CN110607428A - Corrosion-resistant treatment method for face-centered cubic structure metal - Google Patents
Corrosion-resistant treatment method for face-centered cubic structure metal Download PDFInfo
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- CN110607428A CN110607428A CN201910948910.5A CN201910948910A CN110607428A CN 110607428 A CN110607428 A CN 110607428A CN 201910948910 A CN201910948910 A CN 201910948910A CN 110607428 A CN110607428 A CN 110607428A
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
Abstract
The application provides a corrosion-resistant treatment method for a metal with a face-centered cubic structure, belonging to the technical field of metal material processing technologies. The corrosion-resistant treatment method of the face-centered cubic structure metal comprises the steps of carrying out rotary forging treatment on the face-centered cubic structure metal to obtain a first deformation structure; and annealing the first deformation structure. According to the corrosion-resistant treatment method for the face-centered cubic structure metal, the face-centered cubic structure metal is subjected to rotary forging treatment and annealing heat treatment in sequence, so that the crystal boundary structure of the face-centered cubic structure metal is optimized to improve the corrosion resistance of the face-centered cubic structure metal, and the corrosion-resistant treatment method can be widely applied to industry.
Description
Technical Field
The application belongs to the technical field of metal material processing technology, and relates to a corrosion-resistant treatment method for a metal with a face-centered cubic structure.
Background
Common face centered cubic materials include aluminum alloys, copper alloys, austenitic stainless steels, iron-nickel based and nickel based alloys, and the like. Taking austenitic stainless steel as an example, austenitic stainless steel is widely used in industries such as petroleum, chemical industry, power stations and the like because of its excellent mechanical properties and good corrosion resistance under conventional conditions. However, corrosion cracking often occurs during the use of austenitic stainless steel, which results in structural failure, thereby causing great economic loss to enterprises and seriously endangering personal safety. Common corrosion types of austenitic stainless steels include inter-granular corrosion and inter-granular stress corrosion.
At present, a treatment method for improving the corrosion resistance of austenitic stainless steel is generally a surface treatment method, and specifically, a surface film is prepared on the surface of the stainless steel by the technologies of a sol-gel method, deposition, electroplating and the like, so that the surface of a material is isolated from a corrosive medium, and the corrosion resistance of the austenitic stainless steel can be effectively improved. However, in the above surface treatment method, it is difficult to industrially and widely apply the surface treatment method because the treatment equipment is complicated and the preparation of the surface film is difficult. Therefore, how to develop a method for improving the corrosion resistance of austenitic stainless steel suitable for industrial application has been a technical problem in the field, and no better solution is available at present.
Disclosure of Invention
Technical problem to be solved
In view of the above technical problems, the present application provides a corrosion-resistant treatment method for a face-centered cubic metal, which optimizes a grain boundary structure of the face-centered cubic metal by sequentially performing a rotary forging treatment and an annealing heat treatment on the face-centered cubic metal to improve corrosion resistance of the face-centered cubic metal, and the corrosion-resistant treatment method of the present application can also be widely applied in industry.
(II) technical scheme
The application provides a corrosion-resistant treatment method of a face-centered cubic structure metal, wherein the face-centered cubic structure metal is tubular or rod-shaped, and the corrosion-resistant treatment method comprises the following steps:
carrying out rotary forging treatment on the face center cubic structure metal to obtain a first deformation structure;
and annealing the first deformation structure.
Further, before the rotary forging process is performed on the face-centered cubic structure metal, the method further comprises the following steps:
and carrying out solution treatment on the face-centered cubic structure metal.
Further, the cooling treatment in the solution treatment is a first quenching treatment.
Further, the solution treatment includes:
performing first heating treatment on the face-centered cubic structure metal, wherein the heating temperature of the first heating treatment is 1050-;
and carrying out first quenching treatment on the face-centered cubic structure metal subjected to the first heating treatment.
Further, the cooling treatment in the annealing treatment is a second quenching treatment.
Further, the annealing treatment includes:
carrying out second heating treatment on the first deformation structure, wherein the heating temperature of the second heating treatment is 1000-1150 ℃, and the heating time is 2-60 min;
and carrying out second quenching and water quenching treatment on the first deformed structure after the second heating treatment.
