CN112763296B - Three-dimensional etching method for chromium-manganese stainless steel inclusions - Google Patents
Three-dimensional etching method for chromium-manganese stainless steel inclusions Download PDFInfo
- Publication number
- CN112763296B CN112763296B CN202011610844.XA CN202011610844A CN112763296B CN 112763296 B CN112763296 B CN 112763296B CN 202011610844 A CN202011610844 A CN 202011610844A CN 112763296 B CN112763296 B CN 112763296B
- Authority
- CN
- China
- Prior art keywords
- inclusions
- etching
- percent
- stainless steel
- steel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/32—Polishing; Etching
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- ing And Chemical Polishing (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses a three-dimensional current corrosion method for inclusions in chromium-manganese stainless steel, and belongs to the field of metal material detection. According to the invention, a novel three-dimensional etching solution is given, and current directional etching is carried out in the novel etching solution prepared from a neutral solvent, a complexing agent and a conductive agent according to a given method and etching parameters, so that a steel matrix is partially dissolved, inclusions are not dissolved, the spatial morphology of the inclusions is exposed, and the spatial position information of the inclusions is retained, thereby the morphology and the distribution rule of the inclusions in the stainless steel can be observed in situ without extraction. The method needs small samples, usually a few grams; the etching time is short, the efficiency is high, and etching can be completed within dozens of minutes usually; the device is simple and flexible to operate, and after etching is finished, the device can be matched with scanning electron microscope equipment to observe, shoot and count inclusions, so that the three-dimensional form of the inclusions and the in-situ distribution information in steel are obtained, the spatial distribution and the morphological characteristics of the inclusions in the steel are accurately determined, and the in-situ distribution characteristics of the inclusions are obtained.
Description
Technical Field
The invention relates to the field of metal material detection, in particular to a method for in-situ electrolytic etching of nonmetallic inclusions in Mn stainless steel.
Background
According to the national standard GB/T13304-1991 Steel Classification and the international general classification method, the stainless steel is divided according to the metallographic structure of the steel, and is divided into 5 types of austenite type, ferrite type, martensite type, austenite-ferrite dual phase and precipitation hardening type.
Austenitic stainless steels are classified into two series of chromium-nickel (300 series in the U.S.) austenitic stainless steels and chromium-manganese (200 series in the U.S.) austenitic stainless steels according to their chemical compositions. The austenitic stainless steel of chrome-manganese series (200 series) is developed by adding manganese and/or nitrogen to the steel to replace the noble metal nickel element on the basis of the austenitic stainless steel of chrome-nickel series, the austenitic element of the austenitic stainless steel also contains nitrogen besides manganese and a proper amount of nickel (4-6 percent) generally, and the manganese in the steel plays a role of stabilizing austenite. The series of stainless steel is suitable for equipment and parts which bear heavier load and have low corrosion resistance requirement because nitrogen strongly forms and stabilizes austenite and has good solid solution strengthening effect to improve the strength of the austenitic stainless steel.
Along with the improvement of the quality and performance requirements of customers on steel materials, the removal and control of inclusions in steel are more and more emphasized by metallurgy workers, and how to effectively remove the inclusions and control the shapes of the inclusions needs to be clear understanding on the real size and the shape characteristics of the inclusions. The non-continuous non-metallic inclusion in the stainless steel is a main factor which harms the corrosion resistance and other structure performances of the stainless steel, and the size, the shape, the distribution and other parameters of the non-metallic inclusion in the steel have important influence on the structure uniformity of the steel. Generally, a metallographic microscope or a scanning electron microscope is adopted to observe parameters such as size, morphology, distribution and the like of the nonmetallic inclusions. However, after grinding and polishing the sample, only a certain cross section of the nonmetallic inclusion is often seen under an electron microscope, and the real three-dimensional appearance of the nonmetallic inclusion in the steel cannot be observed. Therefore, the three-dimensional representation of the nonmetallic inclusion in the chromium-manganese stainless steel is an important means for accurately mastering the spatial distribution and morphological size of the inclusion, and has important significance for improving the quality of steel.
At present, there have been reported methods for extracting nonmetallic inclusions, roughly two of which are an acid dissolution method and an electrolysis method. The acid dissolution method has been developed early and widely applied, and adopts HNO with various concentrations 3 、H 2 SO 4 The aqueous solution of HCl, and the metal matrix dissolves, while some stable inclusions not dissolved by the acid remain. The acid dissolution method is disclosed in the literature, "study of three-dimensional morphology of ultrafine oxide inclusions in steel by acid dissolution method" (reported in the academic Steel works, 2007,4). The electrolytic etching technology is a sulfide three-dimensional characterization means different from the electrolytic extraction technology. The electroextraction is a characterization method for obtaining inclusions through extraction after completely dissolving a steel matrix by adopting two modes of aqueous solution large sample electrolysis and non-aqueous solution small sample electrolysis. The electrolysis time is long, sulfide filtration is complex and difficult to operate, and the main processes are as follows: sample electrolysis → anode cleaning → elutriation → magnetic separation → reduction → washing → drying → weighing → sulfide composition or performance detection. Compared with electrolytic extraction, the electrolytic three-dimensional etching technology is characterized in that only part of matrix is electrolyzed, and the three-dimensional appearance of the inclusion in the matrix is exposed in situ.
