CN116818482A - Electrolytic extraction analysis method for precipitated phase in cobalt-based superalloy - Google Patents
Electrolytic extraction analysis method for precipitated phase in cobalt-based superalloy Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims abstract description 74
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 59
- 239000010941 cobalt Substances 0.000 title claims abstract description 58
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 58
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000004458 analytical method Methods 0.000 title claims abstract description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 150
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 130
- 239000003792 electrolyte Substances 0.000 claims abstract description 76
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 235000011187 glycerol Nutrition 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 19
- 235000015165 citric acid Nutrition 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 70
- 239000002775 capsule Substances 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 34
- 239000005486 organic electrolyte Substances 0.000 claims description 32
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 239000012153 distilled water Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
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- 238000005303 weighing Methods 0.000 claims description 15
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- QJWQYOHBMUQHGZ-UHFFFAOYSA-N ethanol;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound CCO.OC(=O)CC(O)(C(O)=O)CC(O)=O QJWQYOHBMUQHGZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000001680 brushing effect Effects 0.000 claims description 12
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- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
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- 238000005363 electrowinning Methods 0.000 claims 1
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- 238000001556 precipitation Methods 0.000 abstract description 3
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- 230000000052 comparative effect Effects 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
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- 238000004090 dissolution Methods 0.000 description 15
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- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 3
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 150000001450 anions Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
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- 150000001768 cations Chemical class 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 238000005485 electric heating Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
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- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
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- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses an electrolytic extraction analysis method of a precipitated phase in a cobalt-based superalloy, belongs to the technical field of metal material analysis, and solves the problem that the extraction rate of gamma' is very low when the precipitated phase in the existing cobalt-based superalloy is analyzed. The electrolytic extraction analysis method comprises the step of carrying out electrolysis by adopting an aqueous electrolyte of an aqueous solution of three components of ammonium chloride, citric acid and glycerol. In the water-based electrolyte, the mass concentration of ammonium chloride is 47-52 g/L, the mass concentration of citric acid is 17-22 g/L, and the volume concentration of glycerin is 4-6%. The method can be used for effectively extracting the gamma '-phase in the cobalt-based superalloy, and further realizing accurate analysis of the gamma' -phase, thereby providing technical support for exploring the influence of the relative material performance of precipitation and optimizing the material.
Description
Technical Field
The invention belongs to the technical field of metal material analysis, and particularly relates to an electrolytic extraction analysis method for a precipitated phase in cobalt-based superalloy.
Background
The cobalt-based superalloy is an austenitic superalloy with the cobalt content of 40-65%, is a superalloy for an aeroengine fastener which is used below 600 ℃ for a long time at present, has certain high-temperature strength and good hot corrosion resistance and oxidation resistance, and is suitable for manufacturing guide blades, nozzle guide vanes, diesel nozzles and the like of aerojet engines, industrial gas turbines and ship gas turbines. Under the proper heat treatment process conditions, the cobalt-based superalloy can form a small amount of carbide phase and a fine dispersion gamma' phase, thereby strengthening the material. The electrolytic extraction method of cobalt-based superalloy precipitated phase has been reported recently, when the electrolytic extraction is carried out under the common electrolytic extraction conditions of iron-based or nickel-based alloy, carbide and boride can be extracted, but the extraction rate of gamma' is very low; when the common extraction electrolysis conditions of nickel base alloy or iron-nickel base alloy are adopted, gamma' phase in cobalt base superalloy is electrolyzed together with the base body, when other electrolyte is used, the extraction rate is very low, and ions dissolved in the base body react with electrolyte components to generate undissolved substances which interfere with the measurement of precipitated phases.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide an electrolytic extraction analysis method for a precipitated phase in a cobalt-based superalloy, which can solve at least one of the following technical problems: (1) When the existing cobalt-based superalloy is analyzed by precipitated phase, carbide and boride can be extracted by adopting the common electrolytic extraction conditions of iron base or nickel base alloy, but the extraction rate of gamma' is very low; (2) When the common extraction electrolysis conditions of nickel base alloy or iron-nickel base alloy are adopted, the gamma' phase in the cobalt-base superalloy is electrolyzed together with the matrix; the existing electrolysis method can not accurately analyze the precipitated phase in the cobalt-based superalloy.
The aim of the invention is mainly realized by the following technical scheme:
in one aspect, the invention provides an electrolytic extraction analysis method of a precipitated phase in a cobalt-based superalloy, which comprises the step of carrying out electrolysis by adopting an aqueous electrolyte of an aqueous solution of three components of ammonium chloride, citric acid and glycerol.
Further, in the aqueous electrolyte, the mass concentration of ammonium chloride is 47-52 g/L, the mass concentration of citric acid is 17-22 g/L, and the volume concentration of glycerin is 4-6%.
Further, the preparation method of the aqueous electrolyte comprises the following steps: weighing ammonium chloride and citric acid, adding into water, stirring for dissolving, adding glycerol, and stirring uniformly to obtain water-based electrolyte.
Further, the electrolytic extraction analysis method also comprises an organic electrolyte electrolytic sample which adopts a methanol solution with three components of LiCl, sulfosalicylic acid and glycerol.
In addition, in the organic electrolyte, the mass concentration of LiCl is 8-12 g/L, the mass concentration of sulfosalicylic acid is 38-42 g/L, and the volume concentration of glycerin is 4-6%.
Further, the electrolytic extraction analysis method comprises:
s1, preparing a sample to be detected into an electrolysis sample required by electrolysis extraction;
s2, pre-electrolyzing the electrolytic sample by adopting an organic electrolyte, then electrolyzing the electrolytic sample,
s3, after the electrolysis of the organic electrolyte is finished, brushing the non-shedding precipitated phase powder into a beaker by using a citric acid ethanol solution, carrying out suction filtration on the powder in the beaker and the precipitated phase powder which falls into the capsule by using an inlet microporous filter membrane, respectively washing for a plurality of times by using a citric acid ethanol washing liquid and a citric acid water washing liquid in sequence, finally washing by using distilled water, and drying;
s4, continuously performing electrolytic extraction on the sample subjected to the electrolysis of the organic electrolyte by adopting a water-based electrolyte;
s5, turning off a power supply after the electrolysis is finished, taking out a sample electrolyzed by the water-based electrolyte, putting the sample into a beaker, directly brushing non-fallen precipitated phase powder into the beaker by using a citric acid aqueous solution, carrying out suction filtration on the precipitated phase powder in the beaker and the precipitated phase powder fallen into a capsule by using an inlet microporous filter membrane, sequentially washing the powder for a plurality of times by using a washing solution containing citric acid, washing residues by using distilled water, and drying;
s6, respectively adopting an X-ray diffractometer to analyze the precipitated phase powder collected by the twice electrolysis, and determining the type of the precipitated phase.
