CN113884410A - Device for observing hydrogen diffusion process of local tissue in material by using SKPFM (scanning electron fluorescence microscopy) - Google Patents
Device for observing hydrogen diffusion process of local tissue in material by using SKPFM (scanning electron fluorescence microscopy) Download PDFInfo
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Abstract
The invention relates to the field of hydrogen energy utilization, and aims to provide a device for observing a hydrogen diffusion process of a local tissue in a material by using SKPFM. The device includes: the device comprises an electrochemical hydrogen charging module, a micro-area hydrogen permeation module, an atomic force microscope observation module and a computer control system. According to the principle that hydrogen invades materials to cause the change of the local contact potential difference of the materials, the scanning Kelvin probe force microscope module is used for observation, and conditions are created for measuring and calculating the hydrogen diffusion coefficient of local tissues in the materials through the observation behavior. The device can obtain the image data observed by SKPFM by observing the hydrogen permeation condition in the range of micron or even nanometer and observing the electrochemical hydrogen permeation process in situ. The image data can be further used to calculate hydrogen diffusion coefficients in the material, thereby enabling measurement of hydrogen diffusion coefficients at different temperature ranges. Compared with the traditional method, the method belongs to nondestructive testing and has the advantages of high testing accuracy, simplicity and convenience in operation and the like.
Description
Technical Field
The invention relates to the field of hydrogen energy utilization, relates to an observation technology of hydrogen diffusion processes of metal materials in different temperature ranges under electrochemical hydrogen charging or other simulated corrosion environments, and particularly relates to a device for observing the hydrogen diffusion processes of local structures in the materials by using SKPFM.
Background
The hydrogen energy has the characteristics of various sources, high utilization efficiency, cleanness, environmental protection and the like, is a main carrier for constructing a multi-energy supply system mainly based on clean energy, and is an important choice for realizing carbon peak reaching and carbon neutralization. Hydrogen fuel cell vehicles have become an important trend in the development of the vehicle industry as one of the important ways to utilize hydrogen energy. However, the hydrogen storage, hydrogen transportation and hydrogen utilization related devices in the automobile industry chain of the hydrogen fuel cell face the threat of hydrogen brittleness of the materials.
Due to the special physical and chemical properties of hydrogen, hydrogen-induced damage can be caused to equipment in contact with the hydrogen. In the hydrogen environment, hydrogen molecules are adsorbed on the surface of the metal and dissociated into hydrogen atoms, and the hydrogen atoms permeate into the metal, so that the mechanical property of the material is reduced, even seriously reduced, and the material is called hydrogen embrittlement in the industry. In order to research and design hydrogen environment-friendly materials and equipment, a material hydrogen compatibility test experiment needs to be carried out, and hydrogen permeation conditions, hydrogen diffusion rates and diffusion coefficients of different materials in a hydrogen environment are researched so as to screen materials or treatment processes more suitable for being used in a hydrogen environment.
The hydrogen embrittlement process is controlled by diffusion and concentration of hydrogen in the locally embrittled region, such as crack tips and grain boundaries. Therefore, understanding the behavior of hydrogen on the micro-and nano-scale is crucial to fully understanding the mechanism of hydrogen embrittlement. At present, a great deal of research is carried out in the field at home and abroad, for example, Chinese patent application 'a device and a method for researching metal hydrogen permeation behavior' (201510202110.0), Chinese patent application 'a device and a method for measuring metal hydrogen permeation performance' (201010185642.5) and the like are all centimeter-level macroscopic experiment measurements, and microscopic hydrogen permeation behavior is difficult to observe. Although the Chinese patent application 'metal local region hydrogen permeation behavior experimental device' (201310286355.6) can carry out micron-scale local hydrogen permeation curve measurement, the hydrogen permeation degree can not be accurately observed in a permeation micro-region in a positioning way and the hydrogen diffusion coefficient can not be quantitatively calculated.
The research on the behaviors of hydrogen on the micrometer scale and the nanometer scale is less at home and abroad, the crystal orientation dependence of in-situ direct observation on the diffusion of the hydrogen in crystal grains is lacked, the diffusion coefficient is calculated by in-situ direct observation on electrochemical hydrogen permeation, and the like, because the measurement of local hydrogen distribution in metal is still a difficult task.
Therefore, a device for observing the hydrogen diffusion process of local tissues in the material by using the SKPFM is designed, and the hydrogen permeation behaviors of different materials or different tissues under different temperature conditions are directly observed; therefore, the method makes a preliminary preparation for the next step of analyzing and calculating the corresponding diffusion coefficient and screening the material or the treatment process with good hydrogen adaptability in the hydrogen environment, and is an important research direction for technicians in the technical field at present.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a device for observing the hydrogen diffusion process of local tissues in a material by using SKPFM (transient phase shift keying) and is used for observing the hydrogen permeation behavior in the material in a micrometer and nanometer scale.
