CN113943970B - Electrolytic polishing solution and electrolytic polishing method for preparing nickel-based high-temperature alloy needle point sample - Google Patents
Electrolytic polishing solution and electrolytic polishing method for preparing nickel-based high-temperature alloy needle point sample Download PDFInfo
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- CN113943970B CN113943970B CN202010687235.8A CN202010687235A CN113943970B CN 113943970 B CN113943970 B CN 113943970B CN 202010687235 A CN202010687235 A CN 202010687235A CN 113943970 B CN113943970 B CN 113943970B
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Abstract
The invention relates to the technical field of electrolytic polishing, in particular to an electrolytic polishing solution and an electrolytic polishing method for preparing a nickel-based high-temperature alloy needle point sample. The electrolytic polishing solution is divided into a rough polishing electrolyte and a fine polishing electrolyte, and the rough polishing electrolyte and the fine polishing electrolyte both consist of perchloric acid and ethylene glycol monobutyl ether; in the rough polishing electrolyte, the perchloric acid accounts for 8 to 15 percent and the ethylene glycol monobutyl ether accounts for 92 to 85 percent by volume percentage; in the fine polishing electrolyte, the perchloric acid accounts for 2-4 percent and the ethylene glycol monobutyl ether accounts for 98-96 percent by volume percentage. The electrolytic polishing method comprises two steps: the first step is rough polishing, polishing the blank to form a 'necking'; the second step is fine polishing, the neck is polished off to form a sharp needle point. The electrolytic polishing solution disclosed by the invention is simple in preparation, normal in electrolytic temperature, easy to operate and remarkable in polishing effect, and greatly improves the efficiency of preparing a nickel-based superalloy needle point sample and the success rate of carrying out a related three-dimensional atom probe experiment.
Description
Technical Field
The invention relates to the technical field of electrolytic polishing, in particular to an electrolytic polishing solution and an electrolytic polishing method for preparing a nickel-based high-temperature alloy needle point sample.
Background
The three-dimensional atom probe chromatographic technology (3 DAP) can reveal the element space distribution information on the atomic scale and can provide a material three-dimensional analysis map with the atomic scale resolution, is an advanced technology for analyzing the three-dimensional space distribution and component representation of a nanometer precipitated phase, and is one of the analysis and test means with the highest spatial resolution at present. 3DAP has been used to study the precipitation process of phases at the nanoscale, the composition, size, number density, etc. of nanoclusters or precipitated phases. In the field of high-temperature alloys, 3DAP is more used for researching the evolution behavior of a gamma'/gamma interface in a nickel-based high-temperature alloy, and comprises the distribution and evolution characteristics of elements such as Hf, ti, ta and Mo on the interface.
The key point for the smooth operation of the 3DAP experiment is to obtain a high-quality pinpoint sample, and the pinpoint of the 3DAP sample requires the curvature radius to be less than 100nm. There are generally two methods of preparing a needle tip: firstly, a two-step electrolytic polishing method is adopted; the method comprises the steps of processing a sample into a fine-line sample, roughly polishing the middle part of the sample to be in a necking shape by using an electrolyte, and finely polishing the sample to be separated from top to bottom to obtain two needle point samples. One is to cut the sample directly at a specific area using a Focused Ion Beam (FIB). FIB-prepared samples are expensive and may cause some degree of ion damage to the sample. For experiments which do not require a specific area, the sample can be prepared by an electrolytic polishing method, the operation is convenient and simple, and the cost price is low. The rough polishing electrolyte of the nickel-based superalloy reported at present generally consists of perchloric acid and glacial acetic acid, but in the polishing process, black corrosion products are easily generated on the surface of a sample, the corrosion products are attached to the sample and are not easy to fall off, the preparation of a needle point sample is very difficult, the production efficiency is low, the quality of the prepared needle point is not high, and the success rate of a 3DAP experiment is low.
Disclosure of Invention
The invention mainly aims to provide an electrolytic polishing solution and an electrolytic polishing method for preparing a nickel-based superalloy needle point sample, and the quality of the 3DAP needle point sample and the success rate of an experiment are improved.
The purpose of the invention is realized by the following technical scheme:
an electrolytic polishing solution for preparing a nickel-based superalloy needle point sample is divided into a rough polishing electrolyte and a fine polishing electrolyte, wherein the rough polishing electrolyte and the fine polishing electrolyte are both composed of perchloric acid and ethylene glycol butyl ether; in the rough polishing electrolyte, according to volume percentage, perchloric acid is 8-15%, butyl cellosolve is 92-85%, and the volume content of the perchloric acid and the butyl cellosolve is 100%; in the fine polishing electrolyte, the volume percentage of perchloric acid is 2-4%, the volume percentage of ethylene glycol monobutyl ether is 98-96%, and the volume percentage of the perchloric acid and the ethylene glycol monobutyl ether is 100%.
