CN111238915A - Method for extracting non-metallic inclusions in high-temperature alloy - Google Patents
Method for extracting non-metallic inclusions in high-temperature alloy Download PDFInfo
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- G—PHYSICS
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Abstract
The invention provides a method for extracting nonmetallic inclusion in high-temperature alloy, which relates to the technical field of metal materials, wherein the extracted inclusion has high purity and few doping items, and can realize better qualitative extraction effect of nonmetallic inclusion in high-temperature alloy; the method comprises the following steps: determining the proportion and the electrolysis system of the electrolyte according to the polarization curve of the high-temperature alloy; the electrolyte and the electrolysis system are adopted to carry out non-aqueous weak acid solution electrolysis on the high-temperature alloy sample; a dialysis membrane for collecting nonmetallic inclusions is arranged on the periphery of the high-temperature alloy sample during electrolysis; refluxing and boiling the solution containing the nonmetallic inclusion by using a hydrochloric acid-ethanol solution to remove the interference item; collecting nonmetallic inclusions by adopting a vacuum filtration mode, and removing magazine ions capable of being dissolved in ethanol by using an ethanol solution to obtain the nonmetallic inclusions. The technical scheme provided by the invention is suitable for the process of extracting the nonmetallic inclusion of the high-temperature alloy.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of metal materials, in particular to a method for extracting nonmetallic inclusions in high-temperature alloy.
[ background of the invention ]
The high-temperature alloy has good mechanical property, comprehensive strength and toughness indexes, and good thermal fatigue resistance, thermal corrosion resistance and abrasion resistance. Therefore, the composite material is widely applied to key parts in the heavy industrial fields of aerospace, industrial gas turbines, petrochemical industry, ships and warships, nuclear power equipment and the like. The high-temperature alloy contains more active elements Al and Ti, and is very easy to react with O and N in alloy melt and smelting atmosphere to generate Al2O3、TiO2And oxide and nitride inclusions such as TiN.
With the continuous advance of research work, a plurality of research results show that the non-metallic inclusion defects in the high-temperature alloy obviously reduce the mechanical property and the processing property of the high-temperature alloy part, and become a key problem which hinders the improvement of the comprehensive performance of the high-temperature alloy part. In order to investigate the influence of inclusions on the mechanical properties of superalloys, it is first necessary to investigate the characteristics, in particular the three-dimensional characteristics, of the inclusions.
The study of nonmetallic inclusions in superalloys is not mature compared to the study of nonmetallic inclusions in steel. At present, the research on the nonmetallic inclusion in the high-temperature alloy adopts the same electrolyte and electrolysis system as the electrolytic extraction of the nonmetallic inclusion in the steel. Such a method can cause severe matrix shedding problems in the electrolysis of the nickel-base superalloy. Because the high-temperature alloy contains high content of strong carbide forming elements such as Ti, Nb, Mo, W, Ta and the like, the electrolyzed extract is often a mixture of carbide and non-metallic inclusions, the carbide accounts for the most part, and part of the carbide covers the surface of the non-metallic inclusions, thus seriously hindering the observation and analysis of the non-metallic inclusions. Therefore, for the high-temperature alloy, the influence of carbide is effectively removed, and obtaining the nonmetallic inclusion with the original size and shape is the key point and difficulty of observation and analysis of the nonmetallic inclusion in the high-temperature alloy.
Accordingly, there is a need to develop a method for extracting nonmetallic inclusions from a superalloy that addresses the deficiencies of the prior art to address or mitigate one or more of the above-mentioned problems.
[ summary of the invention ]
In view of the above, the invention provides a method for extracting nonmetallic inclusions in a high-temperature alloy, the extracted inclusions are high in purity and few in doping items, and a better qualitative extraction effect of nonmetallic inclusions in the high-temperature alloy can be realized.