In order to solve the technical problem, the solution of the invention is as follows:
the device for observing the hydrogen diffusion process of local tissues in the material by using SKPFM comprises: the electrochemical hydrogen charging module takes a sample made of a material to be detected as a working electrode, so that the lower surface of the sample generates electrochemical reaction in an electrochemical hydrogen charging solution; the micro-area hydrogen permeation module utilizes the clamping device to horizontally fix the sample in the electrochemical hydrogen charging solution, so that the electrochemical hydrogen charging reaction can be continuously and stably carried out; the atomic force microscope observation module is used for observing contact potential difference change generated on the upper surface of the sample in the electrochemical hydrogen permeation process; and the computer control system is used for controlling the electrochemical reaction condition, observing the change process of the sample and recording the measurement data.
As a preferable scheme of the invention, the electrochemical hydrogen charging module comprises an electrochemical hydrogen charging tank, a stirrer, a platinum electrode, a reference electrode, a vent pipe, a working electrode connecting piece and an electrochemical workstation; the main structure of the micro-area hydrogen permeation module is an upper connector in a clamping device, the upper connector covers an upper opening of an electrochemical hydrogen charging groove to be used as an upper cover, and electrochemical hydrogen charging solution is filled in the electrochemical hydrogen charging groove; the stirrer, the platinum electrode, the reference electrode and the vent pipe are all fixed in a mounting hole on the upper connector, the tail ends of the stirrer, the platinum electrode and the reference electrode extend into the electrochemical hydrogen charging solution, and the tail end of the vent pipe is positioned in a gap between the electrochemical hydrogen charging solution and the upper connector; the working electrode connecting piece is fixed on the clamping device and is in close contact with the lower surface of the sample; each electrode is respectively connected with an electrochemical workstation through a lead, and the stirrer and the electrochemical workstation are connected with a computer control system through leads.
As a preferred scheme of the invention, the micro-area hydrogen permeation module comprises a clamping device, a temperature control system, an atmosphere control system and a sample balance control system; the main structure of the clamping device is an upper connecting body which covers an opening of an electrochemical hydrogen charging groove of the electrochemical hydrogen charging module, and a sinking boss which is hollow inside is arranged at the middle part of the clamping device; the sample is clamped at the through hole in the center of the boss, the lower surface of the sample is soaked in a hydrogen charging solution, and the upper surface of the sample is exposed out of the inner space on the upper side of the boss through the through hole; the temperature control system is used for keeping the temperature of the sample stable and comprises a temperature sensor, a copper ring heating cooler, a cooling controller and a heating control power supply, wherein the cooling controller and the heating control power supply are connected with the computer control system through leads; the atmosphere control system is used for forming a nitrogen environment in the inner space on the upper side of the boss and the observation area on the surface of the sample, and comprises a micro-area vent pipe, a vent valve, a nitrogen bottle and a communicating pipeline; the sample balance control system is used for keeping a sample horizontal and comprises a plurality of positioning rulers arranged on the clamping device.
As a preferred scheme of the present invention, the clamping device has a specific structure that: the boss is hollow, the cross section of the boss is circular, and surrounding steps are arranged on the periphery of the lower surface of the boss; the upper surface and the lower surface of the sample are respectively provided with protective clamping rubbers, and the protective clamping rubbers are clamped at a through hole in the center of the boss by a lower connecting body; the lower connecting body is fixed on the lower surface of the upper connecting body by a screw, and the lower connecting body, the surrounding step of the upper connecting body, the lower surface of the upper connecting body, the protective clamping rubber and the sample form an annular cavity together in an enclosing manner; the copper ring heating cooler of the temperature control system is arranged in the annular cavity, and the tail end of the temperature sensor extends into the annular cavity; a micro-area vent pipe in the atmosphere control system is adhered to the side wall of the inner space of the boss, and the tail end of the micro-area vent pipe is spaced from the upper surface of the boss; a plurality of positioning rulers in the sample balance control system are arranged at intervals along the outer side wall of the boss, the lower ends of the positioning rulers are fixedly connected with the lower connecting body, and the upper ends of the positioning rulers penetrate through calibration through holes arranged on the upper connecting body; and scale marks are arranged on the positioning scale, and the scale exposing the calibration through hole is used as a measuring reference.
As a preferable aspect of the present invention, the lower connector is made of a glass fiber heat insulating material.
In a preferred embodiment of the present invention, a screw hole for mounting a screw is provided around the step of the upper connecting body, and an O-ring rubber for sealing is provided between the upper connecting body and the lower connecting body.
As a preferable scheme of the invention, the edge of the upper connecting body is wedge-shaped, and the bevel edge is downward, so that the upper connecting body is matched with the open edge of the electrochemical hydrogen charging groove to realize installation.
As a preferable scheme of the present invention, the number of the plurality of positioning scales is four, and the positioning scales are uniformly arranged around the sinking boss.
As a preferable scheme of the invention, the atomic force microscope observation module comprises a scanning probe and a scanning probe, wherein the scanning probe is connected with the computer control system through a lead.
In a preferred embodiment of the present invention, the scanning probe is a MESP probe or a SCM-PIT probe.