The electrolytic polishing solution for preparing the nickel-based superalloy needle point sample has the perchloric acid concentration of 70.0-72.0 wt% and the ethylene glycol monobutyl ether concentration of 99.0wt%.
The electrolytic polishing solution for preparing the nickel-based high-temperature alloy needle point sample is prepared by adding ethylene glycol monobutyl ether into perchloric acid at room temperature according to a preparation ratio and uniformly stirring to form the electrolytic polishing solution.
The electrolytic polishing method of the electrolytic polishing solution for preparing the nickel-based superalloy needle point sample comprises the following specific steps:
(1) Preparing the nickel-based high-temperature alloy into a filament-shaped sample blank with the thickness of 0.5mm multiplied by 15mm by utilizing wire cutting, and connecting the sample blank serving as an anode with the positive electrode of a direct-current power supply; a platinum wire ring is used as a cathode and is connected with the negative electrode of the direct current power supply; inserting a sample blank into a platinum wire ring, dripping rough polishing electrolyte into the platinum wire ring, moving the platinum wire ring up and down, and roughly polishing the middle part of the sample blank within a length range of 3-5 mm;
(2) Roughly polishing the sample according to the step (1) until the middle part of the sample appears in a necking shape with the diameter of 0.5-1 mm, and stopping roughly polishing; and replacing the rough polishing electrolyte with the fine polishing electrolyte, continuing fine polishing, and breaking the sample blank into two halves from the middle to obtain the nickel-based superalloy needle point sample.
The electrolytic polishing method of the electrolytic polishing solution for preparing the nickel-based superalloy needle point sample has the rough polishing voltage of 10-20V; the polishing voltage is 4-10V.
According to the electrolytic polishing method of the electrolytic polishing solution for preparing the nickel-based high-temperature alloy needle point sample, after the electrolytic polishing is finished, the needle point of the needle point sample is downwards washed by absolute ethyl alcohol from top to bottom, and the needle point sample is naturally air-dried.
The design idea of the invention is as follows: the nickel-based high-temperature alloy is easy to generate black corrosion products in an electrolytic polishing solution with higher acidity, the black corrosion products are attached to a sample and are not easy to fall off, the sample material cannot be removed when the corrosion products are accumulated more in the polishing process, and the needle tip preparation efficiency is low or even cannot be completed. The ethylene glycol monobutyl ether is almost non-corrosive, can effectively reduce the concentration of perchloric acid when used as a solvent, and has bright sample surface, simple operation and high efficiency of preparing a needle point sample in the electrolytic polishing process.
The invention has the advantages and beneficial effects that:
1. the nickel-based superalloy electrolytic polishing solution comprises perchloric acid and ethylene glycol monobutyl ether. The electrolytic polishing method comprises two steps: the first step is rough polishing, polishing the blank to form a 'necking'; the second step is fine polishing, which breaks the neck to form a sharp needle point. The electrolytic polishing solution disclosed by the invention is simple in preparation, easy to operate and obvious in polishing effect, and the electrolytic temperature is normal temperature, so that the efficiency of preparing the nickel-based high-temperature alloy needle point sample and the success rate of carrying out related three-dimensional atom probe experiments are greatly improved.
2. The invention can be used for needle point samples required by three-dimensional atom probe experiments or transmission electron microscope observation and the like, and the samples can be used in analytical means such as transmission electron microscope observation, three-dimensional atom probe experiments and the like.
3. The invention can be applied to the field of nickel-based high-temperature alloy electrolytic polishing.
Drawings
FIG. 1 shows a distribution pattern of some alloying elements such as Ni, al and Ti in three-dimensional space, which is obtained by performing 3DAP experiments on samples of the Ni-based superalloy GH4169 tip prepared in example 1.
FIG. 2 shows a distribution pattern of some alloying elements (such as Ni, al and Ti) in three-dimensional space, which is obtained by performing 3DAP (Dacron) experiments on samples of the Ce-doped Ni-based superalloy GH4169 tip prepared in example 2.
Fig. 3 is a 3DAP experiment performed on a sample of the nickel-base superalloy K416B needle tip prepared in example 3, and shows a distribution pattern of all alloying elements in a three-dimensional space.
Detailed Description
The present invention will be explained in further detail below by way of examples and figures.