In one aspect, the present invention provides a method for extracting nonmetallic inclusions from a superalloy, the method comprising the steps of:
s1, carrying out nonaqueous weak acid solution electrolysis on the high-temperature alloy sample; a dialysis membrane for collecting nonmetallic inclusions is arranged on the periphery of the high-temperature alloy sample during electrolysis;
during electrolysis, a high-temperature alloy sample is used as an anode for electrolysis;
the electrolysis adopts a direct current potentiostatic method, and the current density is 10-60mA/cm2Continuously electrolyzing for 8-12h at 15-25 deg.C; injecting electrolyte into the anode electrolytic tank at a speed of 0.1-0.2L/h in the electrolytic process;
s2, refluxing and boiling the solution containing the nonmetallic inclusion by using a hydrochloric acid-ethanol solution to remove the interference item;
and S3, collecting the nonmetallic inclusion in a vacuum filtration mode, and removing impurity ions capable of being dissolved in ethanol by using an ethanol solution to obtain the nonmetallic inclusion.
The above aspect and any possible implementation manner further provide an implementation manner, and the mass ratio of the electrolyte used in the electrolysis in S1 is: 80-95% of absolute ethyl alcohol, 1-8% of methanol, 1-10% of glycerol and 1-15% of citric acid, wherein the sum of the absolute ethyl alcohol, the methanol, the glycerol and the citric acid is 100%.
The above aspects and any possible implementation manners further provide an implementation manner that argon gas is injected into the solution in the dialysis membrane at a speed of 0.1-0.3L/min during electrolysis, so as to promote the separation of carbide and nonmetallic inclusion while protecting the original appearance of nonmetallic inclusion.
As for the above-mentioned aspect and any possible implementation manner, further providing an implementation manner, the S2 includes: centrifuging the solution containing the impurities to remove the lower suspension, and refluxing and boiling for 5-8h to dissolve the carbide.
As for the above-mentioned aspect and any possible implementation manner, further providing an implementation manner, the specific content of S3 includes: repeatedly carrying out vacuum filtration for 3-5 times by using a filter membrane, and washing away impurity ions attached to the filter membrane and dissolved in the ethanol solution to obtain the final non-metallic inclusion.
The above aspect and any possible implementation manner further provide an implementation manner, wherein the dialysis membrane needs to be pretreated before use, and the pretreatment process comprises: boiling the dialysis membrane in the pretreatment solution for 10-15 min; the pretreatment solution is an EDTA solution with the pH value of 8.
The above-mentioned aspects and any possible implementation manner further provide an implementation manner that the superalloy sample needs to be pretreated before electrolysis, and the pretreatment process comprises the following steps: firstly, polishing the surface of a high-temperature alloy sample, and then placing the high-temperature alloy sample in an acetone solution to clean for 10-15min by ultrasonic oscillation.
The above aspects and any possible implementation manners further provide an implementation manner, wherein a polarization curve of the high-temperature alloy sample is measured before electrolysis, a ratio and an electrolysis system of the electrolyte are determined according to the polarization curve, and then the high-temperature alloy sample is electrolyzed according to the ratio and the electrolysis system of the electrolyte.
The above aspects and any possible implementations further provide an implementation that measures a polarization curve of the superalloy using steady-state potentiostatic methods.
In accordance with the above aspect and any possible implementation manner, there is further provided an implementation manner in which two or more of the electrolyzed superalloy samples are electrolyzed in series.
The above aspects and any possible implementations further provide an implementation in which the extraction method is applicable to nickel-based superalloys and cobalt-based superalloys.
In another aspect, the present invention provides an apparatus for extracting nonmetallic inclusions in a high-temperature alloy, the apparatus being capable of implementing any of the above-described methods for extracting nonmetallic inclusions in a high-temperature alloy.