Further, in the rotary forging process, the radial reduction ratio is 2% to 10%.
(III) advantageous effects
According to the technical scheme, the method has at least one of the following beneficial effects:
(1) according to the corrosion-resistant treatment method for the face-centered cubic structure metal, the face-centered cubic structure metal is subjected to rotary forging treatment and annealing heat treatment in sequence, so that the crystal boundary structure of the face-centered cubic structure metal is optimized to improve the corrosion resistance of the face-centered cubic structure metal.
(2) According to the corrosion-resistant treatment method for the face-centered cubic structure metal, the rotary forging treatment process and the annealing heat treatment process are widely applied in industry, so that the corrosion-resistant treatment method can be widely applied in industry.
(3) According to the corrosion-resistant treatment method for the face-centered cubic structure metal, the face-centered cubic structure metal is subjected to rotary forging treatment, so that the face-centered cubic structure metal is high in forging efficiency, good in forging structure performance and high in forging size precision. Meanwhile, the method is favorable for introducing larger pre-strain to the face-centered cubic structure metal.
Drawings
FIG. 1 is a flow chart of a method for corrosion-resistant treatment of a face centered cubic structured metal in an embodiment of the present application;
fig. 2 is a grain boundary reconstructed pattern of the austenitic stainless steel according to the present embodiment, wherein (a) is a raw material and (b) is a processed product.
Detailed Description
The application provides a corrosion-resistant treatment method for a face-centered cubic structure metal, which is characterized in that the face-centered cubic structure metal is subjected to rotary forging treatment and annealing heat treatment in sequence, so that the crystal boundary structure of the face-centered cubic structure metal is optimized to improve the corrosion resistance of the face-centered cubic structure metal, and the corrosion-resistant treatment method can be widely applied to industry.
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further described in detail below with reference to the accompanying drawings in combination with specific embodiments.
In an exemplary embodiment of the present disclosure, a method for corrosion-resistant treatment of a face-centered cubic structure metal is provided, and each component of the present embodiment is described in detail below:
in this embodiment of the present application:
as shown in fig. 1 to 2, an embodiment of the present application provides a method for corrosion-resistant treatment of a face-centered cubic structure metal, the face-centered cubic structure metal being tubular or rod-shaped, the method comprising:
carrying out rotary forging treatment on the face center cubic structure metal to obtain a first deformation structure;
and annealing the first deformation structure.
In this embodiment, the face-centered cubic structure metal is a tubular or rod-like structure. The material of the face-centered cubic structure metal comprises aluminum alloy, copper alloy, austenitic stainless steel, iron-nickel base, nickel base alloy and the like. Here, austenitic stainless steel is taken as an example, and it is needless to say that the corrosion-resistant treatment method in each example herein can be applied to a face-centered cubic structure metal of other materials.
In this example, the austenitic stainless steel is first subjected to a rotary forging process to introduce a pre-strain to the austenitic stainless steel. The austenitic stainless steel is subjected to rotary forging treatment to obtain austenitic stainless steel which is different from the austenitic stainless steel before processing, namely the first deformed austenitic stainless steel. The first deformed austenitic stainless steel is then annealed. Through the combination of stress introduced by rotary forging and subsequent annealing heat treatment, the grain boundary structure of the austenitic stainless steel is optimized, and the corrosion resistance of the austenitic stainless steel is further improved.
In addition, the face-centered cubic structure metal is processed by adopting a rotary forging treatment process in the embodiment, and the following technical effects are included: (1) the forging efficiency is high. The forging process is automatically controlled, the process steps are uninterrupted, the forging piece is formed at one time, and repeated remelting and heating of the face-centered cubic structure metal are avoided. (2) The forging piece has good structure performance. The three-dimensional compressive stress is borne in the deformation process of the face-centered cubic structure metal, so that the internal defects of the face-centered cubic structure metal are eliminated, the tissue segregation is improved, and uniform and fine tissues with ideal fiber flow directions are obtained. (3) The forging size precision is high. The traditional forging process is limited by the precision of a forging tool and a size control system, the size deviation of a forged piece is large, the cutting machining amount is too large, the material waste is caused, and the benefit maximization of the downstream machining industry is not facilitated. The size precision of the forged piece produced by the rotary forging technology is obviously improved, and near-net forming can be realized. (4) The rotary forging technology can forge two directions of the face-centered cubic structure metal at the same time, restrain the transverse deformation of the face-centered cubic structure metal, limit the expansion of cracks, improve the processing efficiency, enable a forge piece to bear three-dimensional compressive stress, and be more beneficial to introducing larger pre-strain to the face-centered cubic structure metal. Meanwhile, the rotary forging focuses on the processing treatment of the outer surface of the face-centered cubic structure metal, so that the pre-strain introduced at the outer wall of the first deformation structure is larger than the internal pre-strain, and the corrosion resistance of the outer wall of the face-centered cubic structure metal is obviously better than that of the internal part of the face-centered cubic structure metal.
