WO2013159669A1 - 一种不锈钢材料及其制造方法 - Google Patents

一种不锈钢材料及其制造方法 Download PDF

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WO2013159669A1
WO2013159669A1 PCT/CN2013/074350 CN2013074350W WO2013159669A1 WO 2013159669 A1 WO2013159669 A1 WO 2013159669A1 CN 2013074350 W CN2013074350 W CN 2013074350W WO 2013159669 A1 WO2013159669 A1 WO 2013159669A1
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nitrogen
steel
smelting
stainless steel
blank
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PCT/CN2013/074350
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English (en)
French (fr)
Inventor
郎宇平
李北
邢长军
鲍贤勇
孙绍华
翁建寅
姚春发
唐海元
陈海涛
曹呈祥
吴林
宁小智
屈华鹏
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钢铁研究总院
飞亚达(集团)股份有限公司
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Publication of WO2013159669A1 publication Critical patent/WO2013159669A1/zh

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32Ferrous alloys, e.g. steel alloys containing chromium with boron
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04Removing impurities by adding a treating agent
    • C21C7/068Decarburising
    • C21C7/0685Decarburising of stainless steel
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/002Heat treatment of ferrous alloys containing Cr
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20Ferrous alloys, e.g. steel alloys containing chromium with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese

Definitions

  • the present invention relates to stainless steel and smelting and processing methods, and more particularly to a stainless steel material and a method of manufacturing the same. Background technique
  • Stainless steel is a steel that is not easily rusted, and the stainless steel's rust and corrosion resistance are formed by a chromium-rich oxide film (passivation film) on its surface. Due to its excellent corrosion resistance, formability, compatibility and toughness over a wide temperature range, stainless steel has achieved a wide range of properties in the heavy industry, light industry, household goods industry and architectural decoration industries. Applications, not only functional materials, but also modern structural materials. Stainless steel has the advantages of long life cycle and low cost, and can be recycled and reused 100%. It is also a green material that does not cause environmental pollution (lead-free, PVC-free, environmental hormone-free). Since the invention of the stainless steel in the 20th century, stainless steel has been the only metal material with an increasing output and demand (6% of the world's annual growth rate). Due to the renewal and advancement of technology, the cost has been reduced and the output of stainless steel has been increasing.
  • Stainless steel materials are widely used in products that come into contact with human bodies, such as watches, jewelry, medical equipment, human organs, etc.
  • the stainless steel grades used in these fields are mainly SUS 304 (06Crl9Ni lO ) and SUS 316L (022Crl7Ni l2Mo2 ), but these two types
  • the nickel content of the material exceeds 8%.
  • Recent studies have shown that nickel may cause dissolution when exposed to human body for a long time, which is mainly caused by the allergic reaction of nickel to the skin and the possible carcinogenic effects of nickel, that is, nickel-containing metal materials are used to make contact with human skin. Items can induce allergic reactions, and when nickel-containing metal materials are used in the human body, diseases may be induced.
  • Nickel-containing metal products are in direct contact with human skin for a long time. Some people may cause different degrees of skin damage at the contact site, slight redness, itching, severe redness, ulceration, etc. This phenomenon is called Nickel allergy. In daily life, people often come into contact with nickel-containing metal products (such as watches, Jewelry, etc., so cases of skin allergies are not uncommon. Studies on the mechanism of skin allergies caused by nickel have shown that metals do not directly react with human skin. The skin absorbs nickel ions released from nickel-containing materials in direct contact with nickel-containing products for a long time, and binds to skin mucosal epithelial proteins. In the epidermis, pathological changes such as eczema appear