Compared with the prior art, the invention can obtain the following technical effects: the impurities extracted by the method have high purity and few doping items, and the good qualitative extraction effect of the nonmetallic impurities in the high-temperature alloy can be realized; compared with the electrolysis process of a large sample for several days, the invention can complete the extraction of various impurities by only several hours, and the preparation method has short flow and high efficiency; compared with the small sample electrolysis which is mainly performed by strong acid solution in the prior art, the preparation method adopts the organic weak acid electrolyte, weak acidolysis can not only keep the original appearance of the inclusions, but also fully ensure experimental safety and environmental friendliness, the extraction of the original appearance of the inclusions is extremely unfavorable by electrolysis performed by strong acid solution, the inclusions are obtained, but the electrolytic waste liquid obtained after the experiment is unfavorable for the environment, and the experimental process has danger.
Of course, it is not necessary for any one product in which the invention is practiced to achieve all of the above-described technical effects simultaneously.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic view of an electrolytic apparatus for extracting nonmetallic inclusions from a superalloy according to an embodiment of the present invention;
FIG. 2 is a graph of a mixed extract collected after electrolysis, substantially skeletal carbides, according to one embodiment of the present invention;
FIG. 3 is a SEM image of chemically separated oxide particles of Al-Mg-O composite oxide inclusions according to an embodiment of the present invention;
FIG. 4 is a scanning electron micrograph of chemically separated oxides, as alumina inclusion particles, according to an embodiment of the present invention;
FIG. 5 is a SEM image of chemically separated oxides of composite nitrogen oxide inclusion particles according to an embodiment of the present invention;
FIG. 6 is a flow chart of a method for extracting nonmetallic inclusions from a superalloy according to an embodiment of the present invention.
Wherein, in the figure:
1-electrolytic workpiece, 2-electrolytic bath, 3-dialysis membrane, 4-thermometer, 5-waste liquid bath, 6-salt bridge, 7-platinum electrode, 8-electrolyte, 9-direct current power supply, 10-electrolyte automatic injector and 11-argon injection pump.
[ detailed description ] embodiments
For better understanding of the technical solutions of the present invention, the following detailed descriptions of the embodiments of the present invention are provided with reference to the accompanying drawings.
It should be understood that the described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
Aiming at the defects of the prior art, the invention provides a method for extracting nonmetallic inclusions in high-temperature alloy, which comprises the steps of selecting proper electrolyte, taking the high-temperature alloy as an anode and taking metal platinum or stainless steel as a cathode, and electrolyzing a high-temperature alloy sample; after the electrolysis is finished, the collected mixture is subjected to a proper separation method, so that the nonmetallic inclusions in the high-temperature alloy are extracted without damage; the obtained non-metallic inclusion is observed under a scanning electron microscope, the granular morphology is obvious, and the inclusion containing oxide, nitride and nitrogen oxygen carbon composite inclusion is obtained by X-ray diffraction and energy spectrum analysis.
The method comprises the following specific steps:
(1) sample preparation
Machining to process the alloy ingot into a sample with a proper size, polishing the surface of the sample, and placing the sample in an acetone solution to wash for 10-15min by ultrasonic oscillation.
(2) Determination of electrochemical curves
And (3) measuring the polarization curve of the high-temperature alloy by adopting a steady-state potentiostatic method, and determining proper electrolyte and an electrolysis system according to the polarization curve. Electrochemical curves were measured using a CS electrochemical workstation. The polarization curve of the metal to be detected is measured, so that the active electrolysis range of the metal is obtained, and the current and the voltage are controlled in the active electrolysis range, so that the rapid electrolysis of the sample to be detected is facilitated to prepare the inclusion, which is the basis for determining the electrolysis system and the electrolyte ratio.
(3) Dialysis Membrane pretreatment
And a dialysis membrane with the pore diameter smaller than 20nm is selected, so that the non-metallic inclusions dissociated from the alloy ingot can be fully reserved while ion exchange is ensured. In order to ensure the activity of the dialysis membrane, it is pretreated. The pretreatment process comprises the following steps: weighing 0.292g EDTA and dissolving in 1000mL distilled water, weighing appropriate amount of NaHCO3Adjusting pH of the solution to 8, and boiling the dialysis membrane in the boiling solution for 10-15 min.