In some embodiments, before the rotary forging process is performed on the face-centered cubic structural metal, the method further comprises: and carrying out solution treatment on the face-centered cubic structure metal. The purpose of the solution treatment is to homogenize the structure of the metal with the face-centered cubic structure, and simultaneously, to re-blend the carbide precipitated in the production process of the metal with the face-centered cubic structure into the matrix, so as to improve the corrosion resistance of the metal with the face-centered cubic structure. Wherein, the cooling treatment in the solid solution treatment is a first quenching treatment, which can help the face-centered cubic structure metal to rapidly pass through the sensitization region and can ensure that the microstructure of the face-centered cubic structure metal at high temperature can be reserved at room temperature.
In some embodiments, the solution treatment comprises:
performing first heating treatment on the face-centered cubic structure metal, wherein the heating temperature of the first heating treatment is 1050-;
and carrying out first quenching treatment on the face-centered cubic structure metal subjected to the first heating treatment.
In some embodiments, the cooling process in the annealing process is a second quench water quench process.
In some embodiments, the annealing process comprises:
carrying out second heating treatment on the first deformation structure, wherein the heating temperature of the second heating treatment is 1000-1150 ℃, and the heating time is 2-60 min;
and carrying out second quenching and water quenching treatment on the first deformed structure after the second heating treatment.
In some embodiments, the radial reduction is 2% to 10% in the rotary forging process.
In order to more directly illustrate the principle and effect of the corrosion-resistant treatment method in the embodiment of the present application, the following is described experimentally:
the application relates to improving corrosion resistance by optimizing a grain boundary structure of a face-centered cubic structure metal. Among them, the grain boundary is an important structural feature of the polycrystalline material, and the corrosion resistance of the material is closely related to the structure of the grain boundary. Based on a Coincidence Site Lattice (CSL) model, the grain boundaries can be divided into low Σ CSL grain boundaries (Σ ≦ 29) (also called special grain boundaries) and Random Boundary (RB) (Σ > 29). Among these, low sigma CSL grain boundaries exhibit strong inhibitory effects on slip, fracture, corrosion and stress corrosion cracking, sensitization and solute segregation (equilibrium and non-equilibrium), some even completely immune. Random grain boundaries, due to their high energy and high mobility, often serve as nuclei for crack growth and as channels for propagation, leading to the occurrence of intergranular corrosion cracks and intergranular stress corrosion cracks. Therefore, controlling and optimizing the Grain Boundary Characteristic Distribution (GBCD) inside the material becomes an important means for improving the corrosion resistance.
In the following examples and comparative examples, the optimization effect of the material on the grain boundary structure characteristics is expressed by low Σ CSL grain boundary ratio (%), and a higher value indicates a better grain boundary optimization effect; the corrosion resistance of the material is represented by a reactivation current ratio (%) and a self-corrosion potential (V), respectively, and the lower the reactivation current ratio is, the more positive the self-corrosion potential tends to be, indicating that the corrosion resistance of the material is better.
Example 1
And (3) rotationally forging the austenitic stainless steel bar or pipe by using a rotary forging machine, wherein the radial relative reduction is 2%, 3%, 6% and 10%. And then, annealing treatment of keeping the temperature of 1050 ℃ for 5min is carried out on the deformation sample in a heat treatment furnace, and quenching water is taken out after heat preservation, wherein specific process parameters are shown in table 1. The low Σ CSL ratio inside the sample after the thermomechanical treatment was changed depending on the rolling reduction, and specific test results are shown in table 1.
