CN114184630A - Universal electrolytic polishing method for preparing SEM (scanning Electron microscope) and EBSD (Electron Back scattered diffraction) samples - Google Patents
Universal electrolytic polishing method for preparing SEM (scanning Electron microscope) and EBSD (Electron Back scattered diffraction) samples Download PDFInfo
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- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/32—Polishing; Etching
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
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Abstract
The invention discloses a general electrolytic polishing method for preparing SEM and EBSD samples, which comprises the following steps: processing a test plane of a sample to be prepared according to requirements; preparing an electrolytic polishing solution and adding ethylene diamine tetraacetic acid into the electrolytic polishing solution; a special container is adopted to contain the prepared electrolytic polishing solution and carry out cooling treatment; connecting the special container with an external direct current power supply; putting the special container and the sample to be prepared into the electrolytic polishing solution and turning on a direct current power supply; whether the preparation is finished or not is judged by observing the degree of light reflection of the test plane. Has the advantages that: the method can be used for universally preparing most metal materials such as magnesium alloy, aluminum alloy, zinc alloy, iron-cobalt-nickel alloy, copper alloy, titanium alloy, high-entropy alloy, stainless steel, complex rare earth alloy and the like, has better universality and universality, and can realize the preparation of different metals by only adjusting the adaptive voltage value in the electrolytic process.
Description
Technical Field
The invention relates to the field of metal material detection, in particular to a general electrolytic polishing method for preparing SEM and EBSD samples.
Background
Scanning Electron Microscopy (SEM) is an observation instrument that is intermediate between transmission electron microscopy and optical microscopy. The method utilizes a focused narrow high-energy electron beam to scan a sample, stimulates various physical information through the interaction between the electron beam and a substance, and collects, amplifies and re-images the information to achieve the purpose of characterizing the microscopic morphology of the substance. The resolution of the novel scanning electron microscope can reach 1 nm; the magnification can reach 30 ten thousand times and can be continuously adjusted; and the depth of field is large, the visual field is large, and the imaging stereo effect is good. In addition, the combination of the scanning electron microscope and other analytical instruments can realize the analysis of the composition of the micro-area of the substance while observing the micro-morphology. The scanning electron microscope has wide application in the research of rock soil, graphite, ceramic, nanometer material, etc. Therefore, scanning electron microscopes play a significant role in the field of scientific research.
Since the 90 s of the 20 th century, the analysis technology of the orientation of the crystal micro-area and the crystal structure of an Electron Back-scattering pattern (EBSP) assembled on an SEM has been greatly developed and widely applied to the characterization of the microstructure and the microtexture of a material. This technique is also called Electron Back Scattering Diffraction (EBSD) or the like. The main feature of EBSD is diffraction at the sub-micron level of spatial resolution while retaining the conventional features of scanning electron microscopy. EBSD changes the conventional texture analysis method and forms a brand new scientific field called microtexture-combining the microstructure with crystallography analysis. The EBSD technology can realize full-automatic acquisition of micro-area orientation information, the sample preparation is simple, the data acquisition speed is high (about 36 ten thousand points/hour or even higher), the resolution is high (the spatial resolution and the angular resolution can respectively reach 0.1nm and 0.5 degrees), a foundation is laid for fast and quantitative statistics and research of the microstructure and the texture of a material, and the EBSD technology becomes an effective analysis means in material research. The field of application of EBSD technology has focused on a variety of polycrystalline materials-industrially produced metals and alloys, ceramics, semiconductors, superconductors, ores-to study various phenomena, such as thermomechanical processing, plastic deformation processes, properties related to orientation (formability, magnetism, etc.), interfacial properties (corrosion, cracking, heat cracking, etc.), phase identification, etc.