(4) Preparing an electrolyte
Adopting non-aqueous solution electrolysis, wherein the electrolyte comprises the following components in percentage by weight: 80-95% of absolute ethyl alcohol, 1-8% of methanol, 1-10% of glycerol and 1-15% of citric acid; the sum of the absolute ethyl alcohol, the methanol, the glycerol and the citric acid is 100 percent.
(5) Electrolysis of non-aqueous solutions
Subjecting the product of step 1 toConnecting the obtained sample with an electrolysis device for electrolysis; the electrolysis is carried out by direct current potentiostatic method with current density of 10-60mA/cm2Continuously electrolyzing for 8-12h, controlling the electrolysis temperature in water bath at 15-25 deg.C, injecting electrolyte into the anode electrolytic tank at 0.1-0.2L/h speed by automatic electrolyte injection pump, and introducing argon into the solution in the dialysis membrane at 0.1-0.3L/min speed by argon injection pump. The method mainly performs qualitative analysis on the inclusions in the sample to be detected, so that the inclusions are extracted, and quantitative analysis is performed without a large amount of extraction, so that the electrolysis time is short, and the method has the advantages of short process, high efficiency and quickness. The electrolysis process mainly comprises the acidolysis process of matrix elements (Ni, Cr, Co, W, Mo and the like) in the high-temperature alloy.
The non-aqueous solution is adopted for electrolysis, so that the original appearance of the inclusions can be fully reserved, acidolysis of the inclusions is prevented, and the oxidizability and reducibility of electrolyte in the adopted electrolyte and the acidity of the solution are different according to different components and contents of the alloy.
Argon gas of 0.1-0.3L/min is introduced into the solution in the dialysis membrane, and the process can bring suspended matters and carbides with lighter density in the anode mud to the surface of the solution, protect the original appearance of the inclusions, and promote the separation of the carbides and nonmetallic inclusions.
The electrolyte is injected into the anode electrolytic tank by an automatic electrolyte injection pump at a rate of 0.1-0.2L/h, so that the electrolytic tank is ensured to keep constant ion concentration in the long-time electrolytic process, the reaction termination caused by the participation of charged ions in the reaction in the electrode reaction process is avoided, and meanwhile, redundant electrolyte is collected into the liquid transfer tank.
If more than two samples are electrolyzed, the electrolysis can be carried out in a serial connection mode, the variable is controlled, and the electrolysis is carried out efficiently.
(6) Collecting the extract
And after the electrolysis is finished, taking out the dialysis membrane, removing the suspension on the upper layer of the solution by using a suction pipe, transferring the rest solution into a 1L beaker, carrying out ultrasonic oscillation on the electrolysis workpiece in an ethanol solution, and collecting the surface anode precipitate and the solution in the beaker. And finally, collecting inclusion solution which comprises two parts, wherein one part is the inclusion in the dialysis membrane, the other part is the solution after the upper suspension is removed and the ultrasonic vibration is carried out, and the two parts are mixed to form the inclusion-containing solution in the step 7.
The removed upper suspension is the primary carbides with lower density in the metal and impurities in the alloy except for non-metal oxides.
(7) Removing interference terms
Centrifuging the solution containing impurities obtained by electrolytic extraction, transferring the lower layer suspension (i.e. non-metallic impurities) to a 250ml triangular flask, adding 100ml 10% -30% hydrochloric acid-ethanol solution, placing the triangular flask on a reflux condenser on a low-temperature electric furnace or a boiling water bath kettle, refluxing and boiling for 5-8h, wherein MC (primary carbide) and part of matrix are dissolved, and Al2O3MgO, TiC, TiN, etc. are retained.
The hydrochloric acid-ethanol solution is specifically as follows: hydrochloric acid is used as a solute, ethanol is used as a solvent, and the hydrochloric acid accounts for 10-30% of the total solution by mass; 100ml of this hydrochloric acid-ethanol solution corresponds to 200ml to 300ml of the above centrifuged solution.
