CN108441783B - Food-grade high-wear-resistance martensitic stainless steel material and preparation method thereof - Google Patents
Food-grade high-wear-resistance martensitic stainless steel material and preparation method thereof Download PDFInfo
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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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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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Abstract
The invention relates to a food-grade high-wear-resistance martensitic stainless steel material and a preparation method thereof, belonging to the field of stainless steel materials. The stainless steel comprises the following components in percentage by weight: c: 0.4-0.5%, Cr: 16.0-16.5%, Ni: 0.4-0.5%, Mo: 0.8-0.9%, Mn: 0.3-0.4%, Si: 0.3-0.4%, P: < 0.03%, S: less than 0.01%, the balance being iron and unavoidable impurities, the stainless steel may further contain Cu: 1.5 to 2.2 percent. The corrosion resistance of the material is balanced by adding higher content of C and Cr; controlling the Cr equivalent to obtain a martensite structure and ensuring that the ferrite content is lower than 2 percent; by adjusting the mass ratio of Mo to C, Mo is used for fixing C to ensure corrosion resistance, and meanwhile, a proper amount of Cu is added and the preparation process of the material is optimized, so that molybdenum-containing carbide and copper-rich phase are dispersed and separated out, and finally a high-hardness martensite matrix is obtained and has broad-spectrum antibacterial performance.
Description
Technical Field
The invention belongs to the field of stainless steel materials, and particularly relates to a food-grade high-wear-resistance martensitic stainless steel material and a preparation method thereof, in particular to a stainless steel material which is scratch-resistant, high-hardness, antibacterial and excellent in corrosion resistance and used for metal tableware products and a preparation method thereof.
Background
With the increasing living standard of people, the quality requirements of daily necessities are also continuously improved. Tableware belongs to the class of products, and people not only require that the tableware has the characteristics of excellent corrosion resistance, recyclability, elegant appearance, easy cleaning, difficult damage and the like, but also require that the tableware has an antibacterial function. In recent years, stainless steel tableware is more and more popular with people due to excellent comprehensive performance, and becomes an indispensable first-choice tableware for household dining tables, Chinese and western restaurants, high-grade hotels and the like.
Food grade stainless steel refers to the portion of food machinery that contacts food and must meet certain food safety requirements. The national standard GB 4806.9-2016 food safety national standard metal materials and products for food contact has strict limit on the migration amount of heavy metal ions in food-grade stainless steel. At present, the materials used for manufacturing food-grade stainless steel tableware on the market can be roughly classified into 430, 304(18-8) and 18-10 grades. The stainless steel used is classified into high-grade, medium-grade and low-grade tableware according to the difference of raw material cost and corrosion resistance. However, they have the common disadvantages of soft material and insufficient hardness. After a period of time, the tableware is easily scratched on the surface through multiple scrubbing, mutual collision and the like, the attractive effect is affected, and the corrosion resistance is reduced. Therefore, the quality of the scratch resistance of the surface of stainless steel tableware is concerned by manufacturers and consumers. In order to solve the problem, some manufacturers return the consumers to the polishing process for free at regular intervals, but the cost of the manufacturers is greatly increased, and the consumers are inconvenient. Therefore, there is a need to provide a new stainless steel material with high hardness, low cost and scratch resistance to solve the problem that the current stainless tableware is easy to scratch.
Disclosure of Invention
In view of the problem, the invention aims to provide a food-grade martensitic stainless steel material with high hardness and scratch resistance for metal tableware products, and simultaneously, the material also has antibacterial performance and excellent corrosion resistance.
The design idea of the invention is as follows:
the corrosion resistance is balanced by adding higher contents of C and Cr; a small amount of expensive Ni element is added to reduce the cost; controlling the Cr equivalent to obtain a martensite structure, avoiding the occurrence of high-temperature ferrite and ensuring that the content of the high-temperature ferrite is lower than 2 percent; the mass ratio of Mo to C is adjusted, Mo is used for fixing C, the C and Cr are prevented from forming carbide, and the corrosion resistance is reduced; adding a proper amount of Cu, and optimizing the material preparation process, thereby obtaining the dispersion precipitation of molybdenum-containing carbide and copper-rich phase in the steel, improving the hardness of the steel and simultaneously enabling the steel to have antibacterial performance. Through a new component design, the stainless steel material with scratch resistance, high hardness, antibiosis and excellent corrosion resistance is provided.