In S4, the current density is controlled to be 0.02-0.03A/cm < 2 >, the total current is 0.35-0.45A, and the temperature is 1-5 ℃.
In S5, the concentration of citric acid in the aqueous solution of citric acid is 8-12 g/L.
In S5, the concentration of citric acid in the citric acid aqueous solution is 5-10 g/L.
Further, the method also comprises the step of analyzing the content of each element in the precipitated phase by adopting quantitative electrolysis.
Compared with the prior art, the invention has at least one of the following beneficial effects:
a) According to the electrolytic extraction analysis method for the precipitated phases in the cobalt-based superalloy, disclosed by the invention, the cobalt-based superalloy is electrolyzed by adopting the aqueous electrolyte of the aqueous solution of (ammonium chloride+citric acid+glycerol), and by accurately controlling the electrolyte components and the electrolysis conditions, the matrix is dissolved, the gamma ' phase is left, the effective extraction of the gamma ' phase is realized, and further, the accurate analysis of the gamma ' phase is realized, so that technical support is provided for exploring the influence of the performance of the precipitated relative materials and optimizing the materials.
b) The method combines pre-electrolysis and electrolysis, and the pre-electrolysis can electrolyze one layer of the surface of an electrolysis sample, so that the problem of sample pollution in the sample preparation process is solved.
c) In the method, the electrolyte is put into the capsule, so that the reduction product of the cathode can be prevented from contaminating a precipitated phase.
d) The method of the invention filters the electrolyte before electrolysis, and can reduce the influence of impurities in the electrolyte on detection and observation of intermetallic compounds.
e) In the method, the type of the precipitated phase is determined by qualitative electrolysis analysis, and then the content of each element in the gamma 'phase can be obtained by quantitative electrolysis, so that the accurate analysis of the gamma' phase is realized.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and other advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the written description.
Drawings
The drawings are only for the purpose of illustrating the invention and are not to be construed as limiting the invention, like reference numerals referring to like parts throughout the several views.
FIG. 1 is a schematic view of an electrolytic sample placed in an electrolytic device;
FIG. 2a is a diffraction pattern of a precipitate phase obtained by electrolytic extraction with an organic electrolyte in example 1;
FIG. 2b is a diffraction pattern of a precipitated phase obtained by electrolytic extraction with an aqueous electrolyte in example 1;
FIG. 3a is a diffraction pattern of a precipitated phase obtained by electrolytic extraction with an organic electrolyte in example 2;
FIG. 3b is a diffraction pattern of a precipitated phase obtained by electrolytic extraction with an aqueous electrolyte in example 2;
FIG. 4 is a diffraction pattern of the precipitated phase in comparative example 1;
FIG. 5 is a diffraction pattern of the precipitated phase in comparative example 2;
FIG. 6 is a diffraction pattern of the precipitated phase in comparative example 3;
FIG. 7 is a diffraction pattern of the precipitated phase in comparative example 4.
Reference numerals
1-beaker, 2-cathode, 3-capsule, 4-electrolysis test sample.
Detailed Description
The following examples illustrate the invention in detail. The examples are illustrative and are intended to describe embodiments of the invention and are not intended to limit the scope of the invention.
Under the proper heat treatment process conditions, the cobalt-based superalloy can form a small amount of carbide phase and a fine dispersion gamma' phase, thereby strengthening the material. The electrolytic extraction method of cobalt-based superalloy precipitated phase has been reported recently, when the electrolytic extraction is carried out under the common electrolytic extraction conditions of iron-based or nickel-based alloy, carbide and boride can be extracted, but the extraction rate of gamma' is very low; when the common extraction electrolysis conditions of nickel base alloy or iron-nickel base alloy are adopted, gamma' phase in cobalt base superalloy is electrolyzed together with the base body, when other electrolyte is used, the extraction rate is very low, and ions dissolved in the base body react with electrolyte components to generate undissolved substances which interfere with the measurement of precipitated phases; therefore, it is desirable to provide an electrolytic extraction analysis method for precipitated phases in cobalt-based superalloys.
The invention provides an electrolytic extraction analysis method of a precipitated phase in cobalt-based superalloy, which comprises the step of carrying out electrolytic extraction of gamma' phase by adopting an aqueous electrolyte of an aqueous solution of three components of ammonium chloride, citric acid and glycerol.
Specifically, in the aqueous electrolyte, the mass concentration of ammonium chloride is 47-52 g/L, the mass concentration of citric acid is 17-22 g/L, and the volume concentration of glycerin is 4-6%.
Specifically, the preparation method of the aqueous electrolyte comprises the following steps: weighing ammonium chloride and citric acid, adding into water, stirring for dissolving, adding glycerol, and stirring uniformly to obtain water-based electrolyte. By adopting the material adding sequence, the ammonium chloride and the citric acid can be dissolved rapidly and fully, and if the glycerol is added first, the viscosity of the solution becomes high, and the dissolution rate of the ammonium chloride and the citric acid becomes low.
Specifically, the aqueous electrolyte is placed in a refrigerating chamber of a refrigerator for 2-2.5 hours after being prepared.
Specifically, the electrolytic extraction analysis method of the precipitated phase in the cobalt-based superalloy further comprises an organic electrolyte electrolytic sample of a methanol solution with three components of LiCl+sulfosalicylic acid+glycerol.