The metallic material SEM samples and EBSD samples have a commonality in preparation requirements: both SEM and EBSD require the sample test surface to be as flat as possible without major undulations. The SEM sample has higher requirement on the surface appearance of the sample, stains and corrosion can be generated when the surface of the sample is observed by a scanning electron microscope after conventional polishing treatment and corrosion of a corrosive liquid, imaging is fuzzy, the appearance information of a metal matrix cannot be presented perfectly, for example, the mechanical polishing consumes time, stains are easily introduced in corrosion operation, and the sample preparation cannot be stabilized; the vibration polishing is time-consuming, and the vibration polishing can hardly be carried out on the magnesium alloy which is easy to corrode; the argon ion grinding sample preparation equipment is expensive, the equipment accessories are consumed greatly and are expensive, and the test area is smaller and is only the area bombarded by the argon ions.
An effective solution to the problems in the related art has not been proposed yet.
Disclosure of Invention
In view of the problems in the related art, the present invention provides a general electropolishing method for preparing SEM and EBSD samples, so as to overcome the above technical problems in the related art.
Therefore, the invention adopts the following specific technical scheme:
a general electropolishing method for preparing SEM and EBSD samples, comprising the steps of:
s1, processing a test plane of the sample to be prepared according to the requirement;
s2, preparing an electrolytic polishing solution and adding ethylene diamine tetraacetic acid into the electrolytic polishing solution;
s3, adopting a special container to contain the prepared electrolytic polishing solution and performing cooling treatment;
s4, connecting the special container with an external direct current power supply;
s5, putting the special container and the sample to be prepared into the electrolytic polishing solution and turning on a direct current power supply;
and S6, judging whether the preparation is finished or not by observing the light reflection degree of the test plane.
Further, in S1, the test plane is processed by grinding or cutting to meet the test requirements of SEM and EBSD.
Further, the electrolytic polishing solution is prepared by adopting perchloric acid and absolute ethyl alcohol, and the concentration of the perchloric acid is 5% -20%.
Further, in the step S2, when the electropolishing solution is at-20 ℃, 10-20 g/L of ethylenediamine tetraacetic acid is added and stirred to make the electropolishing solution reach a saturated state.
Further, in the step S3, the temperature is reduced by adding dry ice particles into the interlayer of the container, and the temperature of the electrolytic polishing solution is reduced to-30 ℃ to-60 ℃.
Further, the dc power supply in S4 is an adjustable dc power supply, and the positive and negative electrodes of the adjustable dc power supply are respectively and correspondingly connected to the positive and negative electrode interfaces of the special container.
Further, the voltage is adjusted in S5 to adapt to the polishing of different metal materials, and a constant voltage mode is adopted in the polishing process.
Further, in S5, before the dc power is turned on, the cathode of the special container is inserted into the electrolyte, and the sample to be prepared is held by the positive electrode of the special container.
Further, the step of observing the degree of light reflection of the test plane to determine whether the preparation is completed in S6 includes the steps of:
s61, observing whether the test plane is covered with fine bubbles;
s62, observing whether the test plane is covered with a layer of grey oxide;
s63, observing whether the test plane generates mirror reflection;
s64, if all the phenomena occur, the sample preparation is finished;
and S65, turning off the power supply to stop the electrolytic polishing.
Further, if the test plane becomes dark or black in S6, the sample preparation fails.
The invention has the beneficial effects that:
(1) the invention adopts a brand new electrolytic polishing process, omits the complicated process of mechanical polishing and has the advantages of convenience and low cost; the sample can be prepared by grinding the flat test surface with sand paper, so that the sample preparation time is greatly shortened, the sample quality is improved, the preparation cost is greatly reduced, the SEM and EBSD samples can be obtained only by a one-step method, and the SEM sample does not need to be obtained by secondary corrosion, thereby improving the polishing efficiency.
(2) The method can be used for universally preparing most metal materials such as magnesium alloy, aluminum alloy, zinc alloy, iron-cobalt-nickel alloy, copper alloy, titanium alloy, high-entropy alloy, stainless steel, complex rare earth alloy and the like, has better universality and universality, and can realize the preparation of different metals only by adjusting the adaptive voltage value in the electrolytic process.
