Metal corrosion measuring device and measuring method

Abstract

The invention provides a metal corrosion measuring device which comprises a circulating mechanism which comprises a storage bottle containing fluid and a water bath kettle connected with the storage bottle, and an experimental mechanism which comprises a circulating pool connected with the storage bottle and the water bath kettle through guide pipes and a metal rod vertically arranged in the circulating pool, and the ultrasonic transmitter is connected with the circulating pool. In addition, the invention also discloses a determination method.

Description

Technical Field

[0001] The present invention relates to the technical field of hazardous chemical testing, and particularly to a metal corrosion determination device and a determination method. Background Art

[0002] Hazardous chemicals refer to highly toxic chemicals and other chemicals with properties such as toxicity, corrosion, explosion, combustion, and combustion support, which are harmful to humans, facilities, and the environment. According to the Globally Harmonized System of Classification and Labelling of Chemicals, a series of standards for chemical hazard classification and labelling specifications, "Chemical Classification and Standard Specifications", have been developed, and a chemical hazard classification system has been established. Currently, in terms of major hazard categories, the hazards of chemicals are divided into 3 major categories and 28 subcategories, namely physical hazards (16 categories), health hazards (a total of 10 categories), and environmental hazards (a total of 2 categories). Among them, metal corrosivity belongs to one of the physical hazards, which refers to the property of significantly damaging or even destroying metals through chemical reactions and is one of the necessary items for the identification of the physical hazards of liquids.

[0003] Currently, according to the traditional coupon method based on GB / T 21621-2008 "Test Method for Metal Corrosivity of Dangerous Goods", this experiment requires up to 1.5 L of liquid to conduct coupon experiments on 3 metal sheets (with dimensions of 50 mm * 20 mm * 2 mm) at different immersion levels (full immersion, half immersion, and exposure to the atmosphere). Two types of metal sheets, steel sheets and aluminum sheets, need to be selected, resulting in a total liquid demand of more than 3 L, thus causing serious waste. Especially when the chemicals produced by some manufacturers are expensive and difficult to provide so many samples, the experiment is difficult to carry out. This experiment also requires a reaction at 55 °C for 168 hours, with a long cycle and poor timeliness, which is not conducive to the rapid output of the identification results. At the same time, this experimental equipment also requires external connection of condensed water, resulting in a large amount of waste. In addition, since the existing experiments mainly rely on methods such as weighing, vernier caliper measurement, and metallography to determine the degree of metal corrosion, it is difficult to deal with metal corrosion caused by displacement reactions, etc. For example, the displacement corrosion of copper sulfate on the coupon, after the reaction, copper covers the inside and surface of the iron sheet, and the total weight actually increases and the thickness also increases to a certain extent. All in all, the current methods have problems such as large sample consumption, waste of water resources, too long determination time, and difficulty in dealing with special situations for the determination method.

[0004] CN102419293B provides a method for rapidly detecting the corrosivity of chemicals by controlling the reaction temperature using microwave radiation. After cleaning and drying a standard test metal sheet, it is suspended in a reactor, and the reactor is placed in a microwave heating device and heated for 10 - 30 h. After the reaction time ends, the metal sheet is taken out, and the corrosive hazard of the corrosive liquid to the metal sheet is judged based on the mass change before and after corrosion. Although this device can reduce the reaction time, there are certain safety risks in placing the metal sheet in the microwave reaction device, and it is very likely to generate electric sparks, which may cause hazards such as combustion and explosion.

[0005] CN102095661B provides a micro metal corrosivity test device, which consists of a cup-shaped water bath glass container and a U-shaped glass tube. Rubber stoppers are provided on the water bath glass container and the U-shaped glass tube. An electric heating rod and a water bath temperature sensor connected to a temperature control device are fixed on the rubber stopper of the water bath glass container. A steam condenser tube, a metal sheet liftable hook, and a reaction container temperature sensor are fixed on the rubber stopper of the U-shaped glass tube. Essentially, this device only reduces the usage amount of the sample, but still needs to use a metal sheet of 50mm * 20mm * 2mm, which is very likely to cause the premature depletion of the corrosive components in the sample, resulting in false negative results. In addition, the position of the liquid seal point in this device is too low, making it difficult for the generated steam to be condensed through the liquid seal, so the metal radiator actually does not play a role.

[0006] CN211505145U provides a micro metal corrosivity tester: including a housing composed of an upper cover and a lower cover. The upper cover includes a front side plate and a top plate connected to each other. The lower cover includes a left side plate, a right side plate, a rear side plate, and a bottom plate connected to each other. An electric heating element is arranged in the inner cavity of the housing. A fixed sleeve is fixedly arranged on the upper surface of the top plate of the upper cover. A through hole is opened at the center position of the fixed sleeve on the top plate of the upper cover. The heating base passes through the fixed sleeve and the through hole of the upper cover and is connected to the electric heating element; the reagent cup passes through the heating base and abuts against the electric heating element. A clamping platform is arranged on the heating base. A transparent glass cover is sleeved on the outer surface of the upper half of the heating base and placed on the clamping platform. The height of the top of the transparent glass cover is greater than the height of the top of the heating base. When the total mass of the metal rod in this device becomes smaller, there will be a problem of increased error when using the weighing method, which is not conducive to the determination of the corrosion degree. In addition, this test equipment can only test one metal rod at a time, and six identical devices are required to conduct experiments simultaneously for seven days at a time, and it cannot cope with the situation of simultaneous determination of a large number of samples.

[0007] Therefore, in this field, it is desired to provide a metal corrosion determination device to solve the above technical problems. Summary of the Invention

[0008] The object of the present invention is to provide a metal corrosion measurement device which can use a smaller volume of metal and a smaller amount of sample liquid, so as to achieve the same mass loss rate as that generated by the traditional coupon method. In addition, a measurement method is also provided.

[0009] According to a first aspect of the present invention, there is provided a metal corrosion measurement device, comprising a circulation mechanism which includes a storage bottle containing a fluid,

[0010] an experiment mechanism which includes a circulation pool connected to the storage bottle through a conduit, a metal rod vertically arranged in the circulation pool, and an ultrasonic transmitter connected to the circulation pool,

[0011] wherein, the circulation pool includes a pool body, a top cover arranged at the upper end surface of the pool body, and ultrasonic emission heads symmetrically arranged on the outer wall of the pool body and used for connecting to the ultrasonic transmitter.