The electrolyte adopted by the aqueous solution electrolysis method is an acidic aqueous solution, and similar to the acid dissolution method, a plurality of inclusions in steel can be damaged in the acidic aqueous solution, and the electrolysis method can only completely retain larger inclusions, and can not accurately evaluate smaller inclusions with higher content in the steel, so that the method also needs to be improved to mention 7 nonaqueous electrolytes in the book 'nonmetallic inclusions in steel', but the steel types and inclusion types which can be extracted by the electrolytes have larger limitations, or aim at one steel type or aim at one type of inclusions. The values of the electrolyte are not described, the damage of the electrolyte to the impurities is hard to be described in the absence of the values, and more importantly, the impurities are extracted by adopting a filtering mode, which is difficult to realize for extracting the nano-scale impurities because the ultra-fine impurities are difficult to separate from the filter paper. In addition, the separation by filtration using filter paper requires a long time and has low separation efficiency, and therefore, these methods are still in need of improvement.
Chinese patent CN101736392A discloses an electrolyte and a method for extracting nonmetallic inclusions in steel by electrolysis, wherein the electrolyte comprises 1-1.5 wt% of tetramethylammonium chloride, 6-10 wt% of triethanolamine, 6-10 wt% of glycerol, 0.6-1 wt% of diphenylguanidine and the balance of anhydrous methanol, and the current density is adjusted to 40-100mA/cm2 during electrolysis; controlling the temperature of the electrolyte at-5 ℃, continuously introducing argon into the electrolytic bath during electrolysis at the flow rate of 0.1-0.3 liter/minute, and then carrying out centrifugal separation on the electrolyte by adopting a centrifugal separator. The invention is different from the above inventions in that: the method adopts an in-situ electrolysis method, and abandons a complex centrifugal-magnetic attraction-separation method, so that the operation is simpler, the distribution difference of non-metallic inclusions in steel in different areas on the surface of a sample can be captured, and errors generated when second-phase particles are observed are avoided; the invention provides a novel three-dimensional etching liquid which is non-toxic, less in time consumption and capable of achieving the purpose of quick electrolysis.
Chinese patent CN106596669A discloses a nondestructive testing device and a nondestructive testing method for sulfide inclusions in steel, and the nondestructive testing device and the nondestructive testing method for sulfide inclusions in steel, wherein the device comprises an electrolytic bath, a low-temperature constant-temperature control bath, a direct-current potentiostat, a hydrogen cylinder, a flowmeter, a computer, a plurality of sample preparations for a cellulose acetate bag detection method, and electrolyte prepared by the electrolyte are uniformly mixed by an anhydrous chlorination file, gamma-Ding Nacu, glycerol and absolute ethyl alcohol to prepare the electrolyte; controlling the pH value of electrolyte to be 7-9 by citric acid solution when the electrolysis is started, electrolyzing for 12-36h, weighing the steel sample after the electrolysis is finished and cleaning the steel sample and the cellulose acetate rubber bag by absolute ethyl alcohol respectively, and performing vacuum classification filtration on the magnetic separation cleaning solution to separate sulfide inclusions. The invention adopts the methods of magnetic separation and graded filtration, and adopts the method of in-situ electrolysis, and has the advantages that the operation process is relatively simple, the direct appearance and the distribution of the nonmetallic inclusion in the chromium-manganese stainless steel can be directly observed, the error analysis generated when the nonmetallic inclusion in the steel is observed can be effectively avoided, the time consumption is less, and the purpose of rapid electrolysis can be achieved.
Chinese patent CN110161066A discloses a method for extracting inclusions in steel by a non-aqueous solution, under certain electrolysis parameters, the inclusions and a steel matrix are electrolyzed into the non-aqueous solution, and then the inclusions are extracted and separated by a centrifugal method. The nonaqueous electrolyte comprises (by mass) acetylacetone 10%, tetramethylammonium chloride 0.7%, ammonium thiocyanate 1-5%, and anhydrous methanol in balance. The electrolysis parameters are as follows: the voltage is 2-5V, and the current is 0.04-0.05A/cm 2 . The invention is different from the above inventions in that: the invention adopts a centrifugal method, so that the operation is complex, and the invention does not need separation operation; the electrolyte disclosed by the invention contains acetylacetone, so that the harm to a human body is large, and the novel electrolyte formula is adopted, the acetylacetone is not adopted, and the electrolyte is harmless to the human body; the method adopts an in-situ electrolysis method, does not need an extraction process, can carry out in-situ electrolysis on the metal matrix, can carry out in-situ analysis, can visually observe the original three-dimensional morphology of inclusions in the steel and the distribution of the inclusions in the steel, and greatly improves the experimental efficiency.