(3) The electrolytic polishing solution is a corrosive solution, the surface of a sample is uniformly corroded in the electrolytic polishing process, the crystal boundary and the second phase of the sample can be perfectly and clearly imaged by a scanning electron microscope, and the electrolytic polishing solution has universality and universality, so that the cost is saved, the difficulty in storage and waste liquid recovery and treatment is reduced, and the huge pressure on environmental protection caused by different electrolytes is reduced.
(4) The EBSD sample treated by the polishing method can effectively remove the stress layer on the surface of the test surface, improve the surface relief of the test surface, effectively improve the flatness of the test surface, ensure that the treated test surface has better surface gloss, and improve the definition and integrity of the chrysanthemum pool pattern in the EBSD test.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a generalized electropolishing method for preparing SEM and EBSD samples in accordance with an embodiment of the present invention;
FIG. 2 is SEM pictures of treated rare earth magnesium alloy nano precipitated phases and grain boundaries in a general electropolishing method for preparing SEM and EBSD samples in accordance with embodiments of the present invention;
FIG. 3 is a photograph of EBSD-IPF of a magnesium alloy of AZ31, AZ61-1Ca processed in a general electropolishing method for preparing SEM and EBSD samples in accordance with embodiments of the present invention;
FIG. 4 is SEM pictures of various stages of an electropolishing process in a generalized electropolishing method for preparing SEM and EBSD samples in accordance with embodiments of the present invention;
FIG. 5 is a surface topography of an EBSD scan area after completion of electropolishing of a second phase magnesium alloy in a generalized electropolishing method for preparing SEM and EBSD samples in accordance with an embodiment of the present invention;
FIG. 6 is a post-treatment EBSD-IPF picture of TA2 titanium alloy in a general electropolishing method for preparing SEM and EBSD samples in accordance with embodiments of the present invention;
FIG. 7 is a photograph of EBSD-IPF of zinc alloy at different processing states in a general electropolishing method for preparing SEM and EBSD samples in accordance with embodiments of the present invention;
FIG. 8 is a surface topography of a zinc alloy grain boundary sample in a general electropolishing method for preparing SEM and EBSD samples in accordance with embodiments of the present invention.
Detailed Description
For further explanation of the various embodiments, the drawings which form a part of the disclosure and which are incorporated in and constitute a part of this specification, illustrate embodiments and, together with the description, serve to explain the principles of operation of the embodiments, and to enable others of ordinary skill in the art to understand the various embodiments and advantages of the invention, and, by reference to these figures, reference is made to the accompanying drawings, which are not to scale and wherein like reference numerals generally refer to like elements.
According to an embodiment of the present invention, a universal electropolishing method for preparing SEM and EBSD samples is provided.
The present invention will now be further described with reference to the accompanying drawings and detailed description, wherein, as shown in FIG. 1, a general electropolishing method for preparing SEM and EBSD samples in accordance with an embodiment of the present invention comprises the steps of:
s1, processing a test plane of the sample to be prepared according to the requirement;
in one embodiment, the test plane is processed by grinding or cutting in S1 to meet the test requirements of SEM and EBSD.
S2, preparing an electrolytic polishing solution and adding ethylene diamine tetraacetic acid into the electrolytic polishing solution;
in one embodiment, the electropolishing solution is prepared using perchloric acid and absolute ethanol, and the concentration of perchloric acid is 5% -20%.
In one embodiment, 10 to 20g/L of EDTA is added into the electropolishing solution of S2 when the electropolishing solution is at-20 ℃ and stirred to make the electropolishing solution reach a saturated state.
Specifically, the added ethylenediamine tetraacetic acid needs to be added into the electrolyte at the temperature of-20 ℃ and stirred to be dissolved while being added until the solution is completely saturated.