[0012] In one embodiment, the metal rod is configured as a square structure, and the experiment mechanism further includes a clamping group composed of a pair of clamping and guiding parts arranged at the diagonals of the metal rod, and a gap is left between the clamping and guiding parts and the metal rod.

[0013] In one embodiment, at least three such clamping groups are arranged along the axial direction of the pool body, and adjacent clamping groups are distributed in a circumferentially offset manner.

[0014] In one embodiment, a receiving chamber allowing the fluid to pass through is formed in the pool body,

[0015] the experiment mechanism further includes a first screen arranged in the pool body and used for supporting the metal rod, a second screen arranged in the top cover, and an inlet radially arranged on the pool body and communicating with the receiving chamber, wherein the inlet is located below the first screen.

[0016] In one embodiment, a first outlet connected to the conduit and used for guiding the liquid in the receiving chamber is provided at the top end of the top cover.

[0017] In one embodiment, a second outlet connected to the conduit and used for guiding the gas in the receiving chamber is provided at the top end of the top cover.

[0018] In one embodiment, the experiment mechanism further includes a plug fixed on the top cover, and a third outlet radially arranged in the middle of the pool body and used for guiding the liquid in the receiving chamber, wherein the third outlet communicates with the receiving chamber.

[0019] In one embodiment, the circulation mechanism further includes a peristaltic pump disposed between the storage bottle and the circulation pool, and pump tubes disposed between the peristaltic pump and the storage bottle and the circulation pool. Wherein, the peristaltic pump is configured to be able to cause the liquid to flow over the surface of the metal rod in a laminar flow manner, and both the conduit and the pump tube are configured as fluororubber peristaltic pump tubes.

[0020] In one embodiment, the storage bottle includes a bottle cap made of polyvinylidene fluoride film and a bottle body made of borosilicate glass.

[0021] In one embodiment, the metal corrosion measuring device further includes a water bath for heating the fluid in the pump tube, a temperature controller for adjusting the liquid temperature in the water bath, and a measuring device for measuring the iron ion content in the liquid in the storage bottle.

[0022] In one embodiment, the output power of the ultrasonic transmitting head is in the range of 0.1 to 0.4 W.

[0023] According to a second aspect of the present invention, there is provided a measuring method using the metal corrosion measuring device as described above, including the following steps:

[0024] S1. Measure the initial content C0 of iron ions in the liquid in the storage bottle through the measuring device; take three metal rods with a mass of M0 and place them in different circulation pools respectively; heat the fluid in the pump tube through the water bath (12);

[0025] S2. Promote the circulation of the fluid in the circulation pool through the peristaltic pump, and the metal rods are respectively fully immersed, half immersed and suspended relative to the liquid level of the fluid; apply ultrasound to the circulation pool through the ultrasonic emitter;

[0026] S3. Stop the reaction, measure the iron ion content Ct in the liquid through the measuring device, and calculate the mass loss of the metal rod through w%=(Ct - C0)*V / M0×100%.

[0027] Compared with the prior art, the advantages of the present invention are as follows:

[0028] First, the present invention uses ultrasound to accelerate the corrosion reaction rate in the circulation pool. Specifically, the present invention symmetrically distributes four ultrasonic transmitting heads on both sides of the pool body, that is, two ultrasonic transmitting heads are arranged on each side of the pool body. In this way, the ultrasound emitted by the ultrasonic transmitting heads can quickly spread throughout the pool body, thereby effectively increasing the metal corrosion rate to achieve the purpose of reducing the corrosion reaction time.

[0029] Second, the present invention places square metal rods with their lengths scaled proportionally in a circulation pool, thus solving the problem in the prior art that metal rods need to be suspended and clamped. Specifically, first, the first sieve in the accommodation chamber can provide good support for the support plate; second, there is a gap between the wall surface of each clamping and guiding part in each clamping group and the outer wall surface of the metal rod, so as to ensure that the clamped metal rod can be in an upright state in the circulation pool and the liquid can fully wet the metal rod, further improving the success rate and accuracy of the simulation experiment.

[0030] In addition, since adjacent clamping groups are misaligned in the circumferential direction and there is a gap between the inner wall surface of each clamping and guiding part in each clamping group and the outer wall surface of the metal rod, the fluid has sufficient flow space in the circulation pool, so that it can more easily circulate from bottom to top in the circulation pool (introduced below), which helps to make the metal rod in a fully immersed, semi-immersed or suspended state in the circulation pool.

[0031] In addition, the present invention uses a peristaltic pump to supply liquid, which can promote the liquid (corrosion sample) to flow over the surface of the metal rod in a laminar flow manner in the accommodation chamber of the circulation pool, thereby strengthening mass transfer and weakening the wall effect in the microenvironment, and reproducing the real corrosion situation. Correspondingly, in the above process, the corrosion effect of the liquid (corrosion sample) on the surface of the metal rod will be more uniform. At the same time, due to the circulation flow mode adopted in the present invention, the usage amount of the liquid is greatly reduced.

[0032] Third, the present invention uses an inductively coupled plasma mass spectrometer / optical emission spectrometer (ICP-MS / OES) as the main analysis means to measure and record the iron ion content in the liquid in the storage bottle, so as to achieve precise analysis of the corrosion degree of the metal rod, and at the same time helps to distinguish special corrosion such as substitution corrosion.

[0033] Fourth, the present invention supplies heat by means of water bath heating, thus realizing a constant temperature reaction in the circulation pool. In addition, by means of water bath heating, it is ensured that the liquid circulating into the circulation pool each time can maintain a constant temperature state, so as to increase the speed of metal corrosion and achieve the purpose of reducing the corrosion reaction time.