Chinese patent CN102818723A discloses a method for electrolyzing and extracting fine inclusions in steel, which is characterized in that an electrolyte mixed with the inclusions is cleaned by absolute ethyl alcohol after electrolysis, the electrolyte after magnetic separation is separated by magnetic separation by a magnet and a centrifuge, the impurities are collected, the collected impurities are put in a volatile solvent for ultrasonic dispersion by an ultrasonic cleaner, then a micropipette is used for dropwise dripping the solution after ultrasonic dispersion on a carrier, and the carrier for dispersing the impurities is put in a scanning electron microscope for analysis after the solvent is volatilized. The invention is different from the above invention in that: the invention adopts the methods of magnetic separation and centrifugation to collect the impurities, and then adopts the method of ultrasonic dispersion, the operation process is relatively complex, but the invention adopts the method of in-situ electrolysis, and abandons the traditional method of magnetic separation and centrifugation to collect the impurities, so that the operation process is relatively simple, and simultaneously, the direct morphology and the distribution of the non-metallic impurities in the chromium and manganese stainless steel can be directly observed in situ.
Chinese patent CN111596094A discloses a three-dimensional etching device and an etching method for nonmetallic inclusions in steel (9 electrolytic formulas are provided), etching operation is carried out according to a given method and etching parameters through a given etching device, current directional etching is carried out in etching liquid prepared by neutral solvent, complexing agent and conductive agent, the steel matrix is partially dissolved, the inclusions are not dissolved, the space morphology of the inclusions is exposed, the space position information of the inclusions is retained, the electrolysis temperature is-15-45 ℃, and the current density is 20-300 mA/cm 2 . The invention is different from the above inventions in that: the invention aims at the chromium-manganese stainless steel, adopts a formula of the etching solution which is completely different from the formula, and the formula comprises 0.8-2.2% of EDTA, 1.1-2.4% of nitrilotriacetic acid (NTA), 0.9-2.2% of quinoline-2-carboxylic acid (QCA), 1.2-2.6% of sodium citrate, 5-6% of lithium chloride and the balance of absolute ethyl alcohol. The method has the advantages of no toxicity, better electrolysis effect for the chromium-manganese stainless steel, and direct in-situ observation of the direct morphology and distribution of the non-metallic inclusions in the chromium-manganese stainless steel.
Disclosure of Invention
In order to realize the rapid electrolytic corrosion of nonmetallic inclusions in austenitic stainless steel, specific electrolytic solution is adopted to electrolyze 200 series stainless steel with different contents.
The invention relates to an electrolytic solution which comprises a neutral solvent, an electrolytic reaction conductive agent and a matrix element complexing agent. And analyzing the three-dimensional shape information of different inclusions in the steel according to different component contents of the steel. In order to realize the observation effect, the invention provides a three-dimensional electrolytic etching method and a device for nonmetallic inclusions in 200 series stainless steel, and the chemical components of the three-dimensional electrolytic etching method and the device suitable for the stainless steel are as follows: c: less than or equal to 0.3 percent, mn:4 to 16%, P: less than or equal to 0.06 percent, si: less than or equal to 0.8 percent, S: less than or equal to 0.5 percent, cr:12 to 18%, N: less than or equal to 0.25 percent.
A three-dimensional etching method for chromium-manganese stainless steel inclusions specifically comprises the following steps:
a. aiming at the chromium-manganese stainless steel, the method has the following chemical components in percentage by mass: the chemical components are as follows: c: less than or equal to 0.3 percent, mn:4 to 16%, P: less than or equal to 0.06 percent, si: less than or equal to 0.8 percent, S: less than or equal to 0.5 percent, cr:12 to 18%, N: less than or equal to 0.25 percent; the microstructure of the material is austenite;
b. the electrolyte adopted by the method comprises the following components: 1.0 to 4.5% of EDTA, 1.2 to 3.2% of nitrilotriacetic acid (NTA), 0.9 to 3.2% of quinoline-2-carboxylic acid (QCA), 1.0 to 3.6% of sodium citrate, 4 to 6% of lithium chloride and the balance of absolute ethyl alcohol;
c. the initial temperature of electrolysis adopted by the method is-10-10 ℃; the electrolytic current density is 200-300mA/cm 2 (ii) a Etching time: 20-40 min.