S3, adopting a special container to contain the prepared electrolytic polishing solution and performing cooling treatment;
in one embodiment, in the step S3, the dry ice particles are added to the interlayer of the container to cool the electrolytic polishing solution to-30 ℃ to-60 ℃, and the electrolytic polishing solution is cooled by the dry ice uniquely, so that the electrolytic polishing solution has a long-time cooling function, is moderate in cooling speed, avoids the disadvantages of quenching by using liquid nitrogen and rapidly heating, and has high safety operability.
S4, connecting the special container with an external direct current power supply;
in an embodiment, the dc power supply in S4 is an adjustable dc power supply, and the positive electrode and the negative electrode of the adjustable dc power supply are respectively connected to the positive electrode interface and the negative electrode interface of the special container.
S5, putting the special container and the sample to be prepared into the electrolytic polishing solution and turning on a direct current power supply;
in one embodiment, the voltage is adjusted in S5 to adapt to polishing of different metal materials, and a constant voltage mode is adopted in the polishing process.
In one embodiment, before the dc power is turned on in S5, the cathode of the specially-made container is inserted into the electrolyte, and the sample to be prepared is held by the anode of the specially-made container.
And S6, judging whether the preparation is finished or not by observing the light reflection degree of the test plane.
In one embodiment, the step of observing the degree of light reflection of the test plane to determine whether the preparation is completed in S6 includes the steps of:
s61, observing whether the test plane is covered with fine bubbles;
s62, observing whether the test plane is covered with a layer of grey oxide;
s63, observing whether the test plane generates mirror reflection;
s64, if all the phenomena occur, the sample preparation is finished;
and S65, turning off the power supply to stop the electrolytic polishing.
In one embodiment, if the test plane is darkened or blackened in S6, the sample preparation fails.
Specifically, the observation method does not need to determine whether the electrolytic polishing is finished by timing, so that whether the electrolytic polishing process is finished by samples with different alloy components can be universally judged. The method is divided into 4 polishing stages: the first stage is a stage showing that fine bubbles are covered, and the polishing stage at the stage proves that the polishing stage can effectively remove surface stress and meets the condition that an EBSD test shows that no excessive stress exists; the second stage is a surface graying stage, fine bubbles covered by the first stage on the surface of the sample disappear and then a layer of thicker oxide is covered on the sample surface during polishing at the stage, and the surface presents a densely distributed discharge tip shape under a scanning electron microscope; in the third stage, gray scale on the surface in one stage gradually disappears and fades, so that the test surface has better mirror reflection capability compared with the previous stage, and the successfully prepared SEM and EBSD samples can be obtained by stopping electrolytic polishing in the third stage; the fourth stage is an overpolishing stage, generally a darkening and blackening of the surface, which is considered as a sample failure due to the excessive time and voltage.
And meanwhile, the initial voltage of electrolytic polishing is not too high, after dense bubbles on the surface of the sample are dispersed in the first stage, the sample enters the second stage, the electrolytic polishing voltage is gradually increased to be twice of the initial voltage and is kept, the gray color of the surface of the sample is observed to gradually fade until the test surface of the sample is completely gray and faded, and the polishing process of the test surface can be seen to be finished like a mirror surface in the electrolyte.
The recitation of values within a range in the present invention should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a temperature of from "-30 ℃ to-40 ℃ should be understood to include not only the explicitly recited temperature range of from about-30 ℃ to about-40 ℃, but also include individual processing temperatures (e.g., -31 ℃, -33 ℃, -36.5 ℃ and-40 ℃) and subranges (e.g., -30 ℃ to-32 ℃, -35.8 ℃ to 39.6 ℃, -39 ℃ to-40 ℃) within the indicated range.
The method mainly adopts an electrolytic polishing method to prepare the metal material SEM and EBSD samples, wherein the electrolytic polishing voltage adjustment and the influence of the sample surface on the stage are very critical. In a preferred embodiment, the electrolyte is formulated from analytically pure perchloric acid, analytically pure anhydrous ethanol and analytically pure ethylenediaminetetraacetic acid; adding the ethylenediamine tetraacetic acid is carried out at the temperature of-20 to-30 ℃ of perchloric acid ethanol solution, so as to avoid that the surface state of the sample is observed because the temperature of the solution is supersaturated and the ethylenediamine tetraacetic acid is separated out due to the reduction of the temperature in electrolytic polishing; the electrolytic polishing must be carried out at a solution temperature below-30 ℃ so as to avoid the heat release of the electrolytic polishing process from influencing the sample preparation quality and generating unnecessary danger; the time node for adjusting the voltage during polishing must be strictly performed as described above, otherwise the quality of the test surface of the sample will be deteriorated and the sample preparation will fail.