Example 1
In the embodiment, a needle point sample is prepared from the nickel-based superalloy GH4169 by an electrolytic polishing method. In the rough polishing electrolyte, the perchloric acid is 8 percent and the ethylene glycol monobutyl ether is 92 percent by volume percentage. In the finish polishing electrolyte, the perchloric acid is 4 percent and the ethylene glycol butyl ether is 96 percent by volume percentage.
The electrolytic polishing solution is used for preparing a nickel-based high-temperature alloy needle point sample and comprises the following specific steps:
(1) Preparing the nickel-based high-temperature alloy into a filament-shaped sample blank with the diameter of 0.5mm multiplied by 15mm by utilizing wire cutting, and connecting the sample blank serving as an anode with the anode of a direct-current power supply; a platinum wire ring is used as a cathode and is connected with the negative electrode of a direct current power supply, the inner diameter of the platinum wire ring is about 3mm, and the outer diameter of the platinum wire ring is about 3.5mm; vertically inserting a sample blank into a horizontal platinum wire ring, dripping rough polishing electrolyte into the platinum wire ring, fixing the sample blank, moving the platinum wire ring up and down, and roughly polishing the middle part of the sample blank within a length range of 3-5 mm, wherein the rough polishing voltage is 15V;
(2) Roughly polishing the sample according to the step (1) until the middle part of the sample is in a necking shape with the diameter of 0.5-1 mm, and stopping roughly polishing; and (3) replacing the rough polishing electrolyte with a fine polishing electrolyte, continuing to perform fine polishing, wherein the fine polishing voltage is 6V, and breaking the sample blank into two halves from the middle to obtain the nickel-based high-temperature alloy needle point sample.
(3) And after the electrolytic polishing is finished, the needle point of the needle point sample is downwards washed by absolute ethyl alcohol from top to bottom, and the sample is naturally dried.
As shown in fig. 1, the nickel-base superalloy GH4169 needle tip sample prepared in example 1 was subjected to a 3DAP experiment, and a distribution pattern of some alloying elements such as Ni, al and Ti in a three-dimensional space was shown. As can be seen from FIG. 1, the tip of the tip sample obtained by using this example has a curvature diameter of about 65nm, an analysis length of 240nm, and the sample is not fractured at the end of the experiment.
Example 2
In the embodiment, a needle point sample is prepared from the Ce-added nickel-based superalloy GH4169 by an electrolytic polishing method. In the rough polishing electrolyte, the perchloric acid is 15% and the ethylene glycol monobutyl ether is 85% by volume percentage. In the finish polishing electrolyte, the content of perchloric acid is 2 percent and the content of ethylene glycol monobutyl ether is 98 percent according to volume percentage. The tip samples were prepared according to the specified electropolishing procedure.
The electrolytic polishing solution is used for preparing a nickel-based high-temperature alloy needle point sample and comprises the following specific steps:
(1) Preparing the nickel-based high-temperature alloy into a filament-shaped sample blank with the thickness of 0.5mm multiplied by 15mm by utilizing wire cutting, and connecting the sample blank serving as an anode with the positive electrode of a direct-current power supply; a platinum wire ring is used as a cathode and is connected with the negative electrode of a direct current power supply, the inner diameter of the platinum wire ring is about 3mm, and the outer diameter of the platinum wire ring is about 3.5mm; vertically inserting a sample blank into a horizontal platinum wire ring, dripping rough polishing electrolyte into the platinum wire ring, fixing the sample blank, moving the platinum wire ring up and down, and roughly polishing the middle part of the sample blank within a length range of 3-5 mm, wherein the rough polishing voltage is 10V;
(2) Roughly polishing the sample according to the step (1) until the middle part of the sample is in a necking shape with the diameter of 0.5-1 mm, and stopping roughly polishing; and (3) replacing the rough polishing electrolyte with a fine polishing electrolyte, continuing fine polishing, wherein the fine polishing voltage is 4V, and breaking the sample blank into two halves from the middle to obtain the nickel-based high-temperature alloy needle point sample.
(3) And after the electrolytic polishing is finished, the needle point of the needle point sample is downwards washed by absolute ethyl alcohol from top to bottom, and the needle point sample is naturally dried.
As shown in FIG. 2, the Ce-added Ni-based superalloy GH4169 tip sample prepared in example 2 was subjected to a 3DAP experiment, and a distribution pattern of some alloying elements (such as Ni, al and Ti) in a three-dimensional space is given. As can be seen from FIG. 2, the tip of the sample obtained by this example has a curvature diameter of about 80nm, an analysis length of 320nm, and the sample is not broken at the end of the experiment.