Description of the inventive principles:
the method comprises the steps of measuring the initial surface potential of a sample by using a Kelvin Probe Force Microscope (KPFM), and then carrying out electrochemical hydrogen charging and continuously scanning in the hydrogen charging process; and (4) taking the change of the real-time contact potential difference larger than 10mV as a sign of hydrogen permeation of the whole sample to obtain image data observed by the SKPFM. The image data can be further used for calculating the hydrogen diffusion coefficient in the material, and measurement of the hydrogen diffusion coefficient in different temperature ranges is realized.
The diffusion behavior of hydrogen in a material is one of the important factors that contribute to the hydrogen embrittlement of the material. At present, for the measurement of the hydrogen diffusion coefficient, the traditional method is usually obtained by processing a hydrogen permeation curve in an electrolytic cell and then deriving through a formula, but the process cannot intuitively and accurately obtain a result, and the hydrogen diffusion coefficient under a high-temperature environment is difficult to reduce.
The inventor team of the application finds that hydrogen can cause the change of the local contact potential difference of the material after invading the material, and the scanning Kelvin probe force microscope module of the atomic force microscope can obtain the surface potential distribution condition and work function information of the sample by scanning the surface of the sample and drawing the Contact Potential Difference (CPD) between the surface and the cantilever probe so as to analyze the material property.
Therefore, according to the principle that hydrogen invades the material to cause the change of the local contact potential difference of the material, the invention utilizes the scanning Kelvin probe force microscope module to observe, and creates conditions for subsequently measuring and calculating the hydrogen diffusion coefficient of the local tissue in the material through the observation behavior.
The measurement of the contact potential difference variation caused by hydrogen intrusion into a material by using the SKPFM involves three processes: firstly, scanning and observing the contact potential difference of an initial sample by a scanning Kelvin probe force microscope, and recording the position; secondly, hydrogen is permeated and diffused into the material; and thirdly, scanning and observing the change of the contact potential difference of the material after the hydrogen is charged by a scanning Kelvin probe force microscope. The change in contact potential difference brought about by hydrogen can be determined by these three steps, but the following problems are involved in the process:
(1) when the local contact potential difference of the initial sample is measured, the same position needs to be selected when the sample is measured again after hydrogen is charged, and the position marking and searching of the micro area are difficult;
(2) the hydrogen charging process is divided into high-pressure hydrogen charging and electrochemical hydrogen charging, the high-pressure hydrogen charging technical requirement is high, the operation is complex, the efficiency is not high, and the electrochemical hydrogen charging is easy to realize;
(3) in the process of placing the sample to an observation position after high-pressure hydrogen charging or electrochemical hydrogen charging, hydrogen in the sample can gradually leak, and the measurement of the variation of the contact potential difference is inaccurate;
(4) when high pressure charging or chemical charging is performed, it is difficult to determine when hydrogen has completely diffused and permeated into the sample, and thus the material diffusion coefficient cannot be obtained in this way.
In order to solve the problems, the invention designs the device for testing the hydrogen diffusion coefficient of the local structure in the material by using the SKPFM. Technical means and technical advantages for solving the problems of the present invention are set forth in view of the above points:
aiming at the problem (1), the hydrogen charging process and the observation process are set to be a whole, and the in-situ observation probe is always in a local area to be observed, so that the problem that the same position is marked or cannot be found is solved;
aiming at the problem (2), because the high-pressure hydrogen charging is difficult to realize in-situ hydrogen charging and observation, the method adopts an in-situ electrochemical hydrogen charging mode, has the advantages of convenient operation, high hydrogen charging speed and the like compared with the high-pressure hydrogen charging, and can observe and calculate the diffusion coefficient of hydrogen in a sample under normal pressure so as to judge the hydrogen brittleness sensitivity of the material;
aiming at the problem (3), the hydrogen charging process and the observation process are set into a whole, the change of the contact potential difference is ensured to be observed in real time in the hydrogen charging process through in-situ observation, and the error caused by hydrogen gas dissipation due to observation after hydrogen charging is avoided;
aiming at the problem (4), in the design of the invention, a sample is placed in the middle, observation is carried out on the upper side, hydrogen is filled on the lower side, the whole process from the lower surface of the sample to the upper surface of the sample can be observed is monitored and controlled in real time by a computer, and the time when the hydrogen is completely diffused and permeated can be completely and accurately judged.