Example 1
Preparing a magnesium alloy structural morphology SEM sample. Taking the rare earth magnesium alloy with higher second phase content as an example, taking the rare earth magnesium alloy to be prepared, carrying out sand paper grinding, and adding the prepared electrolytic polishing solution of 10% perchloric acid ethanol saturated ethylene diamine tetraacetic acid into a special container; adding dry ice particles into the interlayer of the container; a thermometer waiting to be inserted into the electrolytic polishing solution showed a temperature of-40 ℃; connecting the positive electrode and the negative electrode of an adjustable direct current power supply with positive and negative electrode interfaces of a specially-made container, inserting a cathode of the container into electrolyte, and clamping the positive electrode of the container to an alloy to be prepared; turning on a direct current power supply, adjusting to a constant voltage mode, setting a voltage of 7V, inserting an anode into electrolyte, observing a sample testing surface and a cathode to generate a large amount of fine bubbles, slightly shaking a sample clamp, immediately dissipating the fine bubbles, slowly adjusting the voltage to 14V and keeping, observing that only the cathode has dense bubbles to dissipate through a window at the upper end of a container, continuously observing an alloy testing surface to form grey-white color, waiting for the grey-white color of the sample testing surface to gradually fade, slightly shaking the anode to clearly see that the sample testing surface has the characteristic of mirror reflection, immediately taking out an anode sample, immediately putting the anode sample into a beaker containing absolute ethyl alcohol, vibrating and cleaning by using ultrasonic waves, then clamping the sample by using tweezers, blowing the absolute ethyl alcohol on the surface to obtain a perfect sample as shown in figure 2, and clearly observing that a nanoscale phase and a precipitated crystal boundary have no interference on the surface.
Example 2
And preparing an AZ series magnesium alloy EBSD sample. Taking AZ31 and AZ61-1Ca alloy with fine crystal structure after large plastic deformation as an example, taking magnesium alloy to be prepared, carrying out sand paper grinding, and adding the prepared electrolytic polishing solution of 15% perchloric acid ethanol saturated ethylene diamine tetraacetic acid into a special container; adding dry ice particles into the interlayer of the container; a thermometer waiting to be inserted into the electrolytic polishing solution showed a temperature of-45 ℃; connecting the positive electrode and the negative electrode of an adjustable direct current power supply with positive and negative electrode interfaces of a specially-made container, inserting a cathode of the container into electrolyte, and clamping the positive electrode of the container to an alloy to be prepared; turning on a direct current power supply, adjusting to a constant voltage mode, setting a voltage of 8V, inserting an anode into electrolyte, observing a sample testing surface and a cathode to generate a large amount of fine bubbles, slightly shaking a sample clamp, immediately dissipating the fine bubbles, slowly adjusting the voltage to 16V and keeping, observing that only the cathode has dense bubbles to dissipate through a window at the upper end of a container, continuously observing an alloy testing surface to obtain grey-white color, waiting for gradual fading of the grey-white color of the sample testing surface, slightly shaking the anode to clearly see that the sample testing surface has a mirror reflection characteristic, immediately taking out an anode sample, immediately putting the anode sample into a beaker containing absolute ethyl alcohol, vibrating and cleaning by using ultrasonic waves, then clamping the sample by using tweezers, and drying the absolute ethyl alcohol on the surface to obtain a perfect sample as shown in figure 3, wherein the sample rating of AZ31 is 95.67%, and the sample rating of AZ61-1Ca is 98.73%.
