CN109112261B - Duplex stainless steel with strong microbial corrosion resistance - Google Patents
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- 238000005260 corrosion Methods 0.000 title claims abstract description 94
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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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
- 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
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
- C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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Abstract
The invention discloses a microbe corrosion resistant duplex stainless steel and a heat treatment process thereof, wherein the duplex stainless steel comprises the following chemical components (by weight percent): cr: 22.0-25.0; ni: 4.5-7.5; mo: 1.5-3.0; cu: 2.0-4.0; ga 1.0-4.0; n: 0.2 to 0.3; c is less than or equal to 0.03; si is less than or equal to 1.0; mn is less than or equal to 3.0; p is less than or equal to 0.03; s is less than or equal to 0.02; the balance being Fe. The content of impurity elements in the alloy meets the corresponding requirements in the national standard of duplex stainless steel. The new duplex stainless steel material has a unique function of inhibiting the generation of bacterial biofilms, can obviously reduce the risk of microbial corrosion of the duplex stainless steel in different use environments, and can be widely applied to the field of large-scale application of the duplex stainless steel such as oceans, petroleum and natural gas and the like.
Description
Technical Field
The invention relates to duplex stainless steel, and particularly provides a new duplex stainless steel material with strong microbial corrosion resistance, which has a unique function of inhibiting bacterial biofilm formation on the surface of the material and can obviously reduce the risk of microbial corrosion of the duplex stainless steel in different use environments.
Background
The microbial corrosion (MIC) refers to a process of corroding various materials used in the environment due to the life activities of various microorganisms. In the united states alone each year, economic losses of 300- "500 billion dollars are incurred due to microbial corrosion of materials. Of these, microbial induced corrosion accounts for approximately 20% of total metal and building material corrosion. In recent years, microbial corrosion has become a very problematic problem in the industrial fields of oceans, petroleum and gas processing, and water treatment. Microbial corrosion can cause leakage of petroleum pipelines and plugging of injection wells, thereby presenting a potential safety risk to the petroleum production process. In 2007, in Prudhoe gulf of alaska, the crude oil pipeline of BP oil company has a serious oil leakage accident, causing serious pollution of the environment and continuous rise of the international oil price. Later, microbial corrosion is believed to be the primary cause of this accident. With the increasingly severe exploitation conditions of deep oil fields, stainless steel materials with excellent corrosion resistance and comprehensive mechanical properties are required, and the duplex stainless steel can meet the requirements of actual working conditions undoubtedly.
The duplex stainless steel has good mechanical property and corrosion resistance, and is widely applied to marine engineering and ship manufacturing, such as offshore oil field gas, water systems, deep water pumps, offshore drilling platforms, submarine mining equipment, warships, special ships and the like. It has been reported that corrosion caused by marine microorganisms accounts for about 70-80% of the corrosion of marine materials during the development and utilization of marine resources, with losses of up to billions of dollars per year due to such corrosion. Under the marine environment, the problems of microbial corrosion and biological fouling of marine engineering materials cause billions of yuan of economic loss and more than 30 percent of energy waste of navigation bodies in the sea to the country every year, which becomes one of the technical bottlenecks seriously restricting the development of major marine engineering technologies and equipment, and the problem of material failure caused by the problems seriously affects the reliability and the service life of the marine engineering equipment. Therefore, the microbial corrosion failure mechanism and the protection technology of the marine engineering material become problems to be solved urgently in the field of marine engineering in China. The existing duplex stainless steel material has high corrosion resistance, but still belongs to a biological inert material, can only effectively slow down the microbial corrosion rate, and still cannot radically solve the harm caused by the microbial corrosion. Thus, the conventional solution is generally to apply a coating containing a biocide to the surface of the stainless steel. However, the adopted bactericide often has adverse factors of environmental unfriendliness, influence on marine ecological balance, poor durability and the like.
Therefore, by imparting a very strong ability to resist the formation of bacterial biofilm to duplex stainless steel, a novel duplex stainless steel material having a function of resisting microbial corrosion by itself has been developed and studied, and the possibility of microbial corrosion thereof has been eliminated or reduced from a material standpoint. The novel duplex stainless steel is expected to become an ideal marine and oilfield stainless steel material which is resistant to both chloride ion corrosion and microbial corrosion, and the success of the stainless steel has important social and economic significance.