Specifically, in the organic electrolyte, the mass concentration of LiCl is 8-12 g/L, the mass concentration of sulfosalicylic acid is 38-42 g/L, and the volume concentration of glycerin is 4-6%. Lithium chloride in the organic electrolyte serves as an electrolyte, making the solution conductive and providing the appropriate anion, methanol as a solvent. Sulfosalicylic acid is used as a complexing agent to prevent metal ions from being hydrolyzed, pitting corrosion is easy to occur in the electrolytic process of the cobalt-based superalloy, and glycerol is used as a surfactant, so that the electrolytic surface of a sample is smooth and free from pitting corrosion after the sulfosalicylic acid is added.
Specifically, the preparation method of the organic electrolyte comprises the following steps: weighing lithium chloride, adding the lithium chloride into methanol, stirring and dissolving, adding sulfosalicylic acid, stirring and dissolving, adding glycerol, stirring uniformly to obtain an organic electrolyte, and filling the prepared organic electrolyte into a reagent bottle. The reagents used are all analytically pure, and in order to ensure that the precipitated phase is completely reserved, the low-temperature electrolysis is required below-5 ℃, so that the reagent bottle is placed in a freezing chamber of a refrigerator for more than 2 hours.
Specifically, in the preparation method of the organic electrolyte, lithium chloride is firstly added into methanol, stirred and dissolved, and then sulfosalicylic acid is added into the mixture to be stirred and dissolved, so that the lithium chloride and the sulfosalicylic acid can be rapidly and fully dissolved, and if glycerol is firstly added, the viscosity of the solution becomes high, and the dissolution speed of the lithium chloride and the sulfosalicylic acid becomes low.
Specifically, the electrolytic extraction analysis method of the precipitated phase in the cobalt-based superalloy comprises the following steps:
s1, preparing a sample to be detected into an electrolysis sample required by electrolysis extraction;
s2, pre-electrolyzing an electrolysis sample by adopting an organic electrolyte, and then electrolyzing the electrolysis sample, wherein the method comprises the following steps:
s21, placing the electrolysis sample in a beaker for pre-electrolysis, wherein the current density of the pre-electrolysis is 0.03-0.05A/cm 2 The total current is 0.6-0.7A, and the pre-electrolysis time is 8-12 min;
s22, placing the pre-electrolyzed electrolysis sample in an electrolysis device, wherein the current density is 0.03-0.05A/cm 2 Electrolyzing for 0.5-2 h under the condition of 0.6-0.7A total current;
before electrolysis, calculating the surface area of a part to be electrolyzed in electrolysis according to the total current and the current density in electrolysis, and sticking a part which is not electrolyzed on the part to be electrolyzed by using a insulating adhesive tape, wherein only the surface of the part to be electrolyzed is exposed, and the part to be electrolyzed is completely immersed in electrolyte for electrolysis; both the electrolyte and the electrolytic sample are placed in a capsule made of a semipermeable membrane permeable to electrolyte ions;
s3, after the electrolysis of the organic electrolyte is finished, brushing the non-shedding precipitated phase powder into a beaker by using a citric acid ethanol solution, carrying out suction filtration on the powder in the beaker and the precipitated phase powder which falls into the capsule by using an inlet microporous filter membrane, respectively washing for a plurality of times by using a citric acid ethanol washing liquid and a citric acid water washing liquid in sequence, finally washing by using distilled water, and drying;
s4, continuously performing electrolytic extraction on the sample subjected to the electrolysis of the organic electrolyte by adopting a water-based electrolyte;
s5, turning off a power supply after the electrolysis is finished, taking out a sample electrolyzed by the water-based electrolyte, putting the sample into a beaker, directly brushing non-fallen precipitated phase powder into the beaker by using a citric acid aqueous solution, carrying out suction filtration on the precipitated phase powder in the beaker and the precipitated phase powder fallen into a capsule by using an inlet microporous filter membrane, sequentially washing the powder for a plurality of times by using a washing solution containing citric acid, washing residues by using distilled water, and drying;
s6, respectively adopting an X-ray diffractometer to analyze the precipitated phase powder collected by the twice electrolysis, and determining the type of the precipitated phase.
Specifically, in the above step S1, the electrolytic sample may be in a rod shape or a sheet shape, and considering that the electrolytic sample is too large in size, too long or too thick, the sample is inconvenient to be suspended in a capsule for electrolysis, and the total current cannot be too large due to the adoption of organic solution for electrolysis, so that the temperature of the electrolyte is increased in the electrolysis process, and the precipitated phase is prevented from being lost; the sample is too small, the total current is small, the electrolysis time required to collect a sufficient amount of precipitated phase powder is too long, and unstable precipitated phases may be lost. Thus, the dimensions of the electrolysis coupon were controlled as follows: in the case of a rod shape, the diameter is 5-15 mm, and the length is 60-100 mm; when in a sheet shape, the length is 60-100 mm, the width is 15-25 mm, and the thickness is 3-7 mm.
Specifically, in the above step S1, a groove of 2-4 mm is engraved at one end of the electrolysis sample for binding copper wires, and the electrolysis sample needs to be suspended for electrolysis.
Specifically, in the above S2, the volume of the beaker at the time of pre-electrolysis is 200 to 500ml, for example, 200ml, 300ml, 400ml, 500ml.
In S2, the current density during electrolysis was too high, and the analysis was partially unstableThe out-phase may be electrolyzed together with the matrix, and the unstable out-phase cannot be retained; the current density is too small to ensure the complete activation and dissolution of the matrix; therefore, the current density is controlled to be 0.03-0.05A/cm 2 The total current is generally controlled between 0.6 and 0.7A, and the temperature is between 0 ℃ and minus 5 ℃. The surface area of the part to be electrolyzed and the length of the sample of the part to be electrolyzed in electrolysis are calculated according to the total current and the current density in electrolysis. The calculation formula of the surface area S of the required electrolysis portion is: s = total current/current density. The sample of the non-electrolytic portion was stuck to the insulating tape to expose only the surface of the portion to be electrolyzed. The surface area of the part requiring electrolysis is controlled, mainly to control the current density in the electrolysis process to be kept between 0.03 and 0.05A/cm 2 Ensure the complete dissolution of the matrix and the retention of the precipitated phase.