Example 3
And preparing an aging treatment zinc alloy EBSD sample. Taking a heat-treated Zn-0.1Mg alloy with larger grain size as an example, taking the zinc alloy to be prepared, carrying out sand paper grinding, and adding a prepared electrolytic polishing solution of 10% perchloric acid ethanol saturated ethylene diamine tetraacetic acid into a special container; adding dry ice particles into the interlayer of the container; a thermometer waiting to be inserted into the electrolytic polishing solution showed a temperature of-30 ℃; connecting the positive electrode and the negative electrode of an adjustable direct current power supply with positive and negative electrode interfaces of a specially-made container, inserting a cathode of the container into electrolyte, and clamping the positive electrode of the container to an alloy to be prepared; turning on a direct current power supply, adjusting to a constant voltage mode, setting a voltage of 10V, inserting an anode into electrolyte, observing that a sample testing surface generates a small amount of bubbles, observing that a cathode generates a large amount of fine bubbles, slowly adjusting the voltage to 26V and keeping, observing that only the cathode has dense bubbles escaping through a window at the upper end of a container, observing an alloy testing surface that a sand paper is used for polishing scratches, continuously observing and waiting that the sample testing surface is shallow until the sand paper is not seen, slightly shaking the anode to clearly see that the sample testing surface has a mirror reflection characteristic, immediately taking out an anode sample, immediately putting the anode sample into a beaker containing absolute ethyl alcohol, using ultrasonic oscillation for cleaning, then using a clamp to clamp the sample and blow the absolute ethyl alcohol on the surface to obtain a perfect sample as shown in figure 8, clearly observing a zinc alloy crystal boundary, twin crystals in the crystal and no interference of stains on the surface, wherein EBSD-IPF pictures can correspond to the shapes of SEM pictures of the same area one by one, the calibration rate was 99.32%.
Example 4
Titanium alloy EBSD samples were prepared. Taking TA2 titanium alloy with isometric crystal as an example, taking the titanium alloy to be prepared, carrying out sand paper grinding, and adding the prepared electrolytic polishing solution of 20% perchloric acid ethanol saturated ethylene diamine tetraacetic acid into a special container; adding dry ice particles into the interlayer of the container; a thermometer waiting to be inserted into the electrolytic polishing solution showed a temperature of-40 ℃; connecting the positive electrode and the negative electrode of an adjustable direct current power supply with positive and negative electrode interfaces of a specially-made container, inserting a cathode of the container into electrolyte, and clamping the positive electrode of the container to an alloy to be prepared; turning on a direct current power supply, adjusting to a constant voltage mode, setting a voltage to be 15V, inserting an anode into electrolyte, observing that a sample testing surface generates a small amount of bubbles, observing that a cathode generates a large amount of bubbles, slowly adjusting the voltage to be 30V and keeping, observing that only the cathode has a large amount of bubbles escaping through a window at the upper end of a container, observing an alloy testing surface by using abrasive paper to polish scratches, continuously observing and waiting that the sample testing surface is polished by the abrasive paper until the scratches are shallow and disappear, lightly shaking the anode to clearly see that the sample testing surface has the characteristic of mirror reflection, immediately taking out an anode sample, immediately putting the anode sample into a beaker containing absolute ethyl alcohol, vibrating and cleaning by using ultrasonic waves, then clamping the sample by using tweezers and drying the absolute ethyl alcohol on the surface to obtain a perfect sample as shown in figure 6, the grain boundary and the twin crystal in the crystal of the titanium alloy can be clearly observed, the surface is free from dirt interference, and the calibration rate is 96.91%.
Comparative example 1
This comparative example is used to illustrate the effect of the electropolishing step (taking the gray-white step, the later gray-white step, and the mirror-surface step as examples). Taking a heat-treated Zn-0.1Mg alloy with larger grain size as an example, taking the zinc alloy to be prepared, carrying out sand paper grinding, and adding a prepared electrolytic polishing solution of 10% perchloric acid ethanol saturated ethylene diamine tetraacetic acid into a special container; adding dry ice particles into the interlayer of the container; a thermometer waiting to be inserted into the electrolytic polishing solution showed a temperature of-30 ℃; connecting the positive electrode and the negative electrode of an adjustable direct current power supply with positive and negative electrode interfaces of a specially-made container, inserting a cathode of the container into electrolyte, and clamping the positive electrode of the container to an alloy to be prepared; turning on a direct current power supply, adjusting to a constant voltage mode, setting the voltage to be 10V, inserting the anode into the electrolyte, observing that a small amount of bubbles are generated on a sample testing surface, a large amount of fine bubbles appear on the cathode, slowly adjusting the voltage to 26V and keeping, observing that only the dense bubbles escape from the cathode through a window at the upper end of the container, observing a grey-white surface on an alloy testing surface, taking out an anode sample, immediately putting the anode sample into a beaker containing absolute ethyl alcohol, oscillating and cleaning by using ultrasonic waves, then clamping the sample by using tweezers, and drying the absolute ethyl alcohol on the surface by blowing to obtain the surface appearance of the sample as shown in figure 4, a large amount of white oxide with dense tip morphology can be observed, the sample is reground and electropolished again, the gray color gradually disappears through the window at the upper end of the container after the voltage is adjusted, at this time, the sample is taken out, and the beginning of the reduction of the dense tip-like white oxide can be observed after the same treatment as that shown in fig. 4. The same observation of the mirror surface stage sample can obtain the final perfect appearance as shown in figure 4.
Comparative example 2
The comparative example is used for explaining the influence of voltage in electrolytic polishing, and the voltage in the technical scheme of the invention is directly subjected to electrolytic polishing without later regulation. Taking the rare earth magnesium alloy with higher second phase content as an example, taking the rare earth magnesium alloy to be prepared, carrying out sand paper grinding, and adding the prepared electrolytic polishing solution of 10% perchloric acid ethanol saturated ethylene diamine tetraacetic acid into a special container; adding dry ice particles into the interlayer of the container; a thermometer waiting to be inserted into the electrolytic polishing solution showed a temperature of-40 ℃; connecting the positive electrode and the negative electrode of an adjustable direct current power supply with positive and negative electrode interfaces of a specially-made container, inserting a cathode of the container into electrolyte, and clamping the positive electrode of the container to an alloy to be prepared; turning on a direct current power supply, adjusting to a constant voltage mode, setting a voltage to be 14V, inserting an anode into electrolyte, observing a sample testing surface and a cathode to generate a large amount of fine bubbles, slightly shaking a sample clamp, immediately dissipating the fine bubbles, observing that only the cathode has dense bubbles to dissipate through a window at the upper end of a container, continuously observing and waiting for gradual fading of the gray and white of the sample testing surface, slightly shaking the anode to clearly see that the sample testing surface has a mirror reflection characteristic, immediately taking out an anode sample, immediately putting the anode sample into a beaker containing absolute ethyl alcohol, using ultrasonic oscillation to clean, then clamping the sample with tweezers, drying the absolute ethyl alcohol on the surface to obtain the sample shown in figures 5 and 7, clearly observing that the surface has unevenness and a large amount of second phases which are difficult to be electrolyzed and removed, wherein the surface has no interference stains, and clearly showing that the duration of the gray stage after voltage adjustment is shortened by comparing with the mode of adjusting the voltage, the sample has higher flatness, the second phase and the matrix do not have huge fluctuation, and the electrolytic polishing process for adjusting the voltage has better sample quality.