Preferably, the chromium-manganese stainless steel comprises the following components: mn:5.5 to 6%, cr:16 to 17%, and the electrolyte component is preferably: the volume percentage is as follows: 1.8% EDTA, 2.16% nitrilotriacetic acid (NTA), 1.5% quinoline-2-carboxylic acid (QCA), 1.65% sodium citrate, 4.7% lithium chloride and the balance anhydrous ethanol;
preferably, the chromium-manganese stainless steel comprises the following components: mn: 8-9%, cr:17 to 18%, and the electrolyte composition is preferably: the volume percentage is as follows: 2.9% EDTA, 2.5% nitrilotriacetic acid (NTA), 2.1% quinoline-2-carboxylic acid (QCA), 2.3% sodium citrate, 5.5% lithium chloride and the balance anhydrous ethanol.
Preferably, a series circuit and a plurality of electrolytic cells are adopted to electrolyze a plurality of samples simultaneously, so that the experimental efficiency is improved.
The three-dimensional etching device of the invention comprises: anode, clamp, etching liquid, sample, constant current source, cathode, platinum sheet and thermostatic bath. The connection device method comprises the following steps: and pouring the electrolyte into the inner electrolytic tank, pouring the cooling liquid into the outer electrolytic tank, wherein both the cathode and the anode clamps are made of stainless steel materials in order to keep good current stability, and the cathode is a long-strip-shaped stainless steel sheet with the length of 80mm, the width of 15mm and the thickness of 2 mm. The sample was held in the anode by a clamp, and the anode clamp was secured to the bottom of the cathode at the same level. The top positions of the anode clamp and the cathode are fixed by the insulating rubber rod, and the anode and the cathode are fixed on the upper cover, so that the anode and the cathode are not in contact with the inner wall of the electrolytic etching groove, the cathode material in the etching process pollutes less electrolyte, and the observation of impurities on the surface of a sample after the etching is finished is facilitated.
The three-dimensional etching reagent is prepared by a neutral solvent, an electrolytic reaction conductive agent and a matrix element complexing agent according to a certain proportion. The electrolytic etching solution provided by the invention comprises the following components in percentage by volume: 1.0 to 4.5% of EDTA, 1.2 to 3.2% of nitrilotriacetic acid (NTA), 0.9 to 3.2% of quinoline-2-carboxylic acid (QCA), 1.0 to 3.6% of sodium citrate, 4 to 6% of lithium chloride and the balance of absolute ethanol. The main functions of each reagent in the electrolytic process are as follows:
EDTA: can be used for complexing with metal ions such as Fe, mn, cr and the like, and is used as a basic complexing agent (the volume percentage is generally 1.0-4.5%);
nitrilotriacetic acid (NTA): mainly used for complexing Cr ions (the volume percentage is generally 1.2-3.2%);
quinoline-2-carboxylic acid (QCA): the electrolyte additive can prevent the anode metal electrode from being excessively dissolved, greatly improve the service life and the cycle capacity (the volume percentage is generally 0.9 to 2.2 percent);
sodium citrate: mainly used for complexing Mn ions (the volume percentage is generally 1 to 3.6 percent);
lithium chloride: used as an electrolytic reaction conductive agent (the volume percentage is generally 4-6%);
anhydrous ethanol: as a neutral solvent.
For Mn:5.5 to 6 percent, cr: 16-17%, and the preferable proportion is as follows: the volume percentage is as follows: 1.8% EDTA, 2.16% nitrilotriacetic acid (NTA), 1.5% quinoline-2-carboxylic acid (QCA), 1.65% sodium citrate, 4.7% lithium chloride and the balance anhydrous ethanol;
for Mn: 8-9%, cr: 17-18%, and the preferable proportion is as follows: the volume percentage is as follows: 2.9% EDTA, 2.5% nitrilotriacetic acid (NTA), 2.1% quinoline-2-carboxylic acid (QCA), 2.3% sodium citrate, 5.5% lithium chloride and the balance anhydrous ethanol.
The three-dimensional etching process comprises the following specific steps:
(1) Sample preparation and electrolyte preparation
The electrolyte described above was prepared. The sample is made into a regular cube with the volume of 10mm multiplied by 10mm by a cutting device, the surface to be observed of the sample is sequentially polished by 240, 400, 600, 800, 1000, 1500 and 2000 meshes of sand paper, polished by polishing paste, washed by alcohol, dried and electrolyzed. When the sample is thin or irregular, a stainless steel clamp is adopted to enable the surface needing electrolysis to be opposite to the cathode.
(2) Adjusting the electrolysis temperature
Regulating the temperature of the cooling liquid in the electrolysis thermostatic bath to enable the etching temperature to be-10 ℃; the temperature is raised, the reaction speed is accelerated, the reaction time is favorably shortened, the activity of the impurities is also increased, the impurities are easy to dissolve in the etching solution, but the etching effect is difficult to control; the temperature is reduced, the electrochemical reaction speed of the anode Fe is slower than that of ion diffusion in the solution, electrochemical polarization is generated, the etching time is long, the etching efficiency is greatly reduced, and the etching effect is convenient to control; repeatedly verified, the etching effect and the etching efficiency are better in combination when the etching temperature is-10 ℃ to 10 ℃.