[0034] Fifth, the storage bottle in the present invention adopts a thin-layer glass heat dissipation design, which can not only be more easily exchanged with air, but also will not lose the total amount of liquid in the storage bottle, and can also achieve the purpose of eliminating the use of condensed water. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The present invention will be described in detail below with reference to the drawings. In the drawings:

[0036] Figure 1The structure of the metal corrosion measuring device according to the present invention is schematically shown;

[0037] Figure 2 A first embodiment of a circulation pool in a metal corrosion measuring device according to the present invention;

[0038] Figure 2a for Figure 2 Partial view at AA in the middle;

[0039] Figure 2b for Figure 2a Partial view at the middle BB;

[0040] Figure 2c for Figure 2a Partial view at CC in the middle;

[0041] Figure 3 A second embodiment of the circulation pool in the metal corrosion measuring device according to the present invention;

[0042] Figure 3a for Figure 3 Partial view at AA in the middle;

[0043] Figure 3b for Figure 3a Partial view at the middle BB;

[0044] Figure 3c for Figure 3a Partial view at CC in the middle.

[0045] In the drawings, the same reference numerals are used for the same components. The drawings are not drawn to scale.

[0046] The meanings of the reference numerals in the accompanying drawings are as follows:

[0047] 11 storage bottle, 111 bottle cap, 112 bottle body, 12 water bath, 13 peristaltic pump, 14 pump tube,

[0048] 21 metal rod, 22 conduit, 23 clamping guide part, 24 first screen, 25 second screen,

[0049] 30 circulation pool, 31 pool body, 311 inlet, 32 top cover, 321 first outlet, 322 second outlet, 323 third outlet, 324 plug, 325 lock, 33 ultrasonic transmitter, 34 containing chamber,

[0050] 40 Ultrasonic transmitter,

[0051] 50 Thermostat. DETAILED DESCRIPTION

[0052] To make the technical solutions and advantages of the present invention clearer and more understandable, the exemplary embodiments of the present invention will be further described in detail below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than an exhaustive list of all embodiments. And without conflict, the embodiments in the present invention and the features in the embodiments can be combined with each other.

[0053] In the description of the present invention, it should be understood that the terms "first" and "second" are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include one or more of such features.

[0054] In the present invention, unless otherwise clearly specified and limited, terms such as "installed", "connected", "connected to", "fixed" and the like should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected, or indirectly connected through an intermediate medium, and it can be the communication inside two components.

[0055] For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0056] The present invention will be further described below with reference to the accompanying drawings.

[0057] As Figure 1 shown, according to the first aspect of the present invention, a metal corrosion measurement device 100 is provided, which includes a circulation mechanism. The circulation mechanism includes a storage bottle 11 containing a fluid. Among them, the storage bottle 11 includes a bottle cap 111 and a bottle body 112.

[0058] Preferably, the bottle body 112 is a thin wall (2 mm) made of borosilicate glass, so that the bottle body 112 can have a good heat dissipation effect, thereby being able to prevent the evaporation of the liquid to achieve the purpose of avoiding the use of condensed water for condensation.

[0059] In one embodiment, 25 ml of liquid (corrosion sample) is usually placed in the bottle body 112.

[0060] Preferably, the bottle cap 111 is made of a semi-permeable polyvinylidene fluoride film (PVDF), which has good waterproof (including most water vapor) and breathable (mainly air) effects to further achieve the purpose of reducing liquid loss.

[0061] In summary, since the storage bottle 11 in the present invention adopts a thin-layer glass heat dissipation design, it can not only be more easily exchanged with air, but also will not lose the total amount of liquid in the storage bottle 11, and can also achieve the purpose of eliminating the use of condensed water.

[0062] According to the present invention, the metal corrosion measurement device 100 further includes an experimental mechanism. As Figure 1 shown, the experimental mechanism includes a circulation pool 30 connected to the storage bottle 11 through a conduit 22.

[0063] In one embodiment, as Figure 1 shown, the circulation pool 30 is configured as a square structure, and includes a pool body 31 and a top cover 32 provided on the upper end surface of the pool body 31. Preferably, the first end of the top cover 32 is hinged to the pool body 31, and the second end of the top cover 32 is hermetically connected to the pool body 31 through a buckle 325 to help provide a closed experimental environment for the simulation experiment.

[0064] Preferably, the circulation pool 30 is made of polytetrafluoroethylene material, so as to significantly improve the service life of the metal corrosion measurement device 100.

[0065] In one embodiment, as Figure 1 shown, the metal corrosion measurement device 100 further includes an ultrasonic emitter 40 connected to the circulation pool 30. Correspondingly, the experimental mechanism further includes ultrasonic emission heads 33 symmetrically arranged on the outer wall of the pool body 31 and used for connecting to the ultrasonic emitter 40.

[0066] Preferably, the ultrasonic emitter 40 can provide sufficient power support for the ultrasonic emission heads 33 through wires, and the ultrasonic emission heads 33 can apply ultrasonic waves into the circulation pool 30, so as to effectively increase the speed of metal corrosion to achieve the purpose of reducing the corrosion reaction time.

[0067] In a specific embodiment of the present invention, a total of four ultrasonic emission heads 33 are provided, and the four ultrasonic emission heads 33 are symmetrically distributed on both sides of the pool body 31, that is, two ultrasonic emission heads 33 are arranged on each side of the pool body 31. In this way, the ultrasonic waves emitted by the ultrasonic emission heads 33 can quickly spread throughout the pool body 31, so as to effectively increase the speed of metal corrosion to achieve the purpose of reducing the corrosion reaction time.

[0068] In one embodiment of the present invention, the output power of the ultrasonic emission heads 33 is in the range of 0.1-0.4W.

[0069] According to the present invention, as Figure 1 、 2cAs shown in FIGS. 3a and 3c, the experimental mechanism further includes a metal rod 21 vertically arranged in the circulation pool 30, and a clamping group composed of a pair of clamping and guiding parts 23 arranged at the diagonals of the metal rod 21. Among them, the clamping and guiding parts 23 are all radially fixed on the inner wall of the circulation pool 30, so as to have a certain clamping effect on the metal rod 21 to ensure that the metal rod 21 can be in an upright state in the circulation pool 30.

[0070] Preferably, there is a gap (0.2 - 0.5 mm) between the wall surface of each clamping and guiding part 23 in the clamping group and the outer wall surface of the metal rod 21, so as to ensure that the clamped metal rod 21 can be in an upright state in the circulation pool 30 (the first screen 24 can play a supporting role for the metal rod 21, which will be introduced below), and further solve a series of problems leading to inaccurate experiments caused by the suspension method in the prior art.