Disclosure of Invention
The invention aims to provide a duplex stainless steel with strong microbial corrosion resistance and a heat treatment process thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a duplex stainless steel resistant to microbial corrosion comprises the following chemical components in percentage by weight: cr: 18.0-28.0; ni: 3.0-10.0; mo: 1.0-5.0; cu: 0.5-5.5; 0.5 to 5.5 portions of Ga; n: 0.14-0.32; c is less than or equal to 0.03; si is less than or equal to 1.0; mn is less than or equal to 3.0; p is less than or equal to 0.03; s is less than or equal to 0.02; the balance being Fe. Preferred chemical compositions are: cr: 22.0-25.0; ni: 4.5-7.5; mo: 1.5-3.0; cu: 2.0-4.0; ga 1.0-4.0; n: 0.2 to 0.3; c is less than or equal to 0.03; si is less than or equal to 1.0; mn is less than or equal to 3.0; p is less than or equal to 0.03; s is less than or equal to 0.02; the balance being Fe. The content of impurity elements in the steel meets the corresponding requirements in the national standard of the duplex stainless steel.
The Ga element in the invention is an important alloy element in the duplex stainless steel with strong microbial corrosion resistance, and is a necessary condition for ensuring that the duplex stainless steel has the function of inhibiting the formation of a biofilm on the surface of the material, and the Ga element can disturb the metabolism of cells, inhibit the continuous growth of the cells and finally cause the apoptosis of the cells.
The Ga content of the stainless steel material is 0.5-5.5 in percentage by weight; the preferable composition is 1.0-4.0 to ensure that the Ga element can be fully dissolved in the matrix through solution treatment under the heat treatment conditions of solution treatment and aging treatment, and after certain time of aging, supersaturated Ga can be precipitated from the steel to form enough Fe3Ga phase, a duplex stainless steel that is highly resistant to microbial corrosion, is capable of sustained release of Ga in contact with a bacterial environment. Furthermore, the duplex stainless steel of the present invention is intended to avoid an increase in the microbial corrosion resistanceThe corrosion resistance of the alloy itself is reduced at the same time as the strength is increased, and it is necessary to limit the Cu/Ga ratio to a certain range, i.e., 1 to 2.
Different from the preparation method of the traditional antibacterial duplex stainless steel, the duplex stainless steel with strong microbial corrosion resistance is added with Ga element, because the melting point is 29.76 ℃, pure Ga metal exists in a liquid state at room temperature, Fe-Ga alloy is adopted for smelting, and because Ga is easy to volatilize at high temperature, the volatilization amount of Ga must be considered during proportioning, and 1-2% of Fe-Ga alloy is added in each 50 g of smelting alloy. The preparation method of the duplex stainless steel containing the Ga element and having strong microbial corrosion resistance comprises the following steps:
(1) the alloy components are sequentially added into a vacuum smelting furnace for vacuum induction smelting, and due to the volatility of Ga, Fe-Ga alloy is firstly added into the smelting furnace and placed at the bottom, and after refining at 1400-1500 ℃ for 10-20 minutes, magnetic stirring is carried out, and then casting is carried out to form a cast ingot;
(2) because of the addition of Fe-Ga alloy, the heat preservation time before forging needs to be prolonged to ensure the uniformity of components and phase structures in the duplex stainless steel, and the homogenization annealing is carried out by adopting 1050-plus-material 1100 ℃ heat preservation for 8-10 hours to forge the duplex stainless steel into a rod-shaped or block-shaped sample;
(3) air cooling or water cooling to room temperature.
By adopting the mass ratio of the components disclosed by the invention and combining with the corresponding preparation process disclosed by the invention, the duplex stainless steel with strong microbial corrosion resistance is obtained.
The invention also provides a heat treatment process of the duplex stainless steel with strong microbial corrosion resistance, which is an important part of the invention, and the solid solution temperature and the solid solution time influence the solid solubility of Ga element completely melted into Fe matrix, so the proper heat treatment system in the invention is as follows: the temperature of the solution treatment is 1050-. Preferred solid solution temperature and solid solution time are characterized by: the temperature of the solution treatment is 1100-.
The aging temperature and the aging time can influence the size and the quantity of Ga element precipitated phases from the stainless steel, and the method is characterized in that: the temperature of the aging treatment is 550-; preferred ageing temperatures and ageing times are characterized by: the temperature of the aging treatment is 580-680 ℃, the heat preservation time is 3.5-5.5h, and the air cooling is carried out to the room temperature.