In S2, in order to prevent the deposition phase from being stained by the reduction product of the cathode for a long period of time, a semipermeable membrane through which ions can pass may be prepared as a capsule.
In order to eliminate contamination by impurities in the chemical reagents. In the step S2, the organic electrolyte is filtered by a microporous filter membrane with the diameter of 0.2 mu m in advance before electrolysis; then adding the filtered organic electrolyte for electrolysis.
Specifically, in the above S2, the method for manufacturing the capsule includes: and (3) weighing cellulose acetate, adding the cellulose acetate into acetone, uniformly dissolving all the cellulose acetate to obtain capsule liquid, placing the mold cup and the capsule ring into an open container, slowly pouring the prepared capsule liquid from the top of the mold, immersing the capsule liquid into the surfaces of the entire mold cup and the capsule ring, taking down the mold cup after the capsule liquid is dried, immersing the mold cup in aqueous solution for 2-5 min, and separating the prepared capsule from the mold cup. Wherein, the ratio of the cellulose acetate to the acetone is 42 to 48g:500ml. In the electrolytic process, the capsule allows anions and cations to pass normally, but precipitated phase powder and the like falling from an electrolytic sample cannot pass, and are collected in the capsule.
Specifically, in S2, as shown in fig. 1, the electrolytic sample is placed in the electrolytic apparatus and includes:
s201, taking a beaker 1 with the capacity of 500ml as an electrolytic cell, putting sheet or cylindrical stainless steel into the beaker 1 as a cathode 2, then putting a capsule 3, putting an organic electrolyte which is filtered and frozen at a low temperature into the capsule 3, putting the beaker added with the electrolyte and the cathode on an electrolytic frame, and hanging an electrolytic sample 4 into the electrolyte, so that the part of the electrolytic sample which needs to be electrolyzed is completely immersed in the electrolyte;
s202, placing the electrolysis frame in a freezing chamber of a refrigerator, connecting an electrolysis power supply, connecting a cathode with a cathode, connecting a positive electrode to an electrolysis sample, and carrying out electrolysis after electrifying.
Specifically, in the above step S2, the pre-electrolysis is performed by electrolyzing a layer of the surface of an electrolysis sample (also referred to as a sample in the electrolysis sample), so as to eliminate the sample pollution problem caused in the sample preparation process. The pre-electrolysis time is too long, the sample electrolysis loss is too much, the time is relatively long, the time is too short, the sample surface electrolysis amount is too small, and the problem of sample surface pollution cannot be completely eliminated. Thus, the pre-electrolysis is controlled for 8-12 min.
Specifically, in S21, the method further includes: taking out the sample after pre-electrolysis, brushing off precipitated phase powder attached to the surface of the sample, washing the sample, drying the sample, calculating the surface area of a part of the sample needing electrolysis, adhering a part which is not to be electrolyzed to the sample by using a insulating tape, adopting filtered electrolyte (the electrolyte is unused for reducing the influence of impurities in chemical reagents), and then putting the sample into an electrolysis device for electrolysis.
Considering that the electrolysis time is too long, the resistance of the electrolyte is increased, the temperature is increased in the electrolysis process, the precipitated phase is not easy to be completely reserved, the content of lithium chloride and sulfosalicylic acid in the electrolyte can be changed due to the too long time, and the electrolysis effect is affected. Too short, too little precipitated phase powder is collected, inconvenient to observe and not good enough in statistical effect. Therefore, in the above S2, the electrolysis time is controlled to be 0.5 to 2 hours. During electrolysis, the matrix dissolves and the carbide and boride phases remain as insoluble residue powders.
Specifically, in S3, since ions in the electrolyte solution adhere to the surface of the sample and are easily hydrolyzed and precipitated in the ethanol solution without the complexing agent, the precipitated phase powder is brushed into a beaker with the citric acid ethanol solution. Considering that too high a concentration of citric acid and too high acidity can cause loss of partial precipitated phases, too low a concentration of citric acid can not effectively clean ions in electrolyte attached to the surface of a sample; therefore, the concentration of the citric acid in the citric acid ethanol solution is controlled to be 5-10 g/L.
Specifically, in the above step S3, it is considered that the organic solution is used for electrolysis, and the attached electrolyte is washed with citric acid ethanol first, and ions or citric acid are more completely dissolved in water, so that the electrolyte is washed with citric acid ethanol washing solution and citric acid water washing solution in this order, respectively, a plurality of times. Wherein the mass volume ratio of citric acid to ethanol in the citric acid ethanol washing liquid is 8-12 g:1L. The mass volume ratio of citric acid to water in the citric acid aqueous solution is 8-12 g:1L.
Specifically, in the above step S4, the current density during electrolysis is too high, and a part of the precipitated phase may be electrolyzed together with the matrix, and a part of the precipitated phase may not remain; the current density is too small to ensure the complete activation and dissolution of the matrix; therefore, the current density is controlled to be 0.02-0.03A/cm 2 The total current is 0.35-0.45A, and the temperature is 1-5 ℃.
Specifically, in S4, the step of placing the electrolytic sample in the electrolysis apparatus is the same as S2. The electrolysis time is controlled to be 0.3-2 h, and during the electrolysis, the matrix is dissolved, and the gamma' -phase, carbide and boride phases are remained as insoluble residue powder.
Specifically, in the step S5, the concentration of the citric acid in the aqueous solution of citric acid is 8-12 g/L, and the concentration of the citric acid in the washing solution of citric acid is 5-10 g/L.
Specifically, in S6 above, the diffraction conditions are: 2 theta is 20-100 degrees, 5.5mm of anti-scattering slits, the step length is 0.0167 degrees, the time is 20 seconds, the array detector is a Cu target, the tube pressure tube flow is 40kV40mA, diffraction analysis is carried out on precipitated phase powder, diffraction d value and relative strength of the precipitated phase are determined, and accordingly, the structure analysis of the precipitated phase is carried out.