(3) Selecting current density
The proper improvement of the current density is beneficial to accelerating the ion diffusion and improving the electrolysis efficiency, but the current density is too high, the dissolution of a steel matrix is accelerated, the corrosion and etching effect is difficult to control, and meanwhile, nonmetallic inclusions in the steel are easy to fall off from the matrix, so that the observation of the original appearance of the nonmetallic inclusions in the steel is influenced; at lower current densities, the dissolution of the steel matrix is too slow, although better control is possibleThe corrosion making effect is poor, but the efficiency is too low, and the experiment progress is influenced. Aiming at the chromium-manganese stainless steel, the current density is set to be 200-300A/cm 2 At the moment, the etching effect and the etching efficiency can be better controlled.
(4) Etching process
After the etching parameters are adjusted, etching is started; the sample is etched in the electrolyte, the matrix of the observation surface is gradually dissolved, and the nonmetallic inclusion is gradually exposed; under the condition of ensuring that other parameters are the same, the etching time is properly prolonged, the impurities are exposed more, but the impurities fall off from a steel matrix when the time exceeds a certain range, black cavities can be observed under a scanning electron microscope, the appearance of non-metallic impurities in the steel cannot be observed, and the etching time is 25-40 min usually, so that the effect is the best for the chromium-manganese stainless steel.
(5) Sample post-treatment
After etching is finished, cleaning the sample by using absolute ethyl alcohol and drying the sample by using a drying box;
(6) Observation, photographing, analysis and statistics
And observing and shooting inclusions in the corroded sample by using an optical microscope and a scanning electron microscope analyzer, analyzing and counting, adjusting parameters according to corrosion effects, and repeating the operation or the operation of part of the steps until the effect of exposing the inclusions is achieved.
Drawings
FIG. 1: an electrolytic etching device;
FIG. 2 illustrates a first embodiment: 201 stainless steel-etched 200mA/cm 2 SEM photograph of inclusions.
Fig. 3 example two: 201 stainless steel-etched 300mA/cm 2 SEM pictures of inclusions.
Fig. 4 example three: SEM picture of inclusions etched in 202 stainless steel for 30 min.
FIG. 5 example four: SEM picture of inclusions etched in 202 stainless steel for 40min.
Fig. 6 comparative example one: 201 stainless steel-etched 300mA/cm 2 SEM pictures of inclusions.
Fig. 7 comparative example two: SEM picture of 202 stainless steel-etched 30min inclusions.
Detailed Description
The first embodiment is as follows:
an in-situ electrolysis apparatus for etching non-metallic inclusions in chromium-manganese stainless steel, as shown in fig. 1, comprises: 1. anode, 2 clamp, 3 etching liquid, 4 sample, 5 constant current source, 6 cathode, 7 platinum sheet and 8 constant temperature groove. The connecting method of the electrolytic etching device comprises the following steps: (1) Connecting a lead to one end of the anode clamp and one end of the cathode stainless steel sheet, and respectively connecting the other end of the anode clamp and the other end of the cathode stainless steel sheet to a voltage-stabilized power supply; (2) Fixing the sample on the anode to ensure the sample to be firm and not to loosen; (3) Respectively placing the cathode and the anode into a constant temperature bath, and keeping the distance between the cathode and the anode between 30 and 60 mm; (4) Adding electrolyte to ensure that the liquid level of the electrolyte is 8-15mm higher than the highest position of the sample but far lower than the connection point of the lead and the cathode and the anode; (5) The height of the electrolyte is basically consistent with the height of the liquid level of the anti-freezing solution, a thermostatic bath cover (6) is covered to check a circuit, and a power supply is turned on. The electrolysis operation is carried out according to the steps given by the etching method: the steel sample, the etching parameters and the implementation effect of the embodiment are as follows:
carrying out electrolytic etching on 201 stainless steel (chemical components are 0.1 percent of C, 0.8 percent of Si, 5.9 percent of Mn, less than or equal to 0.06 percent of P, 0.03 percent of S, 16.8 percent of Cr and 0.20 percent of N);
polishing 201 stainless steel, the sample size is 10mm multiplied by 10mm, the weight is 7.6g, and the etching parameters are as follows:
for the etching solution, a preferable scheme 1 is adopted, and the etching solution has the volume percentage: 1.8% EDTA, 2.16% nitrilotriacetic acid (NTA), 1.5% quinoline-2-carboxylic acid (QCA), 1.65% sodium citrate, 4.7% lithium chloride and the balance anhydrous ethanol;
etching temperature: 0 ℃;
etching current density: 200mA/cm 2 ；
Etching time: 25min;
the first effect of the embodiment is as shown in figure 2.