The microbial corrosion resistant duplex stainless steel and the heat treatment process thereof provided by the invention innovatively realize the perfect combination of the antimicrobial corrosion effect and the original duplex stainless steel performance, can obviously reduce the microbial corrosion risk of the duplex stainless steel in different use environments, and can be widely applied to the field of large-scale application of duplex stainless steel such as oceans, petroleum and natural gas and the like.
The invention has the beneficial effects that:
1. the heat treatment method of the duplex stainless steel with strong microbial corrosion resistance, disclosed by the invention, is an optimized heat treatment system, and through solid solution and aging heat treatment, the risk of microbial corrosion in different use environments can be reduced for the duplex stainless steel material.
2. The microbe corrosion resistant duplex stainless steel can be widely applied to the fields of massive application of the existing duplex stainless steel such as oceans, petroleum and natural gas and the like.
Detailed Description
According to the chemical composition range set by the duplex stainless steel material with strong microbial corrosion resistance, 10 kg of each of the duplex stainless steel with strong microbial corrosion resistance is forged by adopting a 15 kg vacuum induction furnace for smelting examples and comparative examples, and the chemical compositions are shown in Table 1.
TABLE 1 examples and comparative examples Duplex stainless Steel alloy chemistry (wt%)
The detailed parameters of the solution and aging heat treatment are established according to the parameter ranges of the heat treatment method set by the duplex stainless steel with strong microbial corrosion resistance, and are shown in the table 2.
TABLE 2 Heat treatment Process parameters of examples and comparative examples
The corrosion performance of the strongly microbial corrosion resistant duplex stainless steels of examples and comparative examples after being co-cultured for 14 days with a marine commonly used Pseudomonas aeruginosa medium in 2216E medium was evaluated, and the pitting potential E was measured according to the stainless pitting potential measuring method (national standard: GB/T17899-pWhile corrosion current i is also measuredcorrAnd the deepest pitting depth caused by pseudomonas aeruginosa, wherein the pitting caused by microbial corrosion is the most harmful to the material acknowledged in the world at present, and the pitting depth is regarded as an important index for quantitatively evaluating the corrosion resistance of the material, so that the pitting depth caused by microbial corrosion on the surface of a sample is detected by a laser confocal microscope, and the test result is shown in table 3.
Table 3 results of performance test of duplex stainless steels of examples and comparative examples
As can be seen from the results of Table 3, the strongly microbial corrosion resistant duplex stainless steels of examples 1 to 8 of the present invention all exhibited excellent bacterial microbial corrosion resistance, corrosion current i of examplescorrAnd deepest pitting depth lower than that of comparative example, pitting potential EpAre all higher than the comparative examples. The proper Ga content and the heat treatment process (solid solution and aging heat treatment) are the key points of the strong microbial corrosion resistant duplex stainless steel provided by the invention for exerting the microbial corrosion resistance.
The solid solution treatment has important influence on the microbial corrosion resistance of the duplex stainless steel material with strong microbial corrosion resistance. Under the condition of ensuring that the aging temperature and the aging time are within the application range of the invention, the solid solution temperature is too low, harmful intermetallic phases can be generated in the duplex stainless steel with strong microbial corrosion resistance, the existence of the harmful intermetallic phases greatly reduces the pitting potential of the material per se, and the corrosion resistance of the material per se is seriously reduced after the co-culture with bacteria (comparative example 1-1). The solid solution temperature is too high, the grain boundary is over-burnt, the phenomenon of coarse grains is obvious, the unbalanced tendency of the resistance at the positions of the grains and the grain boundary is increased, and the galvanic cell effect among metal elements in the alloy is caused, so that the self corrosion resistance of the material is reduced, and the corrosion resistance of the duplex stainless steel cultured by the bacterial solution is also reduced (comparative example 1-2). The solid solution time is too short, so that the Ga-rich phase cannot be completely solid-dissolved into the matrix, and the corrosion resistance of the material is reduced (comparative examples 1 to 3); too long solid solution time also causes galvanic effect and seriously deteriorates the corrosion resistance of the duplex stainless steel (comparative examples 1 to 4), so that the corrosion resistance of the duplex stainless steel itself tends to be lowered after co-culture with bacteria in the case that the corrosion resistance is poor.