In order to analyze the content of each element in the γ' phase in the cobalt-based superalloy in detail, the electrolytic extraction analysis method for the precipitated phase in the cobalt-based superalloy further includes quantitative electrolytic analysis of the content of each element in the precipitated phase, and specifically includes:
s7, electrolyzing the sample electrolyzed by the water-based electrolyte, pretreating the surface of the sample by using a small amount of organic electrolyte (because the content of gamma '-in the superalloy is relatively high and the carbide is relatively less), avoiding that the residual gamma' -on the surface of the sample affects the accurate determination of the carbide content, and cleaning and drying the sample after pretreatment;
s8, weighing the cleaned and dried sample, wherein the weighing mass is m 1 Electrolyzing the sample according to the steps S22 and S3, collecting precipitated phase powder to obtain carbide and boride powder, and placing the carbide and boride powder into a first beaker for standby;
s9, cleaning the sample subjected to S8 electrolysis, drying, and weighing the sample with a mass of m 2 The dissolution amount of the sample in the electrolytic process is m 2 -m 1 ；
S10, continuously adopting a water-based electrolyte to quantitatively electrolyze the sample to extract gamma' -phase, carbide and boride phases; the electrolysis time is 15-20 min;
s11, taking out the electrolyzed sample, soaking the sample in a citric acid aqueous solution for 2 times, then soaking the sample in distilled water for 2 times, directly brushing the precipitated phase powder which is not dropped off on the surface of the sample into a second beaker with distilled water for standby, and putting the precipitated phase powder after the anode liquid and the soaking liquid in the capsule are subjected to suction filtration by using a filter membrane with the diameter of 0.2 mu m into the second beaker;
s12, cleaning and drying the sample, weighing the sample, wherein the mass is m 3 The dissolution amount of the sample in the electrolysis process of the water-based electrolyte is m 3 -m 2 ；
S13, respectively carrying out acid dissolution on precipitated phase powder collected in the first beaker and the second beaker to obtain a first analysis test solution and a second analysis test solution;
s14, measuring the first analysis sample solution by using an Inductively Coupled Plasma (ICP) to obtain the content w of each element in carbide and boride phases in the cobalt-based superalloy i1 The method comprises the steps of carrying out a first treatment on the surface of the Determining the second analysis solution to obtain the content w of each element in gamma' + carbide and boride in the cobalt-based superalloy i2 W of each element i2 Subtracting w of each element i1 The content of each element in the gamma' -phase in the cobalt-based superalloy is obtained.
Specifically, in S10, considering that the content of γ' phase in the cobalt-based superalloy is relatively high, the quantitative electrolysis time is generally 15 to 20 minutes.
Specifically, in S11, since the γ' phase particles in the cobalt-based superalloy are small, typically several tens nanometers, in order to prevent loss during suction filtration, the electrolyzed sample is taken out and soaked in aqueous citric acid solution for 2 times, then soaked in distilled water for 2 times, the precipitated phase powder which is not peeled off from the surface of the sample is directly brushed into a second beaker with distilled water for standby, and the precipitated phase powder after suction filtration of the anolyte and the soak solution in the capsule with a filter membrane of 0.2 μm is placed in the second beaker.
Specifically, in S13, the acid dissolution step includes: about 5mL of distilled water, 5mLHCl and 1mLHNO were added to the first beaker 3 The first beaker is placed on an electric hot plate to be heated until precipitated phase powder is completely dissolved, taken down and cooled to room temperature, and then fixed to a volume of 100mL volumetric flask. The precipitated phase in the second beaker was acid-dissolved in the same way.
Specifically, in S14, the measurement process includes: transferring standard solutions of cobalt, nickel, chromium, titanium, iron, molybdenum, boron, niobium and aluminum with concentrations of 1000 mug/mL, respectively, 0mL, 1mL, 3mL, 5mL and 10.00mL into a 100mL volumetric flask, adding 5mL of HCl and 1mL of LHNO 3 Diluting with water to scale, taking yttrium as an internal standard element, and measuring the element content by adopting an inductively coupled plasma emission spectrometer.
Compared with the prior art, the electrolytic extraction analysis method of the precipitated phase in the cobalt-based superalloy provided by the invention has the advantages that the cobalt-based superalloy is electrolyzed by adopting the aqueous electrolyte of the aqueous solution of (ammonium chloride+citric acid+glycerin), the matrix dissolution is realized by precisely controlling the electrolyte components and the electrolysis conditions, the gamma ' phase is left, the effective extraction of the gamma ' phase is realized, the accurate analysis of the gamma ' phase is further realized, and the technical support is provided for exploring the influence of the precipitated relative material performance and the material optimization.
The method combines pre-electrolysis and electrolysis, and the pre-electrolysis can electrolyze one layer of the surface of an electrolysis sample, so that the problem of sample pollution in the sample preparation process is solved.
In the method, the electrolyte is put into the capsule, so that the reduction product of the cathode can be prevented from contaminating a precipitated phase.
The method of the invention filters the electrolyte before electrolysis, and can reduce the influence of impurities in the electrolyte on detection and observation of precipitated phases.
In the method, the type of the precipitated phase is determined by qualitative electrolysis analysis, and then the content of each element in the gamma 'phase can be obtained by quantitative electrolysis, so that the accurate analysis of the gamma' phase is realized.
The method of electrolytic extraction analysis of the precipitated phases in the cobalt-based superalloy of the present invention will be shown in the following specific examples.
