CN113943970A - 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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- CN113943970A CN113943970A CN202010687235.8A CN202010687235A CN113943970A CN 113943970 A CN113943970 A CN 113943970A CN 202010687235 A CN202010687235 A CN 202010687235A CN 113943970 A CN113943970 A CN 113943970A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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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 8-15 percent and the ethylene glycol monobutyl ether accounts for 92-85 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 'neck down'; 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, 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.
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 (3DAP) 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 mainly 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 needle point sample, and the radius of curvature of the needle point of the 3DAP sample is required to be less than 100 nm. There are generally two methods for preparing tips: firstly, a two-step electrolytic polishing method is adopted; the method comprises the steps of processing a sample into a filament 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 both consist 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 99.0 wt%.
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 thin-wire-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 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 0.5-1 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.
According to the electrolytic polishing method of the electrolytic polishing solution for preparing the nickel-based high-temperature alloy needle point sample, the rough polishing voltage is 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 from top to bottom by absolute ethyl alcohol, and the 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 electrolytic polishing solution with high acidity, is not easy to fall off after being attached to a sample, cannot remove sample materials when the corrosion products are accumulated in a large amount in the polishing process, and is low in needle point preparation efficiency 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 'neck down'; 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, 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 shows the distribution pattern of all alloy elements in three-dimensional space of a sample of Ni-based superalloy K416B needlepoint prepared in example 3, which is subjected to a 3DAP experiment.
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 fine polishing electrolyte, the perchloric acid is 4 percent and the ethylene glycol monobutyl 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 thin-wire-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 3.5 mm; vertically inserting a sample blank into a horizontal platinum wire ring, dripping a 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 superalloy 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 Ni-based superalloy GH4169 tip sample prepared in example 1 was subjected to a 3DAP experiment to give a distribution pattern of some alloying elements such as Ni, Al and Ti in three-dimensional space. As can be seen from FIG. 1, the tip of the sample obtained by this example has a curvature diameter of about 65nm, an analysis length of 240nm, and the sample is not broken at the end of the experiment.
Example 2
In the embodiment, a tip 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 fine polishing electrolyte, the perchloric acid content is 2% by volume percentage, and the ethylene glycol monobutyl ether content is 98%. 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 thin-wire-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 3.5 mm; vertically inserting a sample blank into a horizontal platinum wire ring, dripping a 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 sample is naturally dried.
As shown in FIG. 2, the Ce-doped Ni-based superalloy GH4169 tip sample prepared in example 2 was subjected to a 3DAP experiment to give a distribution pattern of some alloying elements (e.g., Ni, Al and Ti) in three-dimensional space. 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 by electropolishing nickel-base superalloy K416B. In the rough polishing electrolyte, the perchloric acid is 10 percent and the ethylene glycol monobutyl ether is 90 percent 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 thin-wire-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 3.5 mm; vertically inserting a sample blank into a horizontal platinum wire ring, dripping a 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 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. 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 (6)
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, 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%.
2. The electropolishing solution for preparing nickel-base superalloy needle tip samples of claim 1, wherein the perchloric acid concentration is 70.0 wt% to 72.0 wt%, and the concentration of butyl cellosolve is 99.0 wt%.
3. 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.
4. An electrolytic polishing method of the electrolytic polishing solution for preparing the nickel-based superalloy needle tip sample as set forth in any one of claims 1 to 3, characterized by comprising the following steps:
(1) preparing the nickel-based high-temperature alloy into a thin-wire-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 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 0.5-1 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.
5. The electrolytic polishing method of the electrolytic polishing solution for preparing the nickel-based superalloy needle tip sample as claimed in claim 4, wherein the rough polishing voltage is 10-20V; the polishing voltage is 4-10V.
6. The electropolishing method using electropolishing solutions for preparing nickel-base superalloy needle tip samples according to claim 4, 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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Non-Patent Citations (4)
| Title |
|---|
| 刘凤岐: "金属样品的电解抛光", 《鞍钢技术》 * |
| 宋元元等: "Fe-Ni基合金时效过程中γ'相析出的原子探针层析技术研究", 《金属学报》 * |
| 左鹏鹏等: "三维原子探针表征淬回火Cr-Mo-V-Ni中合金钢的元素分布", 《材料导报》 * |
| 王晓姣等: "三维原子探针对10Ni3MnCuAl钢中NiAl和Cu析出位置关系的研究", 《上海金属》 * |
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