[0071] In one embodiment, at least three clamping groups are arranged along the axial direction of the pool body 31, and the adjacent clamping groups are distributed in a circumferentially staggered manner. Preferably, there is a gap between the inner wall surface of each clamping and guiding part 23 in each clamping group and the outer wall surface of the metal rod 21, so as to ensure that the clamped metal rod 21 can be in an upright state in the circulation pool 30.

[0072] Through the layout mode of the clamping and guiding part 23 in the pool body 31 in the present invention, it can be ensured that the clamped metal rod 21 can be in an upright state in the circulation pool 30, and the liquid can fully infiltrate the metal rod, so as to further improve the success rate and accuracy of the simulation experiment.

[0073] In addition, since the adjacent clamping groups are distributed in a circumferentially staggered manner, and there is a gap between the inner wall surface of each clamping and guiding part 23 in each clamping group and the outer wall surface of the metal rod 21, the fluid has sufficient flow space in the circulation pool 30, so that it can more easily circulate from bottom to top in the circulation pool 30 (which will be introduced below), thus helping to make the metal rod 21 in a fully immersed, semi-immersed or suspended state in the circulation pool 30.

[0074] In addition, since the space between the clamping and guiding part 23 and the metal rod 21 is narrow, the liquid will pass through in a thin layer state, so that less liquid can be used to complete the metal corrosion measurement operation.

[0075] It should be noted that the axial direction referred to in the present invention is the length direction of the circulation pool 30.

[0076] In a preferred embodiment, the metal rod 21 is configured as a square structure.

[0077] In one embodiment, as Figure 1As shown, a receiving chamber 34 allowing fluid passage is formed within the pool body 31. Further, the experimental mechanism further includes a first screen 24 disposed within the pool body 31. Preferably, the first screen 24 is within the receiving chamber 34 and below the metal rod 21, thereby being able to provide good support for the support plate 21.

[0078] Therefore, the metal rod 21 in the present invention can be stably installed within the circulation pool 30 under the combined action of the first screen 24 and the clamping and guiding portion 23, and can always remain upright within the circulation pool 30, further solving a series of problems in the prior art that lead to inaccurate experiments due to the suspension method.

[0079] According to the present invention, as Figure 1 shown, the circulation mechanism further includes a peristaltic pump 13 disposed between the storage bottle 11 and the circulation pool 30. In the present invention, the method of supplying liquid by the peristaltic pump 13 can cause the liquid to flow over the surface of the metal rod 21 in a laminar flow manner within the receiving chamber 34 of the circulation pool 30, thereby strengthening mass transfer and weakening the wall effect in the microenvironment to reproduce the real corrosion situation. In addition, during the above process, the corrosion effect of the liquid on the surface of the metal rod 21 will be more uniform, and at the same time, due to the use of the circulation flow method in the present invention, the usage amount of the liquid is significantly reduced.

[0080] In one embodiment, as Figure 1 shown, the circulation mechanism further includes a pump tube 14 disposed between the peristaltic pump 13 and the storage bottle 11 and the circulation pool 30. In the present invention, both the conduit 22 and the pump tube 14 are made of fluororubber peristaltic pump tubes, and thus have good corrosion resistance, thereby being able to increase the service life of the metal corrosion measurement device 100.

[0081] In one embodiment, as Figure 1 shown, the metal corrosion measurement device 100 further includes a water bath 12 for heating the fluid within the pump tube 14, and a temperature controller 50 for adjusting the liquid temperature within the water bath 12. It is easy to understand that the present invention heats the pump tube 14 through the water bath 12 to ensure that the fluid entering the circulation pool 30 can have a stable temperature.

[0082] The present invention supplies heat through the water bath heating method, thereby realizing a constant temperature reaction within the circulation pool 30. In addition, through the water bath heating method, it is ensured that the liquid circulating into the circulation pool 30 each time can maintain a constant temperature state, thereby being able to increase the speed of metal corrosion to achieve the purpose of reducing the corrosion reaction time.

[0083] Preferably, the temperature controller 50 in the present invention can ensure that the liquid within the water bath 12 is maintained at a constant temperature of 55 °C.

[0084] In one embodiment, asFigure 1 As shown, the experimental mechanism further includes an inlet 311 radially provided on the pool body 31 and communicating with the accommodation chamber 34. Preferably, the storage bottle 11 can input fluid (liquid and gas) into the accommodation chamber 34 in the circulation pool 30 through the peristaltic pump 13 and the pump tube 14, and can be discharged through the outlets (i.e., the first outlet 321, the second outlet 322, and the third outlet 323 in the following text) to achieve the purpose of circulating flow, thereby effectively increasing the speed of metal corrosion to achieve the purpose of reducing the corrosion reaction time.

[0085] In a specific embodiment of the present invention, the inlet 311 is located below the first screen 24.

[0086] Preferably, the first screen 24 can not only uniformly divert the circulating fluid injected into the circulation pool 30 through the inlet 311 to shorten the contact time between the fluid and the metal rod 21 and increase the speed of metal corrosion, thereby achieving the purpose of reducing the corrosion reaction time; but also can cooperate with the clamping and diversion part 23 to play a good supporting role for the metal rod 21, so that the metal rod 21 can always be in an upright state in the circulation pool 30.

[0087] In one embodiment, as Figure 1 shown, the experimental mechanism further includes a second screen 25 provided in the top cover 32. Preferably, the second screen 25 is configured to disperse the circulating fluid, so as to promote the fluid to be discharged from the circulation pool 30 at a faster speed, thereby increasing the circulation rate of the fluid in the metal corrosion measurement device 100 and further increasing the speed of metal corrosion to achieve the purpose of reducing the corrosion reaction time.

[0088] In one embodiment, as Figure 1 shown, the metal corrosion measurement device 100 further includes a measurement device (not shown) for measuring the iron ion content in the liquid in the storage bottle 11. The measurement device includes an inductively coupled plasma mass spectrometer and an emission spectrometer. Preferably, the present invention uses an inductively coupled plasma mass spectrometer / emission spectrometer (ICP-MS / OES) to measure and record the iron ion content in the liquid in the storage bottle 11, thereby helping to calculate the loss mass of the metal rod 21 after the experiment.

[0089] Preferably, the present invention mainly aims at the problems of large sample consumption, water resource waste, long measurement time, and difficulty in dealing with special situations in the current metal corrosion measurement method.