Example 1
The present embodiment provides an electrolytic extraction analysis method for precipitated phases in cobalt-based superalloy, which determines the type of precipitated phases and elemental analysis in the precipitated phases in GH6159 alloy (mass percentage of each component C: 0.01-0.02%, cr: 17-20%, ni: 23-26%, mo: 6-8%, nb: 0.4-0.6%, ti: 2.5-3.5%, al: 0.15-0.25%, B: 0.01-0.02%, fe: 9-10%, and the balance Co and unavoidable impurities), and includes:
s1, preparing a sample to be detected into an electrolysis sample required by electrolysis extraction; the sample is bar-shaped, the size is 10 x 80mm, a 2mm groove is engraved at one end of the sample and is used for binding copper wires, and the sample is suspended and electrolyzed;
s2, pre-electrolyzing an electrolysis sample by adopting an organic electrolyte, and then electrolyzing the electrolysis sample, wherein the method comprises the following steps:
s21, placing the electrolytic sample in a 200ml beaker for pre-electrolysis for 10min, wherein the pre-electrolysis current density is 0.04A/cm 2 Total current 0.7A, pre-electrolysis time 10min;
s22, brushing off precipitated phase powder attached to the surface of the electrolytic sample after pre-electrolysis, and drying the sample after washing cleanly; placed in an electrolysis apparatus at a current density of 0.04A/cm 2 Electrolyzing for 1h under the condition of 0.7A total current to extract carbide and boride;
before electrolysis, calculating the surface area of a part to be electrolyzed in electrolysis according to the total current and the current density in electrolysis, and sticking a part which is not electrolyzed on the part to be electrolyzed by using a insulating adhesive tape, wherein only the surface of the part to be electrolyzed is exposed, and the part to be electrolyzed is completely immersed in electrolyte for electrolysis; both the electrolyte and the electrolytic sample are placed in a capsule made of a semipermeable membrane permeable to electrolyte ions;
the preparation method of the capsule comprises the following steps: 45g of cellulose acetate is weighed and added into 500mL of acetone, after the cellulose acetate is completely and uniformly dissolved, the capsule liquid is obtained, the mold cup and the capsule ring are placed into an open container, the prepared capsule liquid slowly falls down from the top of the mold, the capsule liquid is immersed into the surfaces of the whole mold cup and the capsule ring, after the capsule liquid is dried, the mold cup is taken down and placed into aqueous solution to be immersed for 5min, and then the prepared capsule is separated from the mold cup.
The preparation method of the organic electrolyte comprises the following steps: weighing 10g of lithium chloride, adding into 900mL of methanol, stirring for dissolving, adding 40g of sulfosalicylic acid, stirring for dissolving, adding 50mL of glycerol, stirring uniformly, filling the prepared electrolyte into a reagent bottle, and placing the reagent bottle into a freezing chamber of a refrigerator for more than 2 hours; the reagents used were all analytically pure;
s3, after the electrolysis of the organic electrolyte is finished, taking out an electrolyzed sample, putting the electrolyzed sample into a 250ml beaker, brushing non-shedding precipitated phase powder into the beaker by using 5g/L citric acid ethanol solution, carrying out suction filtration on the powder in the beaker and the precipitated phase powder falling into the capsule by using an inlet microporous filter membrane, respectively washing 3 times by using 10g/L citric acid ethanol washing liquid and 10g/L citric acid water washing liquid in sequence, finally washing by using distilled water, and drying;
s4, continuously electrolyzing the sample subjected to the electrolysis of the organic electrolyte by adopting a water-based electrolyte to extract gamma' -phase, carbide and boride; the preparation method of the water-based electrolyte comprises the following steps: weighing 50g of ammonium chloride and 20g of citric acid, adding into 880mL of water, stirring for dissolution, adding 50mL of glycerol, stirring uniformly, preparing electrolyte, and placing in a refrigerating chamber of a refrigerator for 2h; current density 0.03A/cm 2 The temperature is 5 ℃;
s5, turning off a power supply after the electrolysis is finished, taking out a sample electrolyzed by the water-based electrolyte, putting the sample into a beaker, directly brushing non-shedding precipitated phase powder into the beaker by using a citric acid aqueous solution, carrying out suction filtration on the precipitated phase powder in the beaker and the precipitated phase powder falling into a capsule by using an inlet microporous filter membrane, washing the sample with a washing solution containing 10g/L citric acid for 3 times in sequence, washing residues by using distilled water, and drying;
s6, respectively adopting an X-ray diffractometer to analyze precipitated phase powder collected by twice electrolysis to determine the type of the precipitated phase; diffraction conditions: 2 theta is 20-100 degrees, an anti-scattering slit with the length of 5.5mm is 0.0167 degrees, the time is 20 seconds, the array detector is a Cu target, the pipe pressure pipe flow is 40kV and 40mA, diffraction analysis is carried out on precipitated phase powder, diffraction d value and relative strength of the precipitated phase are determined, and analysis on the structure of the precipitated phase is carried out according to the diffraction d value and the relative strength;
s7, electrolyzing the sample electrolyzed by the water-based electrolyte, pretreating the surface of the sample by using a small amount of organic electrolyte, avoiding that gamma' remained on the surface of the sample affects the accurate determination of carbide content, and cleaning and drying the sample after pretreatment;
s8, weighing the cleaned and dried sample, wherein the weighing mass is m 1 Electrolyzing the sample according to the steps S22 and S3, collecting precipitated phase powder to obtain carbide and boride powder, and placing the carbide and boride powder into a first beaker for standby;
s9, cleaning the sample subjected to S8 electrolysis, drying, and weighing the sample with a mass of m 2 The dissolution amount of the sample in the electrolytic process is m 2 -m 1 ；
S10, continuously adopting a water-based electrolyte to quantitatively electrolyze the sample to extract gamma' -phase, carbide and boride phases; the electrolysis time is 20min;
s11, taking out the electrolyzed sample, soaking the sample in a citric acid aqueous solution for 2 times, then soaking the sample in distilled water for 2 times, directly brushing precipitated phase powder which is not dropped off on the surface of the sample into a second beaker with distilled water for standby, and putting the precipitated phase powder after the anode liquid and the soaking liquid in the capsule are subjected to suction filtration by using a filter membrane with the diameter of 0.2 mu m into the second beaker;
s12, cleaning and drying the sample, weighing the sample, wherein the mass is m 3 The dissolution amount of the sample in the electrolysis process of the water-based electrolyte is m 3 -m 2 ；
S13, respectively carrying out acid dissolution on precipitated phase powder collected in the first beaker and the second beaker to obtain a firstAn analysis reagent and a second analysis reagent; the acid dissolution method comprises the following steps: about 5mL distilled water, 5mLHCl and 1mLHNO were added to the first beaker and the second beaker, respectively 3 Heating the two beakers on an electric heating plate until precipitated phase powder is completely dissolved, taking down and cooling to room temperature, and respectively fixing the volume into a 100mL volumetric flask to obtain a first analysis test solution and a second analysis test solution;
s14, measuring the first analysis sample solution by using an Inductively Coupled Plasma (ICP) to obtain the content w of each element in carbide and boride phases in the cobalt-based superalloy i1 The method comprises the steps of carrying out a first treatment on the surface of the Determining the second analysis solution to obtain the content w of each element in gamma' + carbide and boride in the cobalt-based superalloy i2 W of each element i2 Subtracting w of each element i1 The content of each element in the gamma' -phase in the cobalt-based superalloy is obtained. The testing process comprises the following steps: transferring standard solutions of cobalt, nickel, chromium, titanium, iron, molybdenum, boron, niobium and aluminum with concentrations of 1000 mug/mL, respectively, 0mL, 1mL, 3mL, 5mL and 10.00mL into a 100mL volumetric flask, adding 5mL of HCl and 1mL of LHNO 3 Diluting with water to scale, taking yttrium as an internal standard element, and measuring the element content by adopting an inductively coupled plasma emission spectrometer.