The technical scheme of the invention is as follows:
a food-grade high-wear-resistance martensitic stainless steel material comprises the following chemical components in percentage by weight: c: 0.4-0.5%, Cr: 16.0-16.5%, Ni: 0.4-0.5%, Mo: 0.8-0.9%, Mn: 0.3-0.4%, Si: 0.3-0.4%, P: < 0.03%, S: less than 0.01 percent, and the balance of iron and inevitable impurities.
The chemical composition of the steel also satisfies the following conditions: the Cr equivalent is less than 8.5, and is calculated according to the following formula:
cr equivalent is Cr% +0.8 xSi% +2 xMo% -2 xNi% -0.4 xMn% -0.6 xCu% -20 xC%.
The chemical composition of the steel can also contain 1.5-2.2% by weight of Cu.
The mass ratio of Mo to C in the chemical components of the steel meets the following requirements: Mo/C is more than 1.8.
The preparation method of the stainless steel material comprises the following steps:
(1) mixing the raw materials according to the chemical components, and carrying out vacuum induction smelting and pouring to obtain a stainless steel ingot;
(2) forging a steel ingot in an austenite single-phase region: the initial forging temperature is 1080-1150 ℃, the final forging temperature is 950-1000 ℃, the forging ratio is 6-8, and the forging is carried out by air cooling to the room temperature;
(3) the heat treatment process after forging comprises the following steps: firstly, preserving heat at 1050-1100 ℃ for 30-60 min, then air cooling, preserving heat at 550-650 ℃ for 90-120 min, and then air cooling; then keeping the temperature at 950-1000 ℃ for 20-30min and cooling by water; finally, the temperature is preserved for 120-.
The stainless steel obtained by the components and the preparation method meets the following requirements:
the structure of the stainless steel is martensite, and the ferrite content in the structure is less than 2 percent.
The stainless steel structure contains molybdenum carbide and copper-rich precipitated phase.
The hardness of stainless steel is greater than 56 HRC.
Stainless steel has excellent corrosion resistance.
The migration amount of heavy metals in the stainless steel meets the following requirements: arsenic (As) <0.004 mg/kg; cadmium (Cd) <0.002 mg/kg; lead (Pb) <0.005 mg/kg; chromium (Cr) <0.2 mg/kg; nickel (Ni) <0.05 mg/kg. The migration quantity meets the limit value specified by the national standard, and meets the requirements of metal materials and products for food contact.
The content ranges of the main elements in the invention are explained as follows:
c: carbon is an austenite forming element, and can enlarge the austenite phase region and reduce the ferrite phase region, thereby suppressing the formation of ferrite in the steel. Carbon is the most economical strengthening element in steel, the main element determining the hardness of steel, promoting the formation of carbides. C forms Mo with Mo2The C-type carbide is uniformly dispersed and precipitated in the matrix to play a role of precipitation hardening. However, carbon is an element that impairs the corrosion resistance of steel, and too high a carbon content results in a decrease in corrosion resistance. Therefore, the carbon content in the steel is 0.4-0.5%.
Cr: chromium is the primary element determining the corrosion resistance of stainless steel, and the higher the chromium content is, the better the corrosion resistance is, but in the present invention, high temperature ferrite is easily formed when the content is too high, which impairs the toughness and workability of stainless steel. Therefore, the chromium content should be strictly controlled within the range of 16.0-16.5%.
Mo: molybdenum is a ferrite-forming element and has a capacity corresponding to chromium. Besides improving the corrosion resistance, the molybdenum mainly improves the hardness and enhances the secondary hardening effect, and the low-temperature quenching is particularly obvious. The addition of molybdenum in the stainless steel can refine grains, homogenize the structure, improve the toughness, improve the strength and the tempering stability of the martensitic stainless steel and inhibit the precipitation of chromium carbide. The combined action of molybdenum and chromium can improve the passivation and re-passivation capability of the stainless steel, improve the stability of a passivation film and enable the stainless steel to have better corrosion resistance. However, too high a molybdenum content will promote the formation of high temperature ferrite, causing some adverse effects. The content of molybdenum in the invention is controlled to be 0.8-0.9%.