[0090] Combined with Figure 1 、 2 ~2c and 3~3c shown, in the present invention, the corrosion conditions of the metal rod 21 in three different situations are simultaneously simulated.

[0091] The first case: The metal rod 21 is in a fully immersed state relative to the liquid level in the storage bottle 11.

[0092] In one embodiment, at the top end of the top cover 32, there is a first outlet 321 connected to the conduit 22 and used to guide the liquid in the circulation pool 30. In this way, the liquid in the storage bottle 11 can enter through the inlet 311 below the pool body 31 and be discharged through the first outlet 321 above the pool body 31, so as to achieve the purpose of circulating the liquid flow, further improve the speed of metal corrosion, and achieve the purpose of reducing the corrosion reaction time.

[0093] The second case: The metal rod 21 is in a suspended state in the storage bottle 11.

[0094] In one embodiment, at the top end of the top cover 32, there is a second outlet 322 connected to the conduit 22 and used to guide the gas in the circulation pool 30. In this embodiment, the gas in the storage bottle 11 can enter through the inlet 311 below the pool body 31 and be discharged through the second outlet 322 above the pool body 31, so as to achieve the purpose of circulating flow, further improve the speed of metal corrosion, and achieve the purpose of reducing the corrosion reaction time.

[0095] The third case: The metal rod 21 is in a semi-immersed state relative to the liquid level in the storage bottle 11.

[0096] In one embodiment, the experimental mechanism further includes a plug 324 fixed on the top cover 32, and a third outlet 323 radially arranged in the middle of the pool body 31 and used to guide the liquid in the circulation pool 30. Among them, the third outlet 323 is communicated with the accommodation chamber 34 in the circulation pool 30.

[0097] In this embodiment, the liquid in the storage bottle 11 can enter through the inlet 311 below the pool body 31 and be discharged through the third outlet 323 in the middle of the pool body 31, so as to achieve the purpose of circulating flow, further improve the speed of metal corrosion, and achieve the purpose of reducing the corrosion reaction time. Since the third outlet 323 is in the middle of the pool body 31, the liquid can only contact with part of the metal rod 21 for corrosion reaction.

[0098] In one embodiment, the metal rod 21 in the present invention is configured as a square metal bar scaled proportionally by length, height, etc., so that it can be smoothly placed in the circulation pool 30.

[0099] Preferably, the metal rod 21 in the present invention has a length, width and height of 2mm×2mm×5mm, and the total corrosion volume is 20mm 3 , and the maximum corrosion surface area is 48mm 2In the prior art, the metal size of the traditional coupon method is usually 50mm×20mm×2mm, and the total corrosion volume is 2000mm 3 , and the maximum corrosion surface area is 2280mm 2 .

[0100] It can be seen that the ratio of the total corrosion volume of the metal rod 21 used in the present invention to the corrosion volume of the metal in the traditional method in the prior art is 1:100, and the ratio of the corrosion area of the metal rod 21 used in the present invention to the corrosion area of the metal in the traditional method in the prior art is 1:47.5. Obviously, using the present invention will greatly save the amount of metal used when the two are compared.

[0101] In one embodiment, the storage bottle 11 in the present invention contains 25 ml of liquid (corrosion sample, such as dilute sulfuric acid), so a total of 75 ml of liquid is used in the three storage bottles 11. In the prior art, the traditional method cannot achieve recycling, so the amount of liquid used at one time needs about 1.5 L. It can be seen that the ratio of the liquid usage in the present invention to the liquid usage in the traditional method in the prior art is 1:20. Obviously, using the present invention will greatly save the amount of liquid (corrosion sample) used when the two are compared.

[0102] In addition, since the corrosion area or volume of the metal rod 21 in the present invention is much smaller than that of the metal in the traditional method in the prior art, and since the present invention adopts the method of circulating liquid, it can ensure that the storage bottle 11 can provide sufficient liquid for the circulation pool 30 during the corrosion reaction process.

[0103] According to the second aspect of the present invention, there is provided a measurement method using the metal corrosion measurement device as described above, including the following steps:

[0104] First, inject a liquid (such as dilute sulfuric acid) with a volume V into three different storage bottles 11 respectively.

[0105] Then, measure the initial content C0 of iron ions in the liquid in the storage bottle 11 through a measuring device.

[0106] In other words, use an inductively coupled plasma mass spectrometer / optical emission spectrometer (ICP-MS / OES) to measure the initial content C0 of iron ions in the liquid.

[0107] After that, take three metal rods 21 with a mass of M0 and place them in different circulation pools 30 respectively.

[0108] After that, ensure that the liquid temperature in the water bath 12 is maintained at 55 °C through the temperature controller 50, and heat the pump tube 14 through the water bath 12.

[0109] After that, a peristaltic pump 13 is used to promote the circulation of the fluid in the circulation pool 30, and the metal rod 21 is in the fully immersed, semi-immersed, and suspended states relative to the liquid level of the fluid in the circulation pool 30. Meanwhile, ultrasound is applied to the circulation pool 30 through an ultrasound emitter 40.

[0110] After 16 h, the reaction is stopped, and an inductively coupled plasma mass spectrometer / optical emission spectrometer (ICP-MS / OES) is used to measure the content Ct of iron ions in the liquid, and the metal mass loss of this experiment can be calculated through the metal mass loss expression: w% = (Ct - C0) * V / M0 × 100%, where V = 25 ml; M0 = 157.4 ± 0.2 mg.

[0111] Among them, V = 25 ml; M0 = 157.4 ± 0.2 mg.

[0112] The following introduces Example 1 of the present invention: the corrosion experiment of a steel bar (metal rod 21) in a dilute sulfuric acid sample.

[0113] First, when using the metal corrosion measurement device 100 to conduct the metal corrosion test of the steel bar (metal rod 21), there are three series, namely fully immersed, suspended, and semi-immersed. Preferably, 2 full-flow support circulation pools and 1 semi-flow support circulation pool are used for the circulation pool 30 respectively.

[0114] Then, dilute sulfuric acid with a volume V = 25 ml is respectively injected into three different storage bottles 11.

[0115] After that, an inductively coupled plasma mass spectrometer / optical emission spectrometer (ICP-MS / OES) is used to measure the initial content C0 of iron ions in the liquid in the storage bottle 11.