Curing the thermomechanically treated sample with an epoxy resinAnd (5) inlaying the agent to prepare a standard electrochemical corrosion sample. At room temperature at 0.5M H2SO4Samples were subjected to Electrokinetic Potential Reactivation (EPR) experiments and polarization curve measurements in +0.01M KSCN solution, with reactivation current ratios and self-corrosion potentials varying with the reduction. The reactivation current ratio and the self-corrosion potential measured after sensitizing the sample at 650 ℃ for 2h are shown in Table 1.
TABLE 1 test results for different radial relative reductions
Example 2
And (3) rotationally forging the austenitic stainless steel bar or pipe by using a rotary forging machine, wherein the radial relative reduction is selected to be 3%. And then, annealing the deformation sample in a heat treatment furnace at 1000 ℃, 1050 ℃, 1100 ℃ and 1150 ℃ for 5min, keeping the temperature, taking out the deformation sample, and performing water quenching, wherein the specific process parameters are shown in Table 2. The low sigma CSL ratio inside the sample after the thermomechanical treatment was varied with the annealing temperature, and the specific test results are shown in Table 2.
And inlaying the sample subjected to the thermomechanical treatment by using epoxy resin and a curing agent to prepare a standard electrochemical corrosion sample. At room temperature at 0.5M H2SO4Samples were subjected to potentiodynamic reactivation (DL-EPR) experiments and polarization curve measurements in +0.01M KSCN solution, with reactivation current ratios and self-corrosion potentials varying with annealing temperature. The reactivation current ratio and the self-corrosion potential measured after sensitizing the sample at 650 ℃ for 2h are shown in Table 2.
TABLE 2 test results for different annealing temperatures
Example 3
And (3) rotationally forging the austenitic stainless steel bar or pipe by using a rotary forging machine, wherein the radial relative reduction is 3%. And then, annealing the deformation sample in a heat treatment furnace at 1050 ℃ for 2min, 5min, 30min and 60min, taking out the deformation sample after heat preservation, and taking out water quenching, wherein the specific process parameters are shown in Table 3. The low sigma CSL ratio inside the samples after thermomechanical treatment varied with the annealing time, and the specific test results are shown in table 3.
And inlaying the sample subjected to the thermomechanical treatment by using epoxy resin and a curing agent to prepare a standard electrochemical corrosion sample. At room temperature at 0.5M H2SO4Samples were subjected to Electrokinetic Potential Reactivation (EPR) experiments and polarization curve measurements in +0.01M KSCN solution, with reactivation current ratios and self-etching potentials varying with annealing time. The reactivation current ratio and the self-corrosion potential measured after sensitizing the sample at 650 ℃ for 2h are shown in Table 3.
TABLE 3 test results for different annealing times
Comparative example 1
In order to compare the difference of the organization and the performance of the material after the deformation heat treatment and the parent material, a piece of original material is taken to be subjected to solution treatment at 1050 ℃ for 30min, then is subjected to sensitization at 650 ℃ for 2h, and then is subjected to an electrochemical corrosion experiment in a 0.5M H2SO4+0.01M KSCN solution at normal temperature, and the test results are shown in Table 4. It can be found that under the same sensitization condition, the corrosion resistance of the crystal boundary structure optimized sample is obviously improved compared with that of the parent metal.
The material processed by the method is made into a standard metallographic specimen, and after grinding, polishing and electrolytic corrosion, the grain boundary characteristic distribution of the material is tested by utilizing a back scattering electron diffraction technology, wherein the low sigma CSL grain boundary proportion in the structure can reach 80.4%; under the same sensitization condition, the reactivation current is reduced to 8.92% from 17.57% of the parent metal, and the corrosion resistance of the material is obviously improved.
Fig. 2(a) shows the distribution of grain boundary characteristics in the matrix structure, in which the low Σ CSL grain boundary is 58.1%, and fig. 2(b) shows the distribution of grain boundary characteristics in the material structure after the thermomechanical treatment by the above-described method, in which the low Σ CSL grain boundary ratio is 80.4%, and in the figure, the black line represents a high-energy free grain boundary, and the gray line represents a low Σ CSL grain boundary.