Besides the technical design of the electrochemical hydrogen charging module and the micro-area hydrogen permeation module, the invention also innovatively designs a balance control system, a temperature control system and an atmosphere control system:
the electrochemical hydrogen charging process needs to ensure that the sample is horizontally placed, so that hydrogen can be uniformly diffused to the other side of the sample across the same thickness at each position at the same time, and therefore, a sample balance control system is designed. A plurality of positioning rulers in the system are arranged at intervals along the outer side wall of a boss, the lower end of each positioning ruler is fixedly connected with a lower connecting body, and the upper end of each positioning ruler penetrates through a calibration through hole formed in an upper connecting body; scale marks are arranged on the positioning scale, and the scale exposing the calibration through hole is used as a measuring reference;
because the hydrogen diffusion rate is influenced by the temperature, the hydrogen diffusion coefficient at the temperature can be accurately observed and calculated only when the temperature is constant, and therefore, a temperature control system is designed. The system can ensure that the hydrogen charging process is carried out in a constant temperature environment, and meanwhile, the hydrogen diffusion coefficients at different temperatures can be observed and calculated by controlling the temperature change, so that the relation between the hydrogen diffusion coefficient of the material and the temperature is obtained;
the contact potential difference scanned by the probe of the scanning Kelvin probe force microscope may be influenced by oxygen, water and other components in the air, and a certain atmosphere environment needs to be controlled in the scanning environment, so that the accuracy of the result is ensured, and therefore, an atmosphere control system is designed. The system can ensure that the scanning of the microscope probe is carried out under a certain atmosphere environment, and related technicians can control different atmospheres to study the relation between the scanning result and the atmosphere environment.
Compared with the prior art, the invention has the beneficial effects that:
1. the observation device provided by the invention can observe the hydrogen permeation condition in the micrometer range or even the nanometer range. The image data observed by the SKPFM can be obtained by in-situ observation of the electrochemical hydrogen permeation process. The image data can be further used to calculate hydrogen diffusion coefficients in the material, thereby enabling measurement of hydrogen diffusion coefficients at different temperature ranges.
2. Compared with the traditional method, the method belongs to nondestructive testing and has the advantages of high testing accuracy, simplicity and convenience in operation and the like.
Drawings
FIG. 1 is a schematic diagram of the overall structure of the apparatus of the present invention;
FIG. 2 is a schematic view of a partial cross-sectional structure of a micro-area hydrogen permeation module;
FIG. 3 is a schematic top view of a partial structure of a micro-area hydrogen permeation module.
In the figure: an electrochemical hydrogen charging tank 1, an electrochemical hydrogen charging solution 2, a stirrer 3, a hydrogen charging tank ring opening 4, an upper connector 5, a vent pipe 6, a stirrer control power supply 7, a micro-area vent pipe 8, a nitrogen gas cylinder 9, a vent valve 10, a copper ring heating cooler 11, a lower connector 12, a scanning probe 13, a scanning probe 14, a heating control power supply 15, a temperature sensor 16, a cooling controller 17, a computer control system 18, an electrochemical workstation 19, a reference electrode 20, a working electrode connector 21, a platinum electrode 22, a stirrer connecting hole 301, a wedge-shaped edge 501, a positioning scale 502, an O-shaped rubber ring, a conical screw groove 504, a sample upper surface protection clamping rubber 505, a sample 506, a screw hole 507, a vent pipe hole 601, a sample lower surface protection clamping rubber 1201, a temperature control system connecting hole 1601, a reference electrode connecting hole 2001, a sample contact connector conducting wire hole 2101, A platinum electrode connection hole 2201.
Detailed Description
The device for observing the hydrogen diffusion process of the local tissue in the material by using the SKPFM according to the present invention is described in detail below with reference to specific embodiments.
The structure of the testing device is shown in figures 1-3, and comprises a micro-area hydrogen permeation module, an atomic force microscope observation module, an electrochemical hydrogen charging module and a computer control system 18; the micro-area hydrogen permeation module comprises a clamping device, a temperature control system, an atmosphere control system, a sample balance control system and the like. The electrochemical hydrogen charging module takes a sample 506 made of a material to be detected as a working electrode, so that the lower surface of the sample generates electrochemical reaction in the electrochemical hydrogen charging solution 2; the micro-area hydrogen permeation module utilizes the clamping device to horizontally fix the sample in the electrochemical hydrogen charging solution 2, so that the electrochemical hydrogen charging reaction can be continuously and stably carried out; the atomic force microscope observation module is used for observing contact potential difference change generated on the upper surface of the sample in the electrochemical hydrogen permeation process; and the computer control system is used for controlling the electrochemical reaction condition, observing the change process of the sample and recording the measurement data.
The micro-area hydrogen permeation module comprises a clamping device, a temperature control system, an atmosphere control system and a sample balance control system:
the main structure of the clamping device is an upper connecting body 5 which covers an opening of an electrochemical hydrogen charging groove 1 in an electrochemical hydrogen charging module, wherein the middle part of the clamping device is provided with a sinking boss with a hollow inner part, and the section of the sinking boss is in a ring shape; the sample 506 is clamped at the through hole in the center of the boss by the lower connecting body 12, the lower surface of the sample is soaked in the hydrogen charging solution, and the upper surface of the sample is exposed out of the inner space on the upper side of the boss through the through hole; the periphery of the lower surface of the boss is provided with a surrounding step; the lower connecting body 12 is fixed on the lower surface of the upper connecting body 5 by screws, and protective clamping rubbers are respectively arranged on the upper surface and the lower surface of the sample 506; the lower connecting body 12, the surrounding step of the upper connecting body 5, the lower surface of the upper connecting body, the protective clamping rubber and the test piece 506 are enclosed to form an annular cavity. An O-ring rubber seal is provided between the upper connecting body 5 and the lower connecting body 12.