In conclusion, by means of the technical scheme, the novel electrolytic polishing process is adopted, the complicated process of mechanical polishing is omitted, and the method has the advantages of convenience and low cost; the sample can be prepared by grinding a flat test surface with sand paper, so that the sample preparation time is greatly shortened, the sample quality is improved, the preparation cost is greatly reduced, the SEM and EBSD samples can be obtained only by a one-step method, and the SEM sample does not need to be obtained by secondary corrosion, so that the polishing efficiency is improved; the method can universally prepare most metal materials such as magnesium alloy, aluminum alloy, zinc alloy, iron-cobalt-nickel alloy, copper alloy, titanium alloy, high-entropy alloy, stainless steel, complex rare earth alloy and the like, has better universality and universality, and can realize the preparation of different metals by only adjusting the adaptive voltage value in the electrolytic process; the electrolytic polishing solution is a corrosive solution, the surface of a sample is uniformly corroded in the electrolytic polishing process, the crystal boundary and the second phase of the sample can be perfectly and clearly imaged by a scanning electron microscope, and the electrolytic polishing solution has universality and universality, so that the cost is saved, the difficulty in storage and waste liquid recovery and treatment is reduced, and the huge pressure on environmental protection caused by different electrolytes is reduced; by adopting the polishing method to process the EBSD sample, the stress layer on the surface of the test surface can be effectively removed, the surface relief of the test surface is improved, the flatness of the test surface is effectively improved, the test surface has better surface gloss after treatment, and the definition and the integrity of the chrysanthemum flower pool pattern in the EBSD test are improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A general electropolishing method for preparing SEM and EBSD samples, comprising the steps of:
s1, processing a test plane of the sample to be prepared according to the requirement;
s2, preparing an electrolytic polishing solution and adding ethylene diamine tetraacetic acid into the electrolytic polishing solution;
s3, adopting a special container to contain the prepared electrolytic polishing solution and performing cooling treatment;
s4, connecting the special container with an external direct current power supply;
s5, putting the special container and the sample to be prepared into the electrolytic polishing solution and turning on a direct current power supply;
and S6, judging whether the preparation is finished or not by observing the light reflection degree of the test plane.
2. The general electropolishing method for preparing SEM and EBSD samples according to claim 1, wherein the test plane is ground or cut in S1 to meet the test requirements of SEM and EBSD.
3. The general electropolishing method for preparing SEM and EBSD samples according to claim 1, wherein the electropolishing solution is prepared using perchloric acid and absolute ethanol, and the concentration of perchloric acid is between 5% and 20%.
4. The general electropolishing method for preparing SEM and EBSD samples according to claim 2 or 3, wherein 10-20 g/L EDTA is added into the electropolishing solution of S2 when the electropolishing solution is at-20 ℃ and stirred to make the electropolishing solution reach saturation.
5. The general electropolishing method for preparing SEM and EBSD samples according to claim 4, wherein the temperature of S3 is reduced by adding dry ice particles into the container sandwich, and the temperature of the electropolishing solution is reduced to-30 ℃ to-60 ℃.
6. The general electropolishing method for preparing SEM and EBSD samples of claim 1, wherein the dc power supply in S4 is an adjustable dc power supply, and positive and negative electrodes of the adjustable dc power supply are respectively and correspondingly connected to positive and negative electrodes of the special container.
7. The general electropolishing method for preparing SEM and EBSD samples according to claim 6, wherein the voltage is adjusted in S5 to adapt to polishing of different metal materials, and a constant voltage mode is adopted during polishing.
8. The general electropolishing method for preparing SEM and EBSD samples of claim 1, wherein the custom container cathode is inserted into the electrolyte solution before the dc power is turned on in S5, and the custom container anode holds the sample to be prepared.
9. The general electropolishing method for preparing SEM and EBSD samples according to claim 1, wherein the step of observing the degree of light reflection of the test plane to determine whether the preparation is completed in S6 comprises the steps of:
s61, observing whether the test plane is covered with fine bubbles;
s62, observing whether the test plane is covered with a layer of grey oxide;
s63, observing whether the test plane generates mirror reflection;
s64, if all the phenomena occur, the sample preparation is finished;
and S65, turning off the power supply to stop the electrolytic polishing.
10. The general electropolishing method for preparing SEM and EBSD samples of claim 9, wherein if the test plane is darkened or blackened at S6, the sample preparation fails.
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