[0116] After that, steel bars with an initial mass m0 of 157.4 ± 0.2 mg, which are uniformly customized, are respectively placed into three different circulation pools 30.

[0117] After that, a thermostat 50 is used to ensure that the temperature of the liquid in the water bath 12 is maintained at 55°C, and the pump tube 14 is heated through the water bath 12.

[0118] After that, a peristaltic pump 13 is used to promote the circulation of dilute sulfuric acid or gas in the circulation pool 30. Meanwhile, ultrasound is applied to the circulation pool 30 through an ultrasound emitter 40 (the power of the ultrasound emitter 40 is controlled at 0.2 W).

[0119] After 16 h, the reaction is stopped, and an inductively coupled plasma mass spectrometer / optical emission spectrometer (ICP-MS / OES) is used to measure the content Ct of iron ions in the liquid, and the metal mass loss of this experiment can be calculated through the metal mass loss expression: w% = (Ct - C0) * V / M0 × 100%, where V = 25 ml; M0 = 157.4 ± 0.2 mg.

[0120] It should be noted that the ultrasonic acceleration method in the present invention is equivalent to the reaction corrosion time of 7 days in the traditional method. In the present invention, 7d means 7 days.

[0121] The following introduces the second embodiment of the present invention: the corrosion experiment of an aluminum rod (metal rod 21) in a dilute sulfuric acid sample.

[0122] First, when using the metal corrosion measurement device 100 to conduct the metal corrosion test on the aluminum rod (metal rod 21), there are three series, namely full immersion, suspension, and semi-immersion. Preferably, the circulation pool 30 uses 2 full-flow type support circulation pools and 1 semi-flow type support circulation pool respectively.

[0123] Then, dilute sulfuric acid with a volume V = 25 ml is respectively injected into three different storage bottles 11.

[0124] After that, an inductively coupled plasma mass spectrometer / optical emission spectrometer (ICP-MS / OES) is used to measure the initial content C0 of aluminum ions in the liquid in the storage bottle 11.

[0125] After that, aluminum strips with a unified initial mass M0 of 54.0 ± 0.2 mg are respectively placed into three different circulation pools 30.

[0126] After that, the temperature controller 50 is used to ensure that the temperature of the liquid in the water bath 12 is maintained at 55 °C, and the pump tube 14 is heated through the water bath 12.

[0127] After that, a peristaltic pump 13 is used to promote the circulation of dilute sulfuric acid or gas in the circulation pool 30. At the same time, ultrasonic waves are applied to the circulation pool 30 through the ultrasonic emitter 40 (the power of the ultrasonic emitter 40 is controlled at 0.2 W).

[0128] After 16 h, the reaction is stopped, and an inductively coupled plasma mass spectrometer / optical emission spectrometer (ICP-MS / OES) is used to measure the content Ct of aluminum ions in the liquid. And through the metal mass loss expression: w% = (Ct - C0) * V / M0 × 100%, the metal mass loss of this experiment can be calculated.

[0129] The following introduces the third embodiment of the present invention: the corrosion experiment of a steel rod (metal rod 21) in a dilute copper sulfate sample.

[0130] First, when using the metal corrosion measurement device 100 to conduct the metal corrosion test on the steel rod (metal rod 21), there are three series, namely full immersion, suspension, and semi-immersion. Preferably, the circulation pool 30 uses 2 full-flow type support circulation pools and 1 semi-flow type support circulation pool respectively.

[0131] Then, dilute copper sulfate with a volume V = 25 ml is respectively injected into three different storage bottles 11.

[0132] Afterwards, the initial content C0 of iron ions in the liquid in the storage bottle 11 is measured using an inductively coupled plasma mass spectrometer / optical emission spectrometer (ICP-MS / OES).

[0133] Afterwards, steel bars with a unified initial mass m0 of 157.4 ± 0.2 mg are respectively placed into three different circulation pools 30.

[0134] Afterwards, a thermostat 50 is used to ensure that the temperature of the liquid in the water bath 12 is maintained at 55°C, and the pump tube 14 is heated through the water bath 12.

[0135] Afterwards, a peristaltic pump 13 is used to promote the circulation of dilute copper sulfate or gas in the circulation pool 30. Meanwhile, ultrasonic waves are applied to the circulation pool 30 through an ultrasonic emitter 40 (the power of the ultrasonic emitter 40 is controlled at 0.2 W).

[0136] After 16 h, the reaction is stopped. The content Ct of iron ions in the liquid is measured using an inductively coupled plasma mass spectrometer / optical emission spectrometer (ICP-MS / OES), and the metal mass loss of this experiment can be calculated through the metal mass loss expression: w% = (Ct - C0) * V / M0 × 100%.

[0137] The following introduces Example 4 of the present invention: the corrosion experiment of a steel bar (metal bar 21) of a dilute acetic acid sample.

[0138] First, when using the metal corrosion measurement device 100 to conduct the metal corrosion test of the steel bar (metal bar 21), there are three series, namely full immersion, suspension, and semi-immersion. Preferably, 2 full-flow type support circulation pools and 1 semi-flow type support circulation pool are respectively used for the circulation pool 30. (For the full-flow type support circulation pool, the fluid in the storage bottle 11 enters through the inlet 311 below the pool body 31 and is discharged through the first outlet 321 or the second outlet 322 above the pool body 31 to achieve the purpose of circulating flow; for the semi-flow type support circulation pool, the liquid in the storage bottle 11 can enter through the inlet 311 below the pool body 31 and is discharged through the third outlet 323 in the middle of the pool body 31 to achieve the purpose of circulating flow).

[0139] Then, dilute acetic acid with a volume V = 25 ml is respectively injected into three different storage bottles 11.

[0140] Afterwards, the initial content C0 of iron ions in the liquid in the storage bottle 11 is measured using an inductively coupled plasma mass spectrometer / optical emission spectrometer (ICP-MS / OES).

[0141] Afterwards, steel bars with a unified initial mass m0 of 157.4 ± 0.2 mg are respectively placed into three different circulation pools 30.

[0142] After that, the temperature controller 50 is used to ensure that the liquid temperature in the water bath 12 is maintained at 55 °C, and the pump tube 14 is heated by the water bath 12.