The temperature control system is used for keeping the temperature of the sample stable and comprises a temperature sensor 16, a copper ring heating cooler 11, a cooling controller 17 and a heating control power supply 15, wherein the cooling controller 17 and the heating control power supply 15 are connected with a computer control system 18 through leads; the copper ring heating and cooling unit 11 of the temperature control system is arranged in the annular cavity, into which the end of the temperature sensor 16 extends.
The atmosphere control system comprises a micro-area vent pipe 8, a vent valve 10, a nitrogen gas bottle 9 and a communicating pipeline, wherein the micro-area vent pipe 8 is adhered to the side wall of the inner space of the boss, and the tail end of the micro-area vent pipe is spaced from the upper surface of the boss and is used for forming a nitrogen environment in the inner space on the upper side of the boss and an observation area on the surface of a sample.
The specimen balance control system, which is used to maintain the level of the specimen 506, includes four positioning scales 502 evenly spaced along the exterior sidewall of the boss; the lower end of the lower connecting body is fixedly connected with a lower connecting body 12, and the upper end of the lower connecting body passes through a calibration through hole arranged on the upper connecting body 5; the positioning scale 502 is provided with scale marks, and the scale marks exposing the calibration through holes are used as measuring reference.
The atomic force microscope observation module comprises a scanning probe 12 and a scanning probe 14, wherein the scanning probe 12 is connected with a computer control system 18 through a lead, and the scanning probe 14 can be selected from a MESP probe or an SCM-PIT probe.
The electrochemical hydrogen charging module comprises an electrochemical hydrogen charging tank 1, a stirrer 3, a platinum electrode 22, a reference electrode 20, a vent pipe 6, a working electrode connecting piece 2 and an electrochemical workstation 19; the upper connecting body 5 is covered on the upper opening of the electrochemical hydrogen charging tank 1 to be used as an upper cover, and the edge of the upper connecting body is wedge-shaped, the inclined edge of the upper connecting body is downward, and the upper connecting body is used for matching with the edge of the opening of the electrochemical hydrogen charging tank 1 to realize installation. An electrochemical hydrogen charging solution 2 is filled in the electrochemical hydrogen charging tank 1; the stirrer 3, the platinum electrode 22, the reference electrode 20 and the vent pipe 6 are all fixed in a mounting hole on the upper connector 5, the tail ends of the stirrer 3, the platinum electrode 22 and the reference electrode 20 extend into the electrochemical hydrogen charging solution 2, and the tail end of the vent pipe 6 is positioned in a gap between the electrochemical hydrogen charging solution 2 and the upper connector 5; the working electrode connecting piece 21 is fixed on the clamping device and is tightly contacted with the lower surface of the sample 506; the electrodes are respectively connected with an electrochemical workstation 19 through leads, and the stirrer 3 and the electrochemical workstation 19 are connected with a computer control system 18 through leads.
The method for realizing the local tissue hydrogen diffusion coefficient in the test material by using the device is briefly described, and specifically comprises the following steps:
(1) a sheet sample 506 made of a metal material is used as a working electrode of the electrochemical hydrogen charging tank 1, and the lower surface of the sample is soaked in an electrochemical hydrogen charging solution 2; the electrochemical hydrogen charging solution can be prepared according to the experimental requirements, for example, a 95-99% volume fraction of 0.5mol/L sulfuric acid solution and 1-5% 1g/L CS (NH) solution2)2A corrosion inhibitor solution.
(2) Observing the upper surface of the sample by using an atomic force microscope under the condition of keeping the level of the sample and the nitrogen environment; starting a hydrogen filling tank to enable the lower surface of the sample to have a hydrogen filling reaction, indicating that hydrogen has completely permeated the sample when the variation of the contact potential difference is more than 10mV, and recording the change time T used as the hydrogen filling lag time;
when the hydrogen charging tank is started, the electrochemical hydrogen charging solution 2 is continuously stirred by the stirrer 3, so that the concentration of the local solution is prevented from being uneven.
(3) According to formula DH＝L2(6T), calculating the hydrogen diffusion coefficient of the material used for the sample;
the meaning and the measurement unit of each symbol in the formula are respectively: dHIs the hydrogen diffusion coefficient of the metal material; l is the sample thickness, cm; t is the charging lag time, s.
The sheet sample can be square sheet with side length of 10 mm and thickness of 1 mm; or a circular sheet having a radial dimension greater than 10 mm. Before observing hydrogen permeation of a sample, the sample is pretreated: grinding the metal sheet to 2000 meshes, then polishing, and then carrying out single-side nickel plating, wherein the thickness of a plating layer is 1-3 microns; the plating side is used as the lower surface to be soaked in the electrochemical hydrogen charging solution 2.
By adjusting the electrochemical hydrogen charging reaction parameters and the sample temperature, the hydrogen diffusion coefficients of the metal material under different conditions can be obtained. By repeating the above-described operation steps by replacing a sheet-like test piece made of a different metal material, the hydrogen diffusion coefficients of the different materials can be obtained.
It should be noted that the technical scheme of the invention only relates to the description of the specific structure and connection relationship of the device, and the device can realize in-situ observation of the electrochemical hydrogen permeation process and obtain image data of SKPFM observation. However, the content of "further calculating the hydrogen diffusion coefficient in the material based on the image data to realize the measurement of the hydrogen diffusion coefficient in different temperature ranges" does not belong to the technical problem to be solved by the present invention. The description of the related content of the present invention is intended to be illustrative only.
A more detailed description is as follows:
the clamping device is arranged on the upper part of the electrochemical hydrogen charging tank 1 and mainly comprises an upper connector 5 and a lower connector 12. An air vent pipe hole 601, a stirrer connecting hole 301, a reference electrode connecting hole 2001, a platinum electrode connecting hole 2201, a sample contact connecting conductor wire hole 2101, a micro-area air vent pipe 8, a temperature control system connecting hole 1601, four positioning through holes 2 and four conical screw grooves 504 are formed in the upper connecting body 5; the lower connector 12 is made of glass fiber heat insulating material and is provided with four conical screw holes 507; the upper connecting body 5 and the lower connecting body 12 are connected by four screws, and an O-shaped rubber ring 503 is sandwiched between the two. Intermediate the two for holding the sample 506. The micro-area vent pipe 8 is adhered to the side wall of the upper part of the boss, and the distance between the pipe orifice and the upper surface of the boss is about 3 mm;
the atomic force microscope observation module adopts an SKPFM scanning mode, is positioned right above the middle of the micro-area hydrogen permeation module, comprises a scanning probe 13 and a scanning probe 14, and the scanning probe 13 extends into the upper side of the sample 506 for observation. The scanning probe 14 enters the upper side of the clamped sample 506 to scan and observe the sample. The probe used by the atomic force microscope observation module is a MESP probe or an SCM-PIT probe. For example, measurement can be performed using a scanning Probe microscope (Kelvin Probe Force Micromicroscope, KPFM) manufactured by Bruker.
In the electrochemical hydrogen charging module, the platinum electrode 22 is used as an anode, the working electrode connecting piece 21 is tightly connected to the lower surface of the sample 506, so that the sample 506 can work as a cathode, and the reference electrode 20 is used as an auxiliary electrode of an electrochemical workstation. The lower surface of the sample is immersed in the electrochemical hydrogen charging solution 2, and the lug boss extends downwards, so that the position of the sample 506 forms a liquid level difference with the surrounding liquid level, and the hydrogen charging solution can be ensured to be capable of soaking the lower surface of the sample all the time. The continuous stirring of the stirrer 3 can also avoid the uneven concentration of the local solution. The adoption of the protective clamping rubber can ensure the sealing effect and prevent the solution from entering the annular cavity. The redundant gas generated in the cavity of the electrochemical hydrogen charging tank 1 is discharged through the vent pipe 6, so as to prevent the internal pressure from influencing the balance of the sample surface.
The temperature control system comprises a copper ring heating cooler 11 arranged in the annular cavity, and the copper ring and the temperature sensor 16 are communicated through a temperature control system connecting hole 1601. The copper ring is used as a conductor for heating during heating, liquid nitrogen is introduced into the copper ring in a proper amount during cooling, and the temperature sensor transmits the temperature of the annular space to the computer control system in real time so as to control the temperature. The lower connector 12 is made of fiberglass insulation material, thereby reducing heat transfer to the underlying electrochemical hydrogen solution over a range of temperatures.
The atmosphere control system controls nitrogen of a nitrogen bottle 9 to be introduced into a micro-area vent pipe 8 through a vent valve 10, and forms a nitrogen environment for a micro-area hydrogen permeation module to scan an observation area, so that various components (such as oxygen, carbon dioxide and other gases or particle impurities) in the air are prevented from influencing the scanning observation contact potential difference.
The electrochemical hydrogen charging tank is horizontally arranged, the wedge-shaped groove of the micro-area hydrogen permeation module is horizontally arranged on the upper part of the electrochemical hydrogen charging tank, and then the level of sample clamping is required to be controlled to ensure the horizontal and uniform hydrogen charging during the hydrogen charging. Four positioning scales 502 are used in the specimen balance control system to maintain specimen level. When a sample is clamped in the micro-area hydrogen permeation module before an experiment, the four vertical scales in the four directions are ensured to be the same by adjusting the four fastening screws for connecting the upper connecting body 5 and the lower connecting body 12. Because the deformation range of the O-shaped ring is large and the water pressure is small, the leakage can be avoided, and meanwhile, the good horizontal control can be realized.
The computer control system comprises a computer controller 18 connected to the scanning probe 13 through a wire to control scanning parameters and receive scanning information, a stirrer control power supply 7 to control stirring speed, a heating control power supply 15, a temperature sensor 16 and a cooling controller 17 to control heating and cooling temperature, and an electrochemical workstation 19 to control hydrogen charging parameters.
When testing, specific operation contents are as follows:
firstly, preparing a square block with the specification of about 10 millimeters of side length and about 1 millimeter of thickness or a round metal sheet with the diameter of about 10 millimeters and the thickness of about 1 millimeter as a sample; grinding to 2000 meshes, polishing, and then carrying out single-side nickel plating, wherein the thickness of a plating layer is 1-3 microns; and soaking the plating layer side serving as the lower surface in an electrochemical hydrogen charging solution.
The upper connecting body 5 is taken down and placed horizontally in the reverse direction, the copper ring heating cooler 11 and the temperature sensor 16 are installed in a temperature control system connecting hole 1601, then a sample is placed on the sample upper surface protective clamping rubber 505, after an O-shaped sealing ring is placed, the lower connecting body 12 is connected to the upper connecting body 5 through screws, and after the sample is appropriately screwed, the level of the sample is further finely adjusted and controlled through four positioning scales 502.
After horizontally clamping the sample, the vent pipe 6, the stirrer 3, the micro-area vent pipe 8 connecting line, the reference electrode 20, the platinum electrode 22, the heating control power supply 15, the cooling controller 17 and the sample contact connection conductor wire hole 2101 are sequentially connected to the corresponding position of the upper connector 5, then the upper connector 5 is horizontally placed on the electrochemical hydrogen charging tank 1, and the wedge-shaped edge 501 can ensure that the upper connector is horizontally placed.
The scanning probe 13 is moved over the sample. The scanning probe 13, stirrer control power supply 7, heating control power supply 15, temperature sensor 16, cooling controller power supply 17 and electrochemical workstation 19 are securely connected to a computer controller 18.
And controlling the nitrogen in the nitrogen bottle 9 by the vent valve 10 to form a scanning nitrogen atmosphere, and controlling the temperature control system to obtain the required experimental condition temperature.
The scanning probe 13 firstly carries out initial potential difference measurement, the electrochemical workstation 19 is opened to start hydrogen charging reaction, and electrochemical micro-area hydrogen permeation is carried out from the lower surface to the upper surface of the sample; when a contact potential difference change of more than 10mV is observed, it is indicated that hydrogen permeation is complete. The time of change T of the contact potential difference is recorded as the charging lag time.
Using the formula: dH＝L2And 6T, obtaining the hydrogen diffusion coefficient required to be measured.
In the formula, the meaning and the measurement unit of each symbol are respectively: dHIs the hydrogen diffusion coefficient; l is the sample thickness, cm; t is the charging lag time, s.
The hydrogen diffusion coefficients of the materials under different conditions can be obtained by adjusting different temperature or electrochemical hydrogen charging parameters (such as hydrogen charging current, hydrogen charging liquid concentration and other parameters). And adjusting different materials (such as dual-phase steel, austenitic stainless steel, martensitic steel and the like), and repeating the steps to obtain the hydrogen diffusion coefficients of the different materials.
Hydrogen diffusion coefficient tests are carried out at different temperatures, and regularity between the hydrogen diffusion coefficient of the material and the temperature can be obtained; and (3) carrying out hydrogen diffusion coefficient test under different hydrogen charging parameters to obtain the correlation between the hydrogen diffusion coefficient of the material and the hydrogen charging parameters. The hydrogen diffusion coefficient, the temperature and the law of hydrogen filling parameters of the material have a direct relation with the hydrogen brittleness sensitivity of the material, and at present, the hydrogen brittleness sensitivity is considered to be consistent: under certain conditions, the higher the hydrogen diffusion coefficient of the material is, the more easily hydrogen gas diffuses, permeates and gathers in the material, so that hydrogen-induced damage (hydrogen embrittlement) is generated. Therefore, the system has important guiding significance for researching the hydrogen brittleness sensitivity of the material, designing the material and selecting the material under different conditions.
As described above, the device for observing the hydrogen diffusion process of the local tissue in the material by using the SKPFM can observe the hydrogen permeation condition in a micrometer or even nanometer range through an atomic force microscope, and realize the observation and the acquisition of image data by using the SKPFM in the in-situ observation of the electrochemical hydrogen permeation process. Compared with the traditional method, the method has the advantages of high test accuracy, simplicity and convenience in operation, capability of performing nondestructive test and the like. If the image data is further utilized, the hydrogen diffusion coefficient in the material is calculated through a formula, and the measurement of the hydrogen diffusion coefficient of different materials in different temperature ranges or different electrochemical hydrogen charging parameters can be realized.
The preferred schematic block diagrams of the present example are shown in fig. 1, 2 and 3, but the technical forms involved in the present invention can be implemented in other similar embodiments, and are not limited to the descriptions given in the specific embodiments of the present invention. More precisely, the implementation flow given by the invention is a better way to fully understand the technical route of the invention in the technical field related to the invention. Any variations, modifications and adaptations of the structures, means or methods according to the teachings of the present invention are within the scope of the present invention.
Claims (10)
1. A device for observing a hydrogen diffusion process of local tissues in a material by using SKPFM (scanning electron microscope), which is characterized by comprising:
the electrochemical hydrogen charging module takes a sample made of a material to be detected as a working electrode, so that the lower surface of the sample generates electrochemical reaction in an electrochemical hydrogen charging solution;
the micro-area hydrogen permeation module utilizes the clamping device to horizontally fix the sample in the electrochemical hydrogen charging solution, so that the electrochemical hydrogen charging reaction can be continuously and stably carried out;
the atomic force microscope observation module is used for observing contact potential difference change generated on the upper surface of the sample in the electrochemical hydrogen permeation process;
and the computer control system is used for controlling the electrochemical reaction condition, observing the change process of the sample and recording the measurement data.
2. The apparatus of claim 1, wherein the electrochemical hydrogen charging module comprises an electrochemical hydrogen charging tank, an agitator, a platinum electrode, a reference electrode, a vent tube, a working electrode connection, and an electrochemical workstation;
the main structure of the micro-area hydrogen permeation module is an upper connector in a clamping device, the upper connector covers an upper opening of an electrochemical hydrogen charging groove to be used as an upper cover, and electrochemical hydrogen charging solution is filled in the electrochemical hydrogen charging groove; the stirrer, the platinum electrode, the reference electrode and the vent pipe are all fixed in a mounting hole on the upper connector, the tail ends of the stirrer, the platinum electrode and the reference electrode extend into the electrochemical hydrogen charging solution, and the tail end of the vent pipe is positioned in a gap between the electrochemical hydrogen charging solution and the upper connector; the working electrode connecting piece is fixed on the clamping device and is in close contact with the lower surface of the sample; each electrode is respectively connected with an electrochemical workstation through a lead, and the stirrer and the electrochemical workstation are connected with a computer control system through leads.
3. The device according to claim 1, wherein the micro-area hydrogen permeation module comprises a clamping device, a temperature control system, an atmosphere control system and a sample balance control system; wherein the content of the first and second substances,
the main structure of the clamping device is an upper connector which covers the opening of an electrochemical hydrogen charging groove of the electrochemical hydrogen charging module, and a sinking boss with a hollow interior is arranged at the middle part of the clamping device; the sample is clamped at the through hole in the center of the boss, the lower surface of the sample is soaked in a hydrogen charging solution, and the upper surface of the sample is exposed out of the inner space on the upper side of the boss through the through hole;
the temperature control system is used for keeping the temperature of the sample stable and comprises a temperature sensor, a copper ring heating cooler, a cooling controller and a heating control power supply, wherein the cooling controller and the heating control power supply are connected with the computer control system through leads;
the atmosphere control system is used for forming a nitrogen environment in the inner space on the upper side of the boss and the observation area on the surface of the sample, and comprises a micro-area vent pipe, a vent valve, a nitrogen bottle and a communicating pipeline;
the sample balance control system is used for keeping a sample horizontal and comprises a plurality of positioning rulers arranged on the clamping device.
4. The device according to claim 3, wherein the clamping device is specifically structured as follows:
the boss is hollow, the cross section of the boss is circular, and surrounding steps are arranged on the periphery of the lower surface of the boss; the upper surface and the lower surface of the sample are respectively provided with protective clamping rubbers, and the protective clamping rubbers are clamped at a through hole in the center of the boss by a lower connecting body;
the lower connecting body is fixed on the lower surface of the upper connecting body by a screw, and the lower connecting body, the surrounding step of the upper connecting body, the lower surface of the upper connecting body, the protective clamping rubber and the sample form an annular cavity together in an enclosing manner; the copper ring heating cooler of the temperature control system is arranged in the annular cavity, and the tail end of the temperature sensor extends into the annular cavity;
a micro-area vent pipe in the atmosphere control system is adhered to the side wall of the inner space of the boss, and the tail end of the micro-area vent pipe is spaced from the upper surface of the boss;
a plurality of positioning rulers in the sample balance control system are arranged at intervals along the outer side wall of the boss, the lower ends of the positioning rulers are fixedly connected with the lower connecting body, and the upper ends of the positioning rulers penetrate through calibration through holes arranged on the upper connecting body; and scale marks are arranged on the positioning scale, and the scale exposing the calibration through hole is used as a measuring reference.
5. The apparatus of claim 3, wherein the lower connector is made of fiberglass insulation.
6. The device as claimed in claim 3, wherein the surrounding step of the upper connecting body is provided with a screw hole for mounting a screw, and an O-shaped rubber ring for sealing is provided between the upper connecting body and the lower connecting body.
7. The device of claim 3, wherein the upper connector has a wedge-shaped edge with a downward bevel for engaging the open edge of the electrochemical hydrogen charging cell.
8. The apparatus of claim 3, wherein the plurality of positioning scales is four and are evenly arranged around the sunken boss.
9. The apparatus of claim 1, wherein the atomic force microscopy observation module comprises a scanning probe and a scanning probe, wherein the scanning probe is connected with the computer control system through a lead.
10. The apparatus of claim 9, wherein the scanning probes are MESP probes or SCM-PIT probes.
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