FIG. 2a is a diffraction pattern of a precipitate phase obtained by electrolytic extraction with an organic electrolyte, the precipitate phase being mainly TiC and M 3 B 2 Fig. 2b shows a diffraction pattern of a precipitated phase obtained by electrolytic extraction with an aqueous electrolyte. Tables 1 and 2 show the analysis of the content of precipitated phases after treatment with different time periods. It can be seen that carbide and boride particles are relatively large, diffraction spectrum peaks are relatively narrow, and gamma 'precipitated phase powder of electrolytic extraction is more, but as gamma' phase particles are very fine, time effect is relatively short, diffraction spectrum peaks of precipitated phase are not obvious, and after 32 hours of time effect, diffraction spectrum peaks are present, but diffraction spectrum peaks are widened. With the increase of the aging time, the carbide and boride contents did not change much, the gamma' -phase precipitation amount gradually increased with the increase of the aging time, and the precipitation phase quantitative results are shown in tables 1 and 2. It can be seen that the method of the present invention achieves efficient extraction of the gamma prime phase.
TABLE 1 post-treatment M at different time effects 3 B 2 The elements in the +MC phase account for the mass fraction of the alloyNumber of digits
TABLE 2 mass fractions of elements in the gamma prime phase after different time-lapse treatments
Example 2
The present example provides an electrolytic extraction analysis method for precipitated phases in cobalt-based superalloy, which measures the types of the precipitated phases, the total amounts of elements in the precipitated phases and the precipitated phases in the Co50 cobalt-based superalloy (mass percentages of each component C: 0.05-0.07%, cr: 28-32%, fe: 2-4%, ni: 9-12%, W: 3-5, nb: 1-2, al: 3-5, and the balance Co and unavoidable impurities), and analyzes the precipitated phases in the cobalt-based superalloy by adopting the method. The method of this example is substantially the same as example 1, except that:
s21, pre-electrolyzing for 12min;
in S4, the aqueous electrolyte includes: 51g of ammonium chloride, 20g of citric acid, 880mL of water and 49mL of glycerol; the current density is 0.03A/cm < 2 >, and the temperature is 4 ℃;
fig. 3a is a diffraction spectrum of a precipitated phase obtained by the electrolytic extraction with an organic electrolyte in this example, the precipitated phase being mainly NbC, and fig. 3b is a diffraction spectrum peak of the precipitated phase obtained by the electrolytic extraction with an aqueous electrolyte in this example. Table 3 shows the mass percent of each element in the gamma' phase in the alloy, and Table 4 shows the NbC phase content.
Table 3 mass fraction of each element in gamma' phase to alloy
TABLE 4 mass fraction of elements in NbC phase to alloy
Comparative example 1
The comparative example provides an electrolytic extraction method of cobalt-based superalloy, which is adopted to carry out electrolytic extraction on cobalt-based superalloy, collect powder and then carry out XRD diffraction to analyze precipitated phase types.
The sample preparation method of this comparative example was substantially the same as the overall procedure of example 1, except that: in this comparative example, only a 1% ammonium sulfate+1% aqueous solution of citric acid was used as the electrolyte.
The cobalt-based superalloy (aged 16 h) sample of example 1 was subjected to electrolytic extraction by this method, and precipitated phase powder was collected, and after electrolysis, it was found that the precipitated phase adhering to the sample surface was very small, substantially similar to that obtained by the organic electrolytic liquid extraction of example 1, and after powder diffraction was collected, it was found that only carbide and boride were found, indicating that the gamma' phase was electrolyzed along with the substrate during electrolysis and did not remain. The diffraction pattern results of the precipitated phases are shown in FIG. 4.
Comparative example 2
The comparative example provides an electrolytic extraction method of cobalt-based superalloy, which is adopted to carry out electrolytic extraction on cobalt-based superalloy, collect powder and then carry out XRD diffraction to analyze precipitated phase types.
The sample preparation method of this comparative example was the same as the overall procedure of example 1, except that: only 1% sodium chloride, 3% ferrous sulfate, 5% sulfuric acid and 5% potassium sodium tartrate aqueous solution was used as the electrolyte.
The cobalt-based superalloy (aged 16 h) sample of example 1 was subjected to electrolytic extraction by the present method, and precipitated phase powder was collected, and after electrolysis, it was found that the precipitated phase adhering to the sample surface was very small, substantially similar to the organic electrolytic liquid extraction used in example 1, and after powder diffraction was collected, only carbides and borides were found, indicating that the gamma' -phase was electrolyzed along with the substrate during electrolysis and did not remain. The diffraction pattern results of the precipitated phases are shown in FIG. 5.
Comparative example 3
The comparative example provides an electrolytic extraction method of cobalt-based superalloy, which is adopted to carry out electrolytic extraction on cobalt-based superalloy, collect powder and then carry out XRD diffraction to analyze precipitated phase types.
The sample preparation method of this comparative example was the same as the overall procedure of example 1, except that: as the electrolyte, 5% copper sulfate+8% sodium citrate+10% aqueous methanol solution was used.