Cu: the addition amount of Cu in the invention is 1.5-2.2%, which is lower than the Cu content in the prior martensite antibacterial stainless steel, but still can ensure certain antibacterial performance. This is because, in the present invention, the Mo content is high, and the increase in the Mo content is advantageous for the precipitation of the copper-rich phase. Multiple tests show that only 1.5-2.2% of Cu is added, and the antibacterial rate of the antibacterial agent to escherichia coli is still higher than 98% through the preparation method provided by the invention, and the antibacterial performance is stable. This not only reduces the amount of Cu added, but also has a positive effect on the workability of the stainless steel according to the invention.
The heat treatment system of the present invention is explained as follows:
and (3) air cooling after the temperature is kept at 1050-1100 ℃ for 30-60 min to ensure that the steel is completely austenitized and the structure is fully homogenized.
And (3) keeping the temperature at 550-650 ℃ for 90-120 min, and then cooling in air to ensure that supersaturated copper precipitates a copper-rich phase with enough volume fraction from the steel, thereby ensuring the antibacterial performance. Simultaneously, a certain amount of molybdenum-containing carbide is precipitated.
Carrying out secondary austenitizing at 950-1000 ℃, and refining prior austenite grains; and (3) performing water cooling after heat preservation for 20-30min, refining the martensite lath, improving the hardness of the matrix, and simultaneously avoiding excessive re-dissolution of a precipitated phase of the first tempering.
And finally, preserving the heat at 150-250 ℃ for 120-.
The preferred heat treatment process is as follows: firstly, keeping the temperature at 1070 ℃ for 30min, then cooling in air, and then keeping the temperature at 580 ℃ for 100min, and then cooling in air; keeping the temperature at 970 ℃ for 25min and then cooling by water; and finally, keeping the temperature at 200 ℃ for 120min and then cooling in air.
The invention has the beneficial effects that:
according to the invention, through mutual restriction and blending of various alloy elements, the food-grade stainless steel material with scratch resistance, high hardness, antibiosis and excellent corrosion resistance can be obtained through a special preparation method, and the problem that scratches are easy to occur on the surface of stainless steel tableware can be solved.
Drawings
FIG. 1 shows the microstructure of example 1 of the present invention.
FIG. 2 is a polarization curve of example 2 of the present invention.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto. The steel in the examples and the steel in the comparative example were subjected to smelting, hot working and heat treatment, and then surface hardness, corrosion resistance, antibacterial property and heavy metal migration amount tests were conducted.
Hardness test was carried out by the Rockwell indentation method under a load of 150kgf for a retention time of 15 s.
The stainless steel is subjected to a polarization curve test, a reference electrode is a KCl saturated calomel electrode, the scanning speed is 0.5mV/s, and the electrolyte solution is 0.9% NaCl solution. And (4) testing the pitting potentials of different examples to investigate the corrosion resistance.
The antibacterial property is tested according to the standard regulation of GB/T2591-2003 'antibacterial property experimental method and antibacterial effect of antibacterial plastics'. The calculation formula of the sterilization rate is as follows: the sterilization ratio (%) (% viable cell count on control sample-viable cell count on stainless steel sample)/viable cell count on control sample ] × 100, wherein the control sample used the following stainless steel of comparative example 1, and the stainless steel sample refers to the stainless steel of examples 1 to 4 according to the present invention.
The test of the heavy metal migration quantity is carried out according to the standard regulation of GB 4806.9-2016 metallic materials and products for food safety national standard food contact. The simulated solution was 4% acetic acid solution, and the migration test conditions were boiling for 30 minutes and standing at room temperature for 24 hours.