The second embodiment:
carrying out electrolytic etching on 201 stainless steel (chemical components are 0.1 percent of C, 0.8 percent of Si, 5.9 percent of Mn, less than or equal to 0.06 percent of P, 0.03 percent of S, 16.8 percent of Cr and 0.20 percent of N);
polishing 201 stainless steel, the sample size is 10mm multiplied by 10mm, the weight is 7.6g, and the etching parameters are as follows:
for the etching solution, a preferable scheme 1 is adopted, and the etching solution has the volume percentage: 1.8% EDTA, 2.16% nitrilotriacetic acid (NTA), 1.5% quinoline-2-carboxylic acid (QCA), 1.65% sodium citrate, 4.7% lithium chloride and the balance anhydrous ethanol;
etching temperature: 0 ℃;
etching current density: 300mA/cm 2 ；
Etching time: 25min;
the etching result is shown in figure 3, and under the same electrolytic etching time and electrolytic etching temperature, along with the increase of the current density, the inclusion exposure effect is increased along with the increase of the current density; at a current density of 200mA/cm 2 、300mA/cm 2 Meanwhile, the morphology of large-sized inclusions is exposed and more complete, and small-sized inclusions can be separated from the matrix, thereby causing analysis errors. Therefore, the current density of the present embodiment is controlled at 200mA/cm 2 The effect is better.
Example three:
carrying out electrolytic etching on 202 stainless steel (chemical components are 0.1 percent of C, 0.7 percent of Si, 8.9 percent of Mn, less than or equal to 0.06 percent of P, 0.03 percent of S, 17.8 percent of Cr and 0.20 percent of N); grinding and polishing 202 stainless steel, wherein the size of a sample is 10mm multiplied by 10mm, the weight is 7.8g, and etching parameters are as follows:
for the etching solution, a preferable scheme 2 is adopted, and the etching solution has the volume percentage: 2.9% EDTA, 2.5% nitrilotriacetic acid (NTA), 2.1% quinoline-2-carboxylic acid (QCA), 2.3% sodium citrate, 5.5% lithium chloride and the balance anhydrous ethanol;
etching temperature: 0 ℃;
etching time: 30min;
selecting etching current density: 300mA/cm 2 ；
The etching effect of this method is shown in fig. 5.
Example four:
carrying out electrolytic etching on 202 stainless steel (chemical components are 0.1 percent of C, 0.7 percent of Si, 8.9 percent of Mn, less than or equal to 0.06 percent of P, 0.03 percent of S, 17.8 percent of Cr and 0.20 percent of N); grinding and polishing 202 stainless steel, wherein the size of a sample is 10mm multiplied by 10mm, the weight is 7.5g, and etching parameters are as follows:
for the etching solution, a preferable scheme 2 is adopted, and the etching solution has the volume percentage: 2.9% EDTA, 2.5% nitrilotriacetic acid (NTA), 2.1% quinoline-2-carboxylic acid (QCA), 2.3% sodium citrate, 5.5% lithium chloride and the balance anhydrous ethanol;
etching temperature: 0 ℃;
etching time: 40min;
selecting etching current density: 300mA/cm 2 ；
The implementation effect is as shown in fig. 6, under the same etching current density and etching temperature, the inclusion exposure effect is better along with the increase of etching time; when the etching time is 40min, small particles are mixed and separated from the matrix. Therefore, the etching time of the embodiment is controlled within 30min, and the effect is better.
Comparative example one:
carrying out electrolytic etching on 201 stainless steel (chemical components are 0.1 percent of C, 0.8 percent of Si, 5.9 percent of Mn, less than or equal to 0.06 percent of P, 0.03 percent of S, 16.8 percent of Cr and 0.20 percent of N);
the etching liquid volume percentage is as follows: 6% (m/V) tetramethylammonium chloride, 18% acetylacetone and the balance methanol;
etching temperature: 0 ℃;
etching current density: 200mA/cm 2 ；
Etching time: 35min;
as shown in fig. 4, compared to the first embodiment, the etching time is longer and the etching effect is not good under the same current density.
Comparative example two:
carrying out electrolytic etching on 202 stainless steel (chemical components are 0.1 percent of C, 0.7 percent of Si, 8.9 percent of Mn, less than or equal to 0.06 percent of P, 0.03 percent of S, 17.8 percent of Cr and 0.20 percent of N);
the etching liquid volume percentage is as follows: 6% (m/V) tetramethylammonium chloride, 18% acetylacetone and the balance methanol;
etching temperature: 0 ℃;
etching current density: 300mA/cm 2 ；
Etching time: 40min;
as shown in figure 7, the etching time is greatly prolonged under the same current density, and the electrolytic etching effect is far inferior to that of the embodiment 3.