The cobalt-based superalloy (aging 16 h) sample in the embodiment 1 is subjected to electrolytic extraction by adopting the method, precipitated phase powder is collected, a small amount of precipitated phase powder is found to adhere to the surface of the sample after electrolysis, a small amount of gamma 'phase is found after diffraction, the gamma' extraction amount is relatively low after quantitative electrolytic measurement, and in the electrolytic process, ions dissolved in a matrix react with electrolyte components to generate undissolved substances, so that the precipitated phase measurement is interfered. The precipitated phase diffraction pattern is shown in fig. 6.
Comparative example 4
The comparative example provides an electrolytic extraction method of cobalt-based superalloy, which is adopted to carry out electrolytic extraction on cobalt-based superalloy, collect powder and then carry out XRD diffraction to analyze precipitated phase types.
The sample preparation method of this comparative example was the same as the overall procedure of example 1, except that:
in S4, the aqueous electrolyte includes: 20g of ammonium chloride, 10g of citric acid, 950mL of water and 20mL of glycerol; the current density was 0.03A/cm2 and the temperature was 4 ℃.
The cobalt-based superalloy (aging 16 h) sample in the embodiment 1 is subjected to electrolytic extraction by adopting the method, precipitated phase powder is collected, the sample precipitated phase powder is found to be obvious after electrolysis, gamma 'phase is found after diffraction, the gamma' phase extraction amount is low after quantitative electrolytic determination, and the precipitated phase diffraction spectrum is shown in figure 7. Table 5 shows the mass percent of each element in the gamma' phase in the alloy.
Table 5 gamma' phase each element comprises the mass fraction of the alloy
Therefore, the cobalt-based superalloy is electrolyzed by adopting the aqueous electrolyte of the aqueous solution of (ammonium chloride+citric acid+glycerin), and the components and electrolysis conditions of the electrolyte are precisely controlled, so that the dissolution of the matrix and the leaving of the gamma ' -phase are realized, the effective extraction of the gamma ' -phase is realized, and the accurate analysis of the gamma ' -phase is further realized.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (10)
1. The electrolytic extraction analysis method of the precipitated phase in the cobalt-based superalloy is characterized by comprising the step of carrying out electrolysis by adopting an aqueous electrolyte of an aqueous solution of three components of ammonium chloride, citric acid and glycerol.
2. The method according to claim 1, wherein the aqueous electrolyte has a mass concentration of ammonium chloride of 47 to 52g/L, a mass concentration of citric acid of 17 to 22g/L, and a volume concentration of glycerin of 4 to 6%.
3. The method of electrolytic extraction analysis according to claim 1, wherein the method of producing an aqueous electrolyte solution comprises: weighing ammonium chloride and citric acid, adding into water, stirring for dissolving, adding glycerol, and stirring uniformly to obtain water-based electrolyte.
4. The method of claim 1, further comprising using an electrolyte sample comprising a methanol solution of three components LiCl + sulfosalicylic acid + glycerol.
5. The method according to claim 4, wherein the mass concentration of LiCl in the organic electrolyte is 8 to 12g/L, the mass concentration of sulfosalicylic acid is 38 to 42g/L, and the volume concentration of glycerin is 4 to 6%.
6. The method of claim 5, wherein the method of electrowinning analysis comprises:
s1, preparing a sample to be detected into an electrolysis sample required by electrolysis extraction;
s2, pre-electrolyzing the electrolytic sample by adopting an organic electrolyte, then electrolyzing the electrolytic sample,
s3, after the electrolysis of the organic electrolyte is finished, brushing the non-shedding precipitated phase powder into a beaker by using a citric acid ethanol solution, carrying out suction filtration on the powder in the beaker and the precipitated phase powder which falls into the capsule by using an inlet microporous filter membrane, respectively washing for a plurality of times by using a citric acid ethanol washing liquid and a citric acid water washing liquid in sequence, finally washing by using distilled water, and drying;
s4, continuously performing electrolytic extraction on the sample subjected to the electrolysis of the organic electrolyte by adopting a water-based electrolyte;
s5, turning off a power supply after the electrolysis is finished, taking out a sample electrolyzed by the water-based electrolyte, putting the sample into a beaker, directly brushing non-fallen precipitated phase powder into the beaker by using a citric acid aqueous solution, carrying out suction filtration on the precipitated phase powder in the beaker and the precipitated phase powder fallen into a capsule by using an inlet microporous filter membrane, sequentially washing the powder for a plurality of times by using a washing solution containing citric acid, washing residues by using distilled water, and drying;
s6, respectively adopting an X-ray diffractometer to analyze the precipitated phase powder collected by the twice electrolysis, and determining the type of the precipitated phase.
7. The method according to claim 6, wherein the current density in S4 is controlled to be 0.02 to 0.03A/cm 2 The total current is 0.35-0.45A, and the temperature is 1-5 ℃.
8. The method according to claim 6, wherein in S5, the concentration of citric acid in the aqueous solution of citric acid is 8 to 12g/L.
9. The method according to claim 6, wherein in S5, the concentration of citric acid in the citric acid aqueous solution is 5 to 10g/L.
10. The method of any one of claims 6 to 9, further comprising analyzing the content of each element in the precipitate phase using quantitative electrolysis.
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| CN117110128A (en) * | 2023-10-24 | 2023-11-24 | 中国航发北京航空材料研究院 | Quantitative test method for gamma' -phase mass fraction in nickel-based powder superalloy |
| CN117110129A (en) * | 2023-10-25 | 2023-11-24 | 中国航发北京航空材料研究院 | Quantitative determination method for trace phase mass fraction in nickel-based powder superalloy |
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2023
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117110128A (en) * | 2023-10-24 | 2023-11-24 | 中国航发北京航空材料研究院 | Quantitative test method for gamma' -phase mass fraction in nickel-based powder superalloy |
| CN117110128B (en) * | 2023-10-24 | 2024-01-30 | 中国航发北京航空材料研究院 | Quantitative test method for gamma' -phase mass fraction in nickel-based powder superalloy |
| CN117110129A (en) * | 2023-10-25 | 2023-11-24 | 中国航发北京航空材料研究院 | Quantitative determination method for trace phase mass fraction in nickel-based powder superalloy |
| CN117110129B (en) * | 2023-10-25 | 2024-02-09 | 中国航发北京航空材料研究院 | Quantitative determination method for trace phase mass fraction in nickel-based powder superalloy |
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