(8) Collecting foreign matters
And (3) carrying out vacuum filtration on the ethanol solution containing the impurities obtained in the step (7) by adopting a Nylon organic filter membrane with the diameter of 60mm and the aperture of 0.2 mu m, repeatedly carrying out vacuum filtration for 3-5 times, cleaning the filter membrane by using alcohol, washing out impurity ions which are attached to the filter membrane and dissolved in the ethanol solution, and finally, attaching all the obtained impurities to the organic filter membrane.
The obtained non-metallic inclusion is fine oxide inclusion, and the non-metallic inclusion in the high-temperature alloy is mainly oxide, nitride and nitrogen-oxygen-carbon composite inclusion.
(9) Analysis by scanning Electron microscope
The size and composition of the non-metallic inclusions obtained by electrolysis were determined by analyzing the organic filter film to which the inclusions adhered by observation and analysis by SEM and EDS and analyzing the composition thereof by energy spectrum.
According to the method, the nonaqueous weak acid solution is adopted to perform electrolytic extraction on the sample in a micro-current environment, so that the problem of collective shedding can be completely avoided, interference items can be removed to a great extent, nonmetallic inclusions in the high-temperature alloy can be retained without damage, qualitative extraction of the inclusions in the high-temperature alloy is realized, and a foundation is provided for analysis of the nonmetallic inclusions in the high-temperature alloy in the future.
Example 1
In the embodiment, the nickel-based superalloy GH4169 is taken as an example, and the GH4169 alloy is produced by a Vacuum Induction Melting (VIM) process. The method for separating the nonmetallic inclusion in the GH4169 alloy provided by the embodiment of the invention is adopted to separate and extract the nonmetallic inclusion in the GH4169 alloy, and comprises the following specific steps:
(1) sample preparation:
machining an alloy ingot into a sample with the diameter of 10 multiplied by 100mm (the diameter is multiplied by the height), putting the sample in an acetone solution, and washing the sample for 10min by ultrasonic oscillation;
(2) determination of electrochemical curves
Measuring the polarization curve of GH4169 by steady-state potentiostatic method, and determining that the electrolyte contains citric acid 5 wt% and current density of 30mA/cm2。
(3) Pretreatment of a dialysis membrane:
and a dialysis membrane with the pore size smaller than 20nm is selected to ensure that nonmetallic inclusions dissociated from the alloy ingot can be fully reserved. In order to ensure the activity of the dialysis membrane, it is subjected to a pretreatment. Weighing 0.292g EDTA and dissolving in 1000mL distilled water, weighing proper amount NaHCO3Adjusting pH of the above solution to 8, and boiling the dialysis membrane in the boiling above solution for 15 min.
(4) Preparing an electrolyte
Adopting non-aqueous solution electrolysis, wherein the electrolyte comprises the following components in percentage by weight: 88% of absolute ethyl alcohol, 2% of glycerol, 5% of methanol and 5% of citric acid;
(5) non-aqueous solution electrolysis:
connecting the sample obtained in the step 1 with an electrolysis device for electrolysis; the electrolysis is carried out by constant potential method with current density of 30mA/cm2Electrolyzing for 8h, controlling the electrolysis temperature at 30 deg.C in water bath, and injecting electricity into the anode electrolytic tank at 0.1L/h speed by automatic electrolyte injection pump during electrolysisSimultaneously introducing argon into the solution in the dialysis membrane at the speed of 0.2L/min by using an argon injection pump;
(6) collecting the extract
After the electrolysis is finished, taking out the dialysis membrane, removing the suspension on the upper layer of the solution by using a suction pipe, transferring the rest solution into a 1L beaker, carrying out ultrasonic oscillation on the electrolytic workpiece in an ethanol solution, and collecting the surface anode precipitate and the solution in the beaker;
(7) removing interference terms
Centrifuging the solution containing impurities, transferring the lower layer suspension to 250ml triangular flask, adding 100ml hydrochloric acid-ethanol solution with mass concentration of 20%, connecting reflux condenser on the triangular flask, placing on low temperature electric furnace or boiling water bath, refluxing and boiling for 5 hr, at which time MC and part of matrix are dissolved, Al2O3MgO, TiC, TiN were retained.