Claims (3)
1. A three-dimensional etching method for chromium-manganese stainless steel inclusions is characterized by comprising the following steps:
a. aiming at the chromium-manganese stainless steel, the method has the following chemical components in percentage by mass: the chemical components are as follows: c: less than or equal to 0.3 percent, mn: 5.5-6%, P: less than or equal to 0.06 percent, si: less than or equal to 0.8 percent, S: less than or equal to 0.5 percent, cr: 16-17%, N: not more than 0.25 percent, and the normal-temperature microstructure of the material is austenite;
b. the electrolyte adopted by the method comprises the following components: 1.8% EDTA, 2.16% nitrilotriacetic acid (NTA), 1.5% quinoline-2-carboxylic acid (QCA), 1.65% sodium citrate, 4.7% lithium chloride and the balance anhydrous ethanol;
c. the electrolysis temperature adopted by the method is-10 ℃; the electrolytic current density is 200-300mA/cm 2 (ii) a Etching time: 20-40 min.
2. A three-dimensional etching method for chromium-manganese stainless steel inclusions is characterized by comprising the following steps:
a. aiming at the chromium-manganese stainless steel, the method has the following chemical components in percentage by mass: the chemical components are as follows: c: less than or equal to 0.3 percent, mn:8 to 9%, P: less than or equal to 0.06 percent, si: less than or equal to 0.8 percent, S: less than or equal to 0.5 percent, cr: 17-18%, N: not more than 0.25 percent, and the normal temperature microstructure of the material is austenite;
b. the electrolyte adopted by the method comprises the following components: 2.9% EDTA, 2.5% nitrilotriacetic acid (NTA), 2.1% quinoline-2-carboxylic acid (QCA), 2.3% sodium citrate, 5.5% lithium chloride and the balance anhydrous ethanol;
c. the electrolysis temperature adopted by the method is-10 ℃; the electrolytic current density is 200-300mA/cm 2 (ii) a Etching time: 20-40 min.
3. The three-dimensional etching method for chromium-manganese stainless steel inclusions according to claim 1 or 2, characterized by comprising the following steps: in order to improve the experimental efficiency, a series circuit and a plurality of electrolytic cells are adopted to electrolyze a plurality of samples simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011610844.XA CN112763296B (en) | 2020-12-30 | 2020-12-30 | Three-dimensional etching method for chromium-manganese stainless steel inclusions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011610844.XA CN112763296B (en) | 2020-12-30 | 2020-12-30 | Three-dimensional etching method for chromium-manganese stainless steel inclusions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112763296A CN112763296A (en) | 2021-05-07 |
| CN112763296B true CN112763296B (en) | 2022-11-18 |
Family
ID=75695919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011610844.XA Active CN112763296B (en) | 2020-12-30 | 2020-12-30 | Three-dimensional etching method for chromium-manganese stainless steel inclusions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112763296B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115144323B (en) * | 2022-08-29 | 2022-11-25 | 中国航发北京航空材料研究院 | Method for detecting content of non-metallic inclusions in metal powder for additive manufacturing |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736392A (en) * | 2008-11-18 | 2010-06-16 | 鞍钢股份有限公司 | Electrolyte and method for extracting nonmetallic inclusion in steel by using same |
| CN102213654A (en) * | 2011-05-13 | 2011-10-12 | 江阴兴澄特种钢铁有限公司 | Electrolytic extraction and detection method of nonmetallic inclusion in steel by utilizing organic solution |
| CN102818723A (en) * | 2012-09-07 | 2012-12-12 | 首钢总公司 | Method of electrolytically extracting and detecting fine inclusions in steel |
| CN102879412A (en) * | 2012-09-15 | 2013-01-16 | 内蒙古包钢钢联股份有限公司 | Method for observing in-situ morphologies of nonmetallic inclusions in steel |
| CN103898596A (en) * | 2014-03-28 | 2014-07-02 | 上海大学 | Organic electrolyte, method for extracting non-metallic inclusions from steel and electrolyzer |
| CN106840802A (en) * | 2017-03-09 | 2017-06-13 | 北京科技大学 | A kind of original appearance analysis method of electrolytic separation high-carbon steel inclusion |
| CN109449486A (en) * | 2018-10-15 | 2019-03-08 | 苏州大学 | A kind of application of electrolysis additive |
| CN111596094A (en) * | 2020-05-12 | 2020-08-28 | 上海大学 | Three-dimensional etching device and method for nonmetallic inclusions in steel |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2572792B2 (en) * | 1987-12-11 | 1997-01-16 | エヌ・イーケムキャット株式会社 | Antioxidant |
| JP4520286B2 (en) * | 2004-11-26 | 2010-08-04 | ニチコン株式会社 | Electrolytic solution for driving electrolytic capacitors |
-
2020