Under the condition of ensuring that the solid solution temperature and the solid solution time are within the application range of the invention, Ga can be completely dissolved into a steel matrix to form a supersaturated solid solution, and after the aging treatment, supersaturated Ga element is separated out from the steel to form enough Fe3Ga phase makes the material play effective antimicrobial action, kills microorganism and simultaneously improves the ability of the material to resist the microbial corrosion. The aging temperature is too low, and enough Fe can not be separated out from the duplex stainless steel with strong microbial corrosion resistance3The Ga phase, which renders the material incapable of antimicrobial properties against a large number of microorganisms in the environment, causes biofilm formation on the surface of the material, resulting in a reduction in the microbial corrosion resistance of the surface (comparative example 2-1). The aging temperature is too high, so that a large amount of Fe is separated out from the duplex stainless steel with strong microbial corrosion resistance3Ga phase, and the size of the phase increases, resulting in a decrease in the corrosion resistance of the material itself (comparative example 2-2). The aging time is too short, and enough Fe can not be separated out from the duplex stainless steel with strong microbial corrosion resistance3The Ga phase is close to the material structure in the solid solution state, so in this case, the duplex stainless steel having strong microbial corrosion resistance cannot obtain excellent microbial corrosion resistance (comparative examples 2 to 3). The aging time is too long, so that the precipitated Fe3The size of Ga phase is rapidly increased, so that the strong microbial corrosion resistance is achievedThe corrosion resistance of the phase stainless steel was greatly reduced (comparative examples 2 to 4).
For the Ga element content in the duplex stainless steel with strong microbial corrosion resistance, the addition amount is too low, so that the antimicrobial function of the duplex stainless steel is reduced, and the effective microbial corrosion resistance can not be achieved (comparative example 3), while the addition amount of Ga is too high, the material can be ensured to have effective antimicrobial performance, but the corrosion resistance of the material is damaged, so that the service life of the material is influenced (comparative example 4).
In the duplex stainless steel with strong microbial corrosion resistance, the content of Cu and Ga is in the range of the claims, and the ratio value of Cu/Ga is required to be between 1 and 2, because the corrosion resistance of the duplex stainless steel material is reduced by adding the Cu element, and the passive film formed in the corrosion environment is firmer by the Ga element, so that the corrosion resistance is improved, and the weakening of the corrosion resistance of the duplex stainless steel material by the Cu element is compensated by adding the Ga element, therefore, when the ratio value of Cu/Ga is too low, the antimicrobial property of the duplex stainless steel with strong microbial corrosion resistance is reduced, the effective microbial corrosion resistance can not be achieved (comparative example 5), and the corrosion resistance of the duplex stainless steel is reduced by excessively high Cu/Ga (comparative example 6).
As can be seen from the results of the above examples and comparative examples, the heat-treated duplex stainless steel having high resistance to microbial corrosion can have excellent resistance to microbial corrosion only when the Ga content, the solid solution temperature and the solid solution time, and the aging temperature and the aging time are in a certain suitable range and complement and cooperate with each other.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (5)
1. The duplex stainless steel with strong microbial corrosion resistance is characterized by comprising the following chemical components in percentage by weight: cr: 18.0-28.0; ni: 3.0-10.0; mo: 1.0-5.0; cu: 0.5-5.5; 0.5 to 5.5 portions of Ga; n: 0.14-0.32; c is less than or equal to 0.03; si is less than or equal to 1.0; mn is less than or equal to 3.0; p is less than or equal to 0.03; s is less than or equal to 0.02; the balance being Fe; according to weight percentage, Cu/Ga is 1-2;
the temperature of the solution treatment is 1050-;
the temperature of the aging treatment is 550-700 ℃, the heat preservation time is 3.0-8.0h, and the air cooling is carried out to the room temperature.
2. A duplex stainless steel having high microbial corrosion resistance according to claim 1, wherein said duplex stainless steel has a chemical composition, in terms of weight percent, of: cr: 22.0-25.0; ni: 4.5-7.5; mo: 1.5-3.0; cu: 2.0-4.0; ga 1.0-4.0; n: 0.2 to 0.3; c is less than or equal to 0.03; si is less than or equal to 1.0; mn is less than or equal to 3.0; p is less than or equal to 0.03; s is less than or equal to 0.02; the balance being Fe.
3. The duplex stainless steel having high microbial corrosion resistance according to claim 1, wherein: the temperature of the solution treatment is 1100-.
4. The duplex stainless steel having high microbial corrosion resistance according to claim 1, wherein: the temperature of the aging treatment is 580-680 ℃, the heat preservation time is 3.5-5.5h, and the air cooling is carried out to the room temperature.
5. Use of the duplex stainless steel according to claim 1 or 2 for the preparation of storage containers or liquid transfer pipes in the field of oil and energy recovery and marine engineering.
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