(8) Collecting foreign matters
And (4) carrying out vacuum filtration on the ethanol solution containing the impurities obtained in the step (7) by adopting a nylon organic filter membrane with the diameter of 60mm and the aperture of 0.2 mu m, repeatedly carrying out suction filtration for 5 times, cleaning the filter membrane by using alcohol, washing off impurity ions which are attached to the filter membrane and dissolved in the ethanol solution, and finally attaching all the obtained impurities to the organic filter membrane.
(9) Scanning electron microscope analysis:
the organic filter film with the inclusions adhered thereto was observed and analyzed by SEM and EDS, and the components thereof were analyzed by energy spectroscopy, as shown in fig. 2 and 3. Thereby determining that the size of the nonmetallic inclusion obtained by electrolysis is 5-10 mu m and the nonmetallic inclusion is a granular composite oxide consisting of Si-Al-Mg-O.
Example 2
In the embodiment, the nickel-based superalloy GH4738 is taken as an example, and the GH4738 alloy is produced by Vacuum Induction Melting (VIM) and electroslag remelting (ESR) processes. The method for separating the nonmetallic inclusions in the GH4738 alloy provided by the embodiment of the invention is used for separating and extracting the nonmetallic inclusions in the GH4738 alloy, and comprises the following specific steps:
(1) sample preparation:
machining an alloy ingot into a sample with the diameter of 10 multiplied by 100mm (the diameter is multiplied by the height), putting the sample in an acetone solution, and washing the sample for 10min by ultrasonic oscillation;
(2) determination of electrochemical curves
Measuring the polarization curve of GH4738 by steady-state potentiostatic method, and determining that the electrolyte contains citric acid 15 wt% and current density of 60mA/cm2。
(3) Pretreatment of a dialysis membrane:
and a dialysis membrane with the pore size smaller than 20nm is selected to ensure that nonmetallic inclusions dissociated from the alloy ingot can be fully reserved. In order to ensure the activity of the dialysis membrane, it is subjected to a pretreatment. Weighing 0.292g EDTA and dissolving in 1000mL distilled water, weighing proper amount NaHCO3Adjusting pH of the above solution to 8, and boiling the dialysis membrane in the boiling above solution for 15 min.
(4) Preparing an electrolyte
Adopting non-aqueous solution electrolysis, wherein the electrolyte comprises the following components in percentage by weight: 80% of absolute ethyl alcohol, 2% of glycerol, 3% of methanol and 15% of citric acid;
(5) non-aqueous solution electrolysis:
connecting the sample obtained in the step 1 with an electrolysis device for electrolysis; the electrolysis is carried out by constant potential method with current density of 60mA/cm2Electrolyzing for 4h, controlling the electrolysis temperature in a water bath at 30 ℃, adopting an automatic electrolyte injection pump to inject electrolyte into the anode electrolytic tank at the speed of 0.1L/h in the electrolysis process, and simultaneously adopting an argon injection pump to introduce argon into the solution in the dialysis membrane at the speed of 0.2L/min;
(6) collecting the extract
After the electrolysis is finished, taking out the dialysis membrane, removing the suspension on the upper layer of the solution by using a suction pipe, transferring the rest solution into a 1L beaker, carrying out ultrasonic oscillation on the electrolytic workpiece in an ethanol solution, and collecting the surface anode precipitate and the solution in the beaker;
(7) removing interference terms
Centrifuging the solution containing impurities, transferring the lower layer suspension into 250ml triangular flask, adding 100ml solution with mass concentrationPlacing 10% hydrochloric acid-ethanol solution on a triangular flask, placing in a reflux condenser on a low temperature electric furnace or a boiling water bath kettle, refluxing and boiling for 5 hr, at which time MC and part of matrix are dissolved, Al2O3MgO, TiC, TiN were retained.
(8) Collecting foreign matters
And (4) carrying out vacuum filtration on the ethanol solution containing the impurities obtained in the step (7) by adopting a nylon organic filter membrane with the diameter of 60mm and the aperture of 0.2 mu m, repeatedly carrying out suction filtration for 5 times, cleaning the filter membrane by using alcohol, washing off impurity ions which are attached to the filter membrane and dissolved in the ethanol solution, and finally attaching all the obtained impurities to the organic filter membrane.
(9) Scanning electron microscope analysis:
the organic filter film with the inclusions adhered thereto was observed and analyzed by SEM and EDS, and the components thereof were analyzed by energy spectroscopy, as shown in fig. 4 and 5. Thereby determining the size of the nonmetallic inclusion obtained by electrolysis to be 3-7 μm, wherein the nonmetallic inclusion comprises oxide, nitride and composite inclusion thereof.
Example 3
In the embodiment, the cobalt-based high-temperature alloy GH159 is taken as an example, and the GH159 alloy is produced by a Vacuum Induction Melting (VIM) process. The method for separating the nonmetallic inclusions in the GH159 alloy provided by the embodiment of the invention is adopted to separate and extract the nonmetallic inclusions in the cobalt-based high-temperature alloy, and the specific steps are as follows:
(1) sample preparation:
machining an alloy ingot into a sample with the diameter of 10 multiplied by 100mm (the diameter is multiplied by the height), putting the sample in an acetone solution, and washing the sample for 10min by ultrasonic oscillation;
(2) determination of electrochemical curves
Measuring the polarization curve of GH159 by steady-state potentiostatic method, and determining that the electrolyte contains citric acid 10 wt% and current density 30mA/cm2。
(3) Pretreatment of a dialysis membrane:
and a dialysis membrane with the pore size smaller than 20nm is selected to ensure that nonmetallic inclusions dissociated from the alloy ingot can be fully reserved. In order to ensure the activity of the dialysis membrane, it is subjected to a pretreatment. 0.292g of EDTA are weighed out and dissolved in 1000mLWeighing appropriate amount of NaHCO in distilled water3Adjusting pH of the above solution to 8, and boiling the dialysis membrane in the boiling above solution for 15 min.
(4) Preparing an electrolyte
Adopting non-aqueous solution electrolysis, wherein the electrolyte comprises the following components in percentage by weight: 85% of absolute ethyl alcohol, 2% of glycerol, 3% of methanol and 10% of citric acid;
(5) non-aqueous solution electrolysis:
connecting the sample obtained in the step 1 with an electrolysis device for electrolysis; the electrolysis is carried out by constant potential method with current density of 30mA/cm2Electrolyzing for 10h, controlling the electrolysis temperature in a water bath at 30 ℃, adopting an automatic electrolyte injection pump to inject electrolyte into the anode electrolytic tank at the speed of 0.1L/h in the electrolysis process, and simultaneously adopting an argon injection pump to introduce argon into the solution in the dialysis membrane at the speed of 0.2L/min;
(6) collecting the extract
After the electrolysis is finished, taking out the dialysis membrane, removing the suspension on the upper layer of the solution by using a suction pipe, transferring the rest solution into a 1L beaker, carrying out ultrasonic oscillation on the electrolytic workpiece in an ethanol solution, and collecting the surface anode precipitate and the solution in the beaker;
(7) removing interference terms
Centrifuging the solution containing impurities, transferring the lower layer suspension to 250ml triangular flask, adding 100ml hydrochloric acid-ethanol solution with mass concentration of 10%, connecting reflux condenser on the triangular flask, placing on low temperature electric furnace or boiling water bath, refluxing and boiling for 5 hr, at which time MC and part of matrix are dissolved, Al2O3MgO, TiC, TiN were retained.
(8) Collecting foreign matters
And (4) carrying out vacuum filtration on the ethanol solution containing the impurities obtained in the step (7) by adopting a nylon organic filter membrane with the diameter of 60mm and the aperture of 0.2 mu m, repeatedly carrying out suction filtration for 5 times, cleaning the filter membrane by using alcohol, washing off impurity ions which are attached to the filter membrane and dissolved in the ethanol solution, and finally attaching all the obtained impurities to the organic filter membrane.
(9) Scanning electron microscope analysis:
the organic filter membrane with the inclusions adhered thereto was observed and analyzed by SEM and EDS, and the components thereof were analyzed by energy spectroscopy. Thereby determining the size and the type of the nonmetallic inclusion obtained by electrolysis.
The method for extracting nonmetallic inclusions from the superalloy provided in the embodiments of the present application is described in detail above. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core ideas; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
As used in the specification and claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a commodity or system that includes the element.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.
Claims (10)
1. A method for extracting nonmetallic inclusions from a superalloy, the method comprising the steps of:
s1, carrying out nonaqueous weak acid solution electrolysis on the high-temperature alloy sample; a dialysis membrane for collecting nonmetallic inclusions is arranged on the periphery of the high-temperature alloy sample during electrolysis;
during electrolysis, a high-temperature alloy sample is used as an anode for electrolysis;
the electrolysis adopts a direct current potentiostatic method, and the current density is 10-60mA/cm2Continuously electrolyzing for 8-12h at 15-25 deg.C; injecting electrolyte into the anode electrolytic tank at a speed of 0.1-0.2L/h in the electrolytic process;
s2, refluxing and boiling the solution containing the nonmetallic inclusion by using a hydrochloric acid-ethanol solution to remove the interference item;
and S3, collecting the nonmetallic inclusion in a vacuum filtration mode, and removing impurity ions capable of being dissolved in ethanol by using an ethanol solution to obtain the nonmetallic inclusion.
2. The method for extracting nonmetallic inclusions from a superalloy as claimed in claim 1, wherein the electrolyte used in the electrolysis in S1 is prepared from the following components in mass ratio: 80-95% of absolute ethyl alcohol, 1-8% of methanol, 1-10% of glycerol and 1-15% of citric acid, wherein the sum of the absolute ethyl alcohol, the methanol, the glycerol and the citric acid is 100%.
3. The method for extracting nonmetallic inclusions from a superalloy as claimed in claim 1, wherein argon gas is injected into the solution in the dialysis membrane at a rate of 0.1-0.3L/min during electrolysis for promoting separation of carbides and nonmetallic inclusions while protecting the original appearance of nonmetallic inclusions.
4. The method of claim 1, wherein S2 comprises: centrifuging the solution containing the impurities to remove the lower suspension, and refluxing and boiling for 5-8h to dissolve the carbide.
5. The method of claim 1, wherein S3 comprises: repeatedly carrying out vacuum filtration for 3-5 times by using a filter membrane, and washing away impurity ions attached to the filter membrane and dissolved in the ethanol solution to obtain the final non-metallic inclusion.
6. The method of claim 1, wherein the dialysis membrane is pre-treated before use, and the pre-treatment comprises: boiling the dialysis membrane in the pretreatment solution for 10-15 min; the pretreatment solution is an EDTA solution with the pH value of 8.
7. The method of claim 1, wherein the superalloy sample is pre-treated prior to electrolysis, the pre-treatment comprising: firstly, polishing the surface of a high-temperature alloy sample, and then placing the high-temperature alloy sample in an acetone solution to clean for 10-15min by ultrasonic oscillation.
8. The method of claim 1, wherein a polarization curve of the superalloy sample is measured before electrolysis, a ratio of the electrolyte solution and an electrolysis system are determined based on the polarization curve, and the superalloy sample is electrolyzed based on the ratio of the electrolyte solution and the electrolysis system.
9. The method of claim 8, wherein the polarization curve of the superalloy is measured by steady-state potentiostatic method.
10. An apparatus for extracting nonmetallic inclusions from a high-temperature alloy, wherein the apparatus is capable of implementing the method for extracting nonmetallic inclusions from a high-temperature alloy as set forth in any one of claims 1 to 9.
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| 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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