- 2020-12-30 CN CN202011610844.XA patent/CN112763296B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736392A (en) * | 2008-11-18 | 2010-06-16 | 鞍钢股份有限公司 | Electrolyte and method for extracting nonmetallic inclusion in steel by using same |
| CN102213654A (en) * | 2011-05-13 | 2011-10-12 | 江阴兴澄特种钢铁有限公司 | Electrolytic extraction and detection method of nonmetallic inclusion in steel by utilizing organic solution |
| CN102818723A (en) * | 2012-09-07 | 2012-12-12 | 首钢总公司 | Method of electrolytically extracting and detecting fine inclusions in steel |
| CN102879412A (en) * | 2012-09-15 | 2013-01-16 | 内蒙古包钢钢联股份有限公司 | Method for observing in-situ morphologies of nonmetallic inclusions in steel |
| CN103898596A (en) * | 2014-03-28 | 2014-07-02 | 上海大学 | Organic electrolyte, method for extracting non-metallic inclusions from steel and electrolyzer |
| CN106840802A (en) * | 2017-03-09 | 2017-06-13 | 北京科技大学 | A kind of original appearance analysis method of electrolytic separation high-carbon steel inclusion |
| CN109449486A (en) * | 2018-10-15 | 2019-03-08 | 苏州大学 | A kind of application of electrolysis additive |
| CN111596094A (en) * | 2020-05-12 | 2020-08-28 | 上海大学 | Three-dimensional etching device and method for nonmetallic inclusions in steel |
Non-Patent Citations (2)
| Title |
|---|
| 用酸溶法研究钢中超细氧化物夹杂的三维形貌;刘自立等;《钢铁研究学报》;20070430(第04期);全文 * |
| 硫系、碲系、铅系易切削钢组织及硫化物对比分析;曹晨巍 等;《冶金分析》;20200715;第40卷(第7期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112763296A (en) | 2021-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111596094B (en) | Three-dimensional etching device and method for nonmetallic inclusions in steel | |
| JP5098843B2 (en) | Method for determining the solid solution content of the element of interest in a metal sample | |
| CN102538703B (en) | Method for extracting and observing three-dimensional appearance of non-metallic inclusion in steel in full-scale mode | |
| CN102213654B (en) | Electrolytic extraction and detection method of nonmetallic inclusion in steel by utilizing organic solution | |
| Fosnacht et al. | Evaluation of zinc sulphate electrolytes containing certain impurities and additives by cyclic voltammetry | |
| RU2698004C1 (en) | Device for electrolytic etching and dissolution and a method for extracting particles of a metallic compound | |
| CN107084870B (en) | The detection method of sulfur-bearing field trash in a kind of steel | |
| RU2703241C1 (en) | Method of extracting metal compound particles, a method of analyzing metal compound particles and an electrolytic solution used | |
| CN112763296B (en) | Three-dimensional etching method for chromium-manganese stainless steel inclusions | |
| CN111638173A (en) | Method for detecting metal magnetic impurities in positive electrode material | |
| US20110240477A1 (en) | Method for analyzing metal material | |
| CN111238916B (en) | Classified extraction and quantitative analysis method for nonmetallic inclusions in high-temperature alloy | |
| CN109295327B (en) | Micron porous copper and preparation method and application thereof | |
| CN106596669A (en) | Device and method for nondestructive testing of sulfide inclusions in steel | |
| JP7020447B2 (en) | A method for analyzing inclusions and / or precipitates in a metal sample, and a method for collecting inclusions and / or precipitates in a metal sample. | |
| CN107576556A (en) | The method of superfine carbide in electroextraction steel | |
| CN112816281A (en) | Method for in-situ three-dimensional etching of sulfide in sulfur-containing special steel | |
| CN113447509A (en) | Sample preparation method of scanning electron microscope sample for inclusions in rare earth weathering steel | |
| CN112763524B (en) | Three-dimensional corrosion method for carbide in GCr15 bearing steel | |
| JP2019039710A (en) | Extraction method of carbide and/or nitride in metal material, analysis method of the carbide and/or nitride, analysis method of quantity of solid solution carbon and/or quantity of solid solution nitrogen in the metal material, and electrolytic solution used therefor | |
| JP2004301605A (en) | Electrolyte for extraction analysis of deposit and/or inclusion in steel, and electrolytic extraction method of deposit and/or inclusion in steel using the same | |
| CN112798386B (en) | In-situ three-dimensional electrolytic etching liquid and electrolytic etching method for second-phase particles in stainless steel | |
| El‐Aziz | Corrosion resistance of Nd‐Fe‐B permanent magnetic alloys. Part 1: Role of alloying elements | |
| JP2009008586A (en) | Method of obtaining solid solution content rate of target element in metal sample | |
| JP2024109140A (en) | Method for electrolytic extraction of inclusions and/or precipitates in metallic materials, method for analyzing inclusions and/or precipitates in metallic materials, and electrolyte for electrolytic extraction of metallic materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |