the distributed multi-channel electrochemical workstation of claim 1 to detect the metal corrosion resistance.

3. The high-throughput assay method of claim 2, wherein, In the distributed multi-channel electrochemical workstation, the multi-channel direct current test electrochemical workstation performs linear polarization method test.

4. The high-throughput assay method of claim 2, wherein, In the distributed multi-channel electrochemical workstation, the multi-channel alternating current test electrochemical workstation performs alternating current impedance method test.

5. The high-throughput assay method of claim 3, wherein, The parameter setting of the multi-channel direct current test electrochemical workstation comprises test potential, scanning rate and direct current test time of each working electrode; the test potential is ± 20 mV vs. OC; the scanning rate is 0.1-0.5 mV / s; and the direct current test time of each working electrode is 2-5 min.

6. The high-throughput assay method of claim 4, wherein, The parameter setting of the multi-channel alternating current test electrochemical workstation comprises frequency scanning range, amplitude and alternating current test time of each working electrode; the frequency scanning range is 0.01-100000 Hz; the amplitude is 8-12 mV; and the alternating current test time of each working electrode is 15-20 min.

7. The high-throughput assay method according to any one of claims 2 to 6, wherein, The method specifically comprises the following steps: grouping the working electrodes to be tested, and making different groups of working electrodes enter different workstations for test simultaneously according to the maximum capacity of the multi-channel direct current test electrochemical workstation and the multi-channel alternating current test electrochemical workstation.

8. The high-throughput assay method of claim 7, wherein, The expression of the grouping of the working electrodes to be tested is as follows: n = min( x , y ); f = ROUNDUP [ m / min( x , y )] In the formulae: n is the number of working electrodes for each group; f For the number of groups, group; ROUNDUP represents a ceiling function; m n is the number of working electrodes to be measured, and x Number of channels for multi-channel DC test electrochemical workstations; y The number of channels for a multi-channel alternating current test electrochemical workstation.

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