The preparation method comprises the following steps:
(1) mixing the raw materials according to the chemical components, and carrying out vacuum induction smelting and pouring to obtain a stainless steel ingot;
(2) forging a steel ingot in an austenite single-phase region: the initial forging temperature is 1080-1150 ℃, the final forging temperature is 950-1000 ℃, the forging ratio is 6-8, and the forging is carried out by air cooling to the room temperature;
(3) selecting optimized parameters for the heat treatment process after forging, namely firstly preserving heat at 1070 ℃ for 30min, then air cooling, and then preserving heat at 580 ℃ for 100min, and then air cooling; keeping the temperature at 970 ℃ for 25min and then cooling by water; and finally, keeping the temperature at 200 ℃ for 120min and then cooling in air.
The chemical compositions of the examples and comparative examples are shown in table 1.
TABLE 1 chemical composition analysis results (weight percentage) of examples and comparative examples
| C | Si | Mn | Cr | Ni | Mo | Cu | S | P | Cr equivalent | Ratio of Mo to C | |
| Example 1 | 0.44 | 0.39 | 0.36 | 16.1 | 0.42 | 0.85 | 2.0 | 0.0012 | 0.019 | 7.1 | 1.9 |
| Example 2 | 0.48 | 0.35 | 0.32 | 16.4 | 0.44 | 0.90 | 1.7 | 0.0018 | 0.019 | 6.9 | 1.9 |
| Example 3 | 0.41 | 0.33 | 0.39 | 16.5 | 0.45 | 0.89 | 1.9 | 0.0013 | 0.020 | 8.1 | 2.2 |
| Example 4 | 0.50 | 0.35 | 0.33 | 16.3 | 0.45 | 0.90 | 2.2 | 0.0017 | 0.021 | 6.0 | 1.8 |
| Comparative example 1 | 0.46 | 0.39 | 0.35 | 18.2 | 0.44 | 0.85 | -- | 0.0012 | 0.019 | 10.0 | 1.8 |
| Comparative example 2 | 0.45 | 0.34 | 0.33 | 15.2 | 0.44 | 0.60 | -- | 0.0015 | 0.021 | 6.7 | 1.3 |
| Comparative example 3 | 0.35 | 0.2 | 0.1 | 16.5 | 0.40 | 0.81 | -- | -- | -- | 10.4 | 2.3 |
| Comparative example 4 | 0.57 | 0.1 | 0.3 | 16.3 | 0.41 | 0.82 | -- | -- | -- | 5.7 | 1.4 |
The results of the performance test of the steels of examples 1 to 4 and comparative examples 1 to 4 are shown in Table 2.
Table 2 results of performance test of examples and comparative examples
Injecting: in the antibacterial test, the control sample was the steel of comparative example 1.
Table 3 results of heavy metal migration amount test for examples and comparative examples
As can be seen from tables 1-2, the invention ensures that the ferrite content is lower than 2% by properly increasing the contents of chromium and carbon, optimizing other components to control the Cr equivalent and adjusting the weight percentage of Mo/C, and compared with a comparative example, the invention maintains excellent corrosion resistance while improving the hardness and high antibacterial property. Comparative examples 1 and 3 have low corrosion resistance and hardness because the chromium equivalent exceeds 8.5 and contains about 5% of ferrite, and comparative example 3 has low content of C and extremely low hardness; comparative examples 2 and 4 do not satisfy the Mo/C ratio of more than 1.8, the volume fraction of Mo carbides in the matrix is small, the hardness is low, and comparative example 4 has too high C content and the corrosion resistance is extremely poor.
As can be seen from table 3, the migration amounts of heavy metals, arsenic (As), cadmium (Cd), lead (Pb), chromium (Cr), and nickel (Ni), in examples 1 to 4 of the present invention, were not detected, and were all lower than the test limit value, and were far lower than the limit value specified by the national standard, so As to achieve the "food grade" condition; the migration amounts of heavy metals of arsenic (As), cadmium (Cd), lead (Pb) and nickel (Ni) in the comparative example 1 are also lower than the test limit values, but the migration amount of chromium (Cr) is 0.3mg/kg, and although the food-grade condition is also achieved, chromium (Cr) ions are separated out; in the comparative example 2, the chromium (Cr) content is less, the Mo/C ratio is small, the corrosion resistance is poor, the migration amount of heavy metal chromium (Cr) exceeds the standard, and the heavy metal chromium (Cr) does not meet the requirements of food-grade materials; comparative example 3 the migration amount of chromium (Cr) meets the standard requirement, but chromium (Cr) ions are also precipitated; comparative example 4 corrosion resistance was very poor, resulting in a severe over-standard chromium (Cr) migration.