Example 3
In this example, a tip sample was prepared from nickel-base superalloy K416B by electropolishing. In the rough polishing electrolyte, the perchloric acid is 10% and the ethylene glycol butyl ether is 90% by volume percentage. In the fine polishing electrolyte, the perchloric acid content is 3% by volume percentage, and the ethylene glycol monobutyl ether content is 97%. The tip samples were prepared according to the specified electropolishing procedure.
The electrolytic polishing solution is used for preparing a nickel-based high-temperature alloy needle point sample and comprises the following specific steps:
(1) Preparing the nickel-based high-temperature alloy into a filament-shaped sample blank with the diameter of 0.5mm multiplied by 15mm by utilizing wire cutting, and connecting the sample blank serving as an anode with the anode of a direct-current power supply; a platinum wire ring is used as a cathode and is connected with the negative electrode of a direct current power supply, the inner diameter of the platinum wire ring is about 3mm, and the outer diameter of the platinum wire ring is about 3.5mm; vertically inserting a sample blank into a horizontal platinum wire ring, dripping rough polishing electrolyte into the platinum wire ring, fixing the sample blank, moving the platinum wire ring up and down, and roughly polishing the middle part of the sample blank within a length range of 3-5 mm, wherein the rough polishing voltage is 20V;
(2) Roughly polishing the sample according to the step (1) until the middle part of the sample is in a necking shape with the diameter of 0.5-1 mm, and stopping roughly polishing; and (3) replacing the rough polishing electrolyte with a fine polishing electrolyte, continuing fine polishing, wherein the fine polishing voltage is 8V, and breaking the sample blank into two halves from the middle to obtain the nickel-based superalloy needle tip sample.
(3) And after the electrolytic polishing is finished, the needle point of the needle point sample is downwards washed by absolute ethyl alcohol from top to bottom, and the needle point sample is naturally dried.
As shown in fig. 3, the ni-based superalloy K416B tip sample prepared in example 3 was subjected to a 3DAP experiment to give a distribution pattern of all alloying elements in three dimensions. As can be seen from FIG. 3, the tip of the sample obtained by this example has a curvature diameter of about 60nm, an analysis length of 320nm, and the sample is not broken at the end of the experiment.
Claims (5)
1. An electrolytic polishing solution for preparing a nickel-based superalloy needle point sample is characterized in that the electrolytic polishing solution is divided into a rough polishing electrolyte and a fine polishing electrolyte, wherein the rough polishing electrolyte and the fine polishing electrolyte are both composed of perchloric acid and ethylene glycol butyl ether; in the rough polishing electrolyte, by volume percentage, perchloric acid is 8-15%, butyl cellosolve is 92-85%, and the volume content of the perchloric acid and the butyl cellosolve is 100%; in the finish polishing electrolyte, according to volume percentage, perchloric acid is 2-4%, butyl cellosolve is 98-96%, and the volume percentage of the perchloric acid and the butyl cellosolve is 100%;
the perchloric acid concentration is 70.0wt% -72.0 wt%, and the ethylene glycol monobutyl ether concentration is 99.0wt%.
2. The electropolishing solution for preparing nickel-based superalloy needle tip samples according to claim 1, wherein butyl glycol ether is added to perchloric acid at room temperature according to a preparation ratio, and the mixture is uniformly stirred to form the electropolishing solution.
3. The electrolytic polishing method of the electrolytic polishing solution for preparing the nickel-based superalloy needle tip sample as recited in any one of claims 1 to 2, comprising the following steps:
(1) Preparing the nickel-based high-temperature alloy into a filament-shaped sample blank with the diameter of 0.5mm multiplied by 15mm by utilizing wire cutting, and connecting the sample blank serving as an anode with the anode of a direct-current power supply; a platinum wire ring is used as a cathode and is connected with the negative electrode of the direct current power supply; inserting a sample blank into a platinum wire ring, dripping a rough polishing electrolyte into the platinum wire ring, moving the platinum wire ring up and down, and roughly polishing the middle part of the sample blank within a length range of 3-5 mm;
(2) Roughly polishing the sample according to the step (1) until the middle part of the sample is in a necking shape with the diameter of 0.5-1mm, and stopping roughly polishing; and replacing the rough polishing electrolyte with the fine polishing electrolyte, continuing fine polishing, and breaking the sample blank into two halves from the middle to obtain the nickel-based superalloy needle point sample.
4. The electropolishing method of claim 3, wherein the rough polishing voltage is 10-20V; the polishing voltage is 4-10V.
5. The electropolishing method using electropolishing solutions for preparing nickel-base superalloy needle tip samples according to claim 3, wherein after electropolishing is completed, the needle tip of the needle tip sample is placed downward, washed with absolute ethyl alcohol from top to bottom, and air-dried.
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