TABLE 5 results of measurements on thermo-mechanical treated materials and base materials
Up to this point, the present embodiment has been described in detail with reference to the accompanying drawings. From the above description, one skilled in the art should clearly recognize the present application.
It is to be noted that, in the attached drawings or in the description, the implementation modes not shown or described are all the modes known by the ordinary skilled person in the field of technology, and are not described in detail. Furthermore, the above definitions of the various elements and methods are not limited to the specific structures, shapes, or configurations shown in the examples.
It is also noted that the illustrations herein may provide examples of parameters that include particular values, but that these parameters need not be exactly equal to the corresponding values, but may be approximated to the corresponding values within acceptable error tolerances or design constraints. Directional phrases used in the embodiments, such as those referring to "upper", "lower", "front", "rear", "left", "right", etc., refer only to the orientation of the attached drawings and are not intended to limit the scope of the present application. In addition, unless steps are specifically described or must occur in sequence, the order of the steps is not limited to that listed above and may be changed or rearranged as desired by the desired design. The embodiments described above may be mixed and matched with each other or with other embodiments based on design and reliability considerations, i.e., technical features in different embodiments may be freely combined to form further embodiments.
The above-mentioned embodiments are further described in detail for the purpose of illustrating the invention, and it should be understood that the above-mentioned embodiments are only illustrative of the present invention and are not to be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A corrosion-resistant treatment method for a face-centered cubic structure metal, characterized in that the face-centered cubic structure metal is tubular or rod-shaped, the corrosion-resistant treatment method comprising:
carrying out rotary forging treatment on the face-centered cubic structure metal to obtain a first deformation structure;
and carrying out annealing treatment on the first deformation structure.
2. The method for corrosion-resistant treatment of a face-centered cubic structure metal according to claim 1, further comprising, before said rotary forging treatment of said face-centered cubic structure metal:
and carrying out solution treatment on the face-centered cubic structure metal.
3. The method for corrosion-resistant treatment of a face-centered cubic structure metal according to claim 2, wherein the cooling treatment in the solution treatment is a first quenching treatment.
4. The method of corrosion resistance treatment of a face centered cubic structured metal according to claim 3, wherein the solution treatment comprises:
carrying out first heating treatment on the face-centered cubic structure metal, wherein the heating temperature of the first heating treatment is 1050-;
and carrying out the first quenching treatment on the face-centered cubic structure metal subjected to the first heating treatment.
5. The method for corrosion-resistant treatment of a face-centered cubic structure metal according to claim 1, wherein the cooling treatment in the annealing treatment is a second quenching treatment by quenching with water.
6. The method for corrosion-resistant treatment of a face-centered cubic structure metal according to claim 5, wherein the annealing treatment comprises:
carrying out second heating treatment on the first deformation structure, wherein the heating temperature of the second heating treatment is 1000-1150 ℃, and the heating time is 2-60 min;
and carrying out second quenching and water quenching treatment on the first deformed structure subjected to the second heating treatment.
7. The method for corrosion-resistant treatment of a face-centered cubic structure metal according to any one of claims 1 to 6, wherein in the rotary forging treatment, a radial reduction ratio is 2% to 10%.
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| CN108193036A (en) * | 2017-12-18 | 2018-06-22 | 南昌大学 | A kind of method for optimizing the distribution of 316L austenitic stainless steels Grain Boundary Character |
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| WO1999007902A1 (en) * | 1997-08-04 | 1999-02-18 | Integran Technologies Inc. | Metallurgical method for processing nickel- and iron-based superalloys |
| CN104278138A (en) * | 2014-09-03 | 2015-01-14 | 上海大学 | Grain boundary engineering technique for enhancing corrosion resistance of 304 stainless steel |
| CN104593571A (en) * | 2015-01-16 | 2015-05-06 | 上海大学 | Grain boundary engineering process method for improving corrosion resistance of stainless steel 316 |
| CN105177262A (en) * | 2015-09-25 | 2015-12-23 | 安阳工学院 | Method for increasing proportion of special grain boundaries in precipitation strengthened austenitic heat-resistance steel |
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