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 (6)
1. A food-grade high-wear-resistance martensitic stainless steel is characterized in that: the chemical components by weight percentage are as follows: c: 0.44-0.5%, Cr: 16.0-16.5%, Ni: 0.4-0.45%, Mo: 0.8-0.9%, Mn: 0.3-0.4%, Si: 0.3-0.4%, Cu: 1.5-2.2%, P: < 0.03%, S: less than 0.01 percent, and the balance of iron and inevitable impurities;
the chemical composition of the stainless steel also satisfies the following conditions: the Cr equivalent is less than 8.5, which is calculated as follows:
cr equivalent is Cr% +0.8 xSi% +2 xMo% -2 xNi% -0.4 xMn% -0.6 xCu% -20 xC%;
the mass ratio of Mo to C satisfies: Mo/C is more than 1.8;
the preparation method of the stainless steel comprises the following steps:
(1) mixing the raw materials according to the requirements of chemical components, and obtaining a stainless steel ingot through vacuum induction smelting and pouring;
(2) forging a steel ingot in an austenite single-phase region: the initial forging temperature is 1080-1150 ℃, the final forging temperature is 950-1000 ℃, the forging ratio is 6-8, and the forging is carried out by air cooling to the room temperature;
(3) performing heat treatment after forging;
the hardness of the stainless steel is greater than 56 HRC.
2. A method for preparing the food-grade high-wear-resistance martensitic stainless steel as claimed in claim 1, which comprises the following steps:
(1) mixing the raw materials according to the requirements of chemical components, and obtaining a stainless steel ingot through vacuum induction smelting and pouring;
(2) forging a steel ingot in an austenite single-phase region: the initial forging temperature is 1080-1150 ℃, the final forging temperature is 950-1000 ℃, the forging ratio is 6-8, and the forging is carried out by air cooling to the room temperature;
(3) and performing heat treatment after forging.
3. The method for producing a food-grade high-wear-resistance martensitic stainless steel as claimed in claim 2, wherein: the heat treatment process in the step (3) comprises the following steps: firstly, preserving heat at 1050-1100 ℃ for 30-60 min, then air cooling, preserving heat at 550-650 ℃ for 90-120 min, and then air cooling; then keeping the temperature at 950-1000 ℃ for 20-30min and cooling by water; finally, the temperature is preserved for 120-.
4. The method for producing a food-grade high-wear-resistance martensitic stainless steel as claimed in claim 3, wherein: the heat treatment process comprises the following steps: firstly, keeping the temperature at 1070 ℃ for 30min, then cooling in air, and then keeping the temperature at 580 ℃ for 100min, and then cooling in air; keeping the temperature at 970 ℃ for 25min and then cooling by water; and finally, keeping the temperature at 200 ℃ for 120min and then cooling in air.
5. The method for producing a food-grade high-wear-resistance martensitic stainless steel as claimed in claim 2, wherein: the structure of the stainless steel is martensite, and the ferrite content in the structure is lower than 2%; the obtained stainless steel structure contains molybdenum carbide and copper-rich precipitated phase.
6. The method for producing a food-grade high-wear-resistance martensitic stainless steel as claimed in claim 2, wherein: the migration amount of heavy metals in the obtained stainless steel meets the following requirements: arsenic <0.004 mg/kg; cadmium is less than 0.002 mg/kg; lead <0.005 mg/kg; chromium <0.2 mg/kg; nickel <0.05 mg/kg.
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| CN113846275B (en) * | 2020-06-28 | 2023-06-13 | 中国科学院金属研究所 | Antibacterial ultra-high strength high toughness stainless steel material and preparation method thereof |
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