[0143] After that, the peristaltic pump 13 is used to promote the circulation of dilute acetic acid or gas in the circulation pool 30. At the same time, ultrasonic waves are applied to the circulation pool 30 by the ultrasonic emitter 40 (the power of the ultrasonic emitter 40 is controlled at 0.2 W).

[0144] After 16 h, the reaction is stopped. The content Ct of iron ions in the liquid is measured by an inductively coupled plasma mass spectrometer / optical emission spectrometer (ICP-MS / OES), and the metal mass loss of this experiment can be calculated through the metal mass loss expression: w% = (Ct - C0) * V / M0 × 100%.

[0145] The following introduces Comparative Example 1 of the present invention: the corrosion experiment of dilute sulfuric acid sample and steel sheet.

[0146] The traditional coupon method is used to test the corrosion of steel sheets by dilute sulfuric acid samples. The specific operation of the traditional coupon method is as follows: a cup-shaped reactor with four necks (not shown) is used. 3 necks are used to hang the steel sheets, and 1 neck is used to connect the external condensed water. 1.5 L of test sample is used, and the reaction is carried out at 55 °C in a water bath for 168 h. The sizes of the 3 metal coupons are all 50 mm * 20 mm * 2 mm, with 3 mm hanging holes. The 3 metals are respectively hung in the cup-shaped reactor with polytetrafluoroethylene wires, showing full immersion, semi-immersion and suspended states.

[0147] The following introduces Comparative Example 2 of the present invention: the corrosion experiment of dilute sulfuric acid sample and aluminum sheet.

[0148] The specific operation method is the same as that of Comparative Example 1, and the steel sheet is replaced by an aluminum sheet in this example.

[0149] The following introduces Comparative Example 3 of the present invention: the specific operation method is the same as the process of Example 1. In this example, only the ultrasonic emitter 40 is turned off, and the corrosion time is changed to 7 d.

[0150] The following introduces Comparative Example 4 of the present invention: Steel rods (metal rods 21) and dilute sulfuric acid samples are directly placed in the three storage bottles 11, and it is ensured that they are placed at a constant temperature of 55 °C for 7 d.

[0151] The following introduces Comparative Example 5 of the present invention: The traditional coupon method is used to test the corrosion of steel sheets by dilute copper sulfate samples. The traditional coupon method can be seen in Comparative Example 1.

[0152] The test results are shown in the table:

[0153]

[0154]

[0155] Note:

[0156] 1. The volume of metal used only records a single piece or single sheet of metal. In fact, 3 pieces or 3 sheets of metal are used in each embodiment.

[0157] 2. The amount of sample used refers to the total amount of sample used for 3 pieces or 3 sheets of metal.

[0158] 3. The mass loss rate in this table mainly counts the metal loss in the full immersion state (generally, the metal mass loss in full immersion is the largest).

[0159] 4. “﹣” indicates an increase in mass.

[0160] The following specifically introduces the comparative test results of all the test experiments.

[0161] According to the test results of Example 1, Example 2, Comparative Example 1, and Comparative Example 2, it can be seen that the mass loss rate of the present invention is basically the same as that of the traditional method (hanging coupon method), but the present invention uses a smaller volume (one percent) of metal and less (one-twentieth) of the sample liquid volume.

[0162] In addition, the present invention does not need to use condensed water during the simulation experiment, and the whole test time only needs 16 h, thereby effectively shortening the experiment time (the traditional method requires 168 h of test time). Obviously, the present invention can not only reduce the usage amount of raw materials (metal and sample liquid volume) to achieve the purpose of saving resources, but also effectively shorten the simulation experiment time (shortened from 168 h to 16 h), thereby significantly improving the reliability and convenience of the experiment.

[0163] According to the test results of Comparative Example 1 and Comparative Example 3, it can be seen that the mass loss rates of the two are basically the same. Therefore, it shows that the simulation experiment requires a test time as long as 168 h without using ultrasonic acceleration. From this, it can be known that ultrasonic acceleration can effectively shorten the simulation test time (by increasing the metal corrosion rate to achieve the purpose of reducing the corrosion reaction time).

[0164] According to the test results of Comparative Example 1 and Comparative Example 4, it can be seen that the metal loss rate of Comparative Example 4 is relatively low. Therefore, it shows that if the liquid is not circulated using the circulation pool 30 and only the metal rod 21 is randomly immersed in the sample solution, the wall effect will seriously affect the metal corrosion process, resulting in a relatively low result.

[0165] According to the test results of Comparative Example 3 and Comparative Example 5, the mass loss rate measured by the test method of the present invention is 9.52%. In Comparative Example 5, the phenomenon of the increase in the mass of the metal rod occurred. Therefore, this indicates that metal replacement corrosion occurred in Comparative Example 5. It can be seen that the present invention can truly reflect the real mass loss of replacement corrosion, which is lacking in the traditional method.

[0166] Compared with the prior art, the advantages of the present invention are as follows:

[0167] First, the present invention uses ultrasonic waves to accelerate the rate of the corrosion reaction in the circulation pool 30. Specifically, the present invention symmetrically distributes four ultrasonic transmitters 33 on both sides of the pool body 31, that is, two ultrasonic transmitters 33 are arranged on each side of the pool body 31. In this way, the ultrasonic waves emitted by the ultrasonic transmitters 33 can quickly reach the entire pool body 31, thereby effectively increasing the rate of metal corrosion to achieve the purpose of reducing the corrosion reaction time.

[0168] Second, the present invention places the square metal rod 21 with its length, width, and height scaled proportionally into the circulation pool 30 to solve the problem in the prior art that the metal rod 21 needs to be suspended and clamped. Specifically, first, the first screen 24 in the accommodation chamber 34 can provide good support for the support plate 21; second, there is a gap between the wall surface of each clamping and guiding portion 23 in each clamping group and the outer wall surface of the metal rod 21, so as to ensure that the clamped metal rod 21 can be in an upright state in the circulation pool 30 and the liquid can fully wet the metal rod, thereby further improving the success rate and accuracy of the simulation experiment.

[0169] In addition, since adjacent clamping groups are misaligned in the circumferential direction and there is a gap between the inner wall surface of each clamping and guiding portion 23 in each clamping group and the outer wall surface of the metal rod 21, the fluid has sufficient flow space in the circulation pool 30, so that it can more easily circulate from bottom to top in the circulation pool 30 (introduced below), which helps to make the metal rod 21 in a fully immersed, semi-immersed or suspended state in the circulation pool 30.

[0170] In addition, the present invention uses a peristaltic pump 13 to supply liquid, which can cause the liquid (corrosion sample) to flow over the surface of the metal rod 21 in a laminar flow manner in the accommodation chamber 34 of the circulation pool 30, thereby strengthening mass transfer and weakening the wall effect in the microenvironment to reproduce the real corrosion situation. Correspondingly, in the above process, the corrosion effect of the liquid (corrosion sample) on the surface of the metal rod 21 will be more uniform. At the same time, due to the use of a circulating flow method in the present invention, the amount of liquid used is greatly reduced.

[0171] Thirdly, the present invention uses an inductively coupled plasma mass spectrometer / optical emission spectrometer (ICP-MS / OES) as the main analytical means to measure and record the iron ion content in the liquid in the storage bottle 11, so as to achieve precise analysis of the corrosion degree of the metal rod 21. At the same time, it also helps to distinguish special corrosion such as replacement corrosion.

[0172] Fourthly, the present invention supplies heat by means of water bath heating, thereby realizing a constant temperature reaction in the circulation pool 30. In addition, by means of water bath heating, it is ensured that the liquid circulating into the circulation pool 30 each time can maintain a constant temperature state, so as to be able to increase the speed of metal corrosion and achieve the purpose of reducing the corrosion reaction time.

[0173] Fifthly, the storage bottle 11 in the present invention adopts a thin-layer glass heat dissipation design, which can not only be more easily exchanged with air, but also will not lose the total amount of liquid in the storage bottle 11, and can also achieve the purpose of eliminating the use of condensed water.

[0174] The above is only the preferred embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art can easily make changes or variations within the disclosure scope of the present invention, and such changes or variations should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. A metal corrosion measurement device, comprising: A circulation mechanism, which includes a storage bottle (11) containing a fluid, An experimental mechanism, which includes a circulation pool (30) connected to the storage bottle (11) through a conduit (22), a metal rod (21) vertically arranged in the circulation pool (30), and an ultrasonic emitter (40) connected to the circulation pool (30), Wherein, the circulation pool (30) includes a pool body (31), a top cover (32) arranged at the upper end surface of the pool body (31), and ultrasonic emission heads (33) symmetrically arranged on the outer wall of the pool body (31) and used for connecting with the ultrasonic emitter (40).

2. The metal corrosion measurement device according to claim 1, characterized in that, The metal rod (21) is configured into a square structure, and the experimental mechanism further includes a clamping group composed of a pair of clamping and guiding parts (23) arranged at the diagonals of the metal rod (21), and there is a gap between the clamping and guiding part (23) and the metal rod (21).

3. The metal corrosion measurement device according to claim 2, characterized in that, At least three such clamping groups are arranged along the axial direction of the pool body (31), and adjacent clamping groups are distributed in a circumferentially offset manner.

4. The metal corrosion measurement device according to claim 3, characterized in that, An accommodation chamber (34) allowing the fluid to pass through is formed in the pool body (31), The experimental mechanism further includes a first screen (24) arranged in the pool body (31) and used for supporting the metal rod (21), a second screen (25) arranged in the top cover (32), and an inlet (311) radially arranged on the pool body (31) and communicating with the accommodation chamber (34), wherein the inlet (311) is below the first screen (24).

5. The metal corrosion measurement device according to claim 4, characterized in that, A first outlet (321) connected to the conduit (22) and used for guiding the liquid in the accommodation chamber (34) is arranged at the top end of the top cover (32).

6. The metal corrosion measurement device according to claim 4, characterized in that, A second outlet (322) connected to the conduit (22) and used for guiding the gas in the accommodation chamber (34) is arranged at the top end of the top cover (32).

7. The metal corrosion measurement device according to claim 4, characterized in that, The experimental mechanism further includes a plug (324) fixed on the top cover (32), and a third outlet (323) radially arranged in the middle of the pool body (31) and used for guiding the liquid in the accommodation chamber (34), wherein the third outlet (323) communicates with the accommodation chamber (34).

8. The metal corrosion measurement device according to any one of claims 5 to 7, characterized in that, The circulation mechanism further includes a peristaltic pump (13) arranged between the storage bottle (11) and the circulation pool (30), and pump tubes (14) arranged between the peristaltic pump (13) and the storage bottle (11) and the circulation pool (30), wherein the peristaltic pump (13) is configured to be able to cause the liquid to flow over the surface of the metal rod (21) in a laminar flow manner, and the conduit (22) and the pump tubes (14) are both configured as fluororubber peristaltic pump tubes.

9. The metal corrosion measurement device according to claim 8, characterized in that, The storage bottle (11) includes a bottle cap (111) made of polyvinylidene fluoride film and a bottle body (112) made of borosilicate glass.

10. The metal corrosion measurement device according to claim 9, characterized in that, The metal corrosion measurement device further includes a water bath (12) for heating the fluid in the pump tube (14), a temperature controller (50) for adjusting the temperature of the liquid in the water bath (12), and a measuring device for measuring the iron ion content in the liquid in the storage bottle (11).

11. The metal corrosion measurement device according to claim 10, characterized in that, The output power of the ultrasonic emitter head (33) is in the range of 0.1 to 0.4 W.

12. A measurement method using the metal corrosion measurement device according to any one of claims 1 to 11, comprising the following steps: S1. Measuring the initial content C0 of iron ions in the liquid in the storage bottle (11) by the measuring device; respectively placing three metal rods (21) with a mass of M0 into different circulation pools (30); heating the fluid in the pump tube (14) by the water bath (12); S2. Promoting the circulation of the fluid in the circulation pool (30) by the peristaltic pump (13), with the metal rods (21) being fully immersed, half-immersed, and suspended relative to the liquid level of the fluid respectively; applying ultrasound to the circulation pool (30) by the ultrasonic emitter (40); S3. Stopping the reaction, measuring the iron ion content Ct in the liquid by the measuring device, and obtaining the mass loss of the metal rod (21) through w% = (Ct - C0) * V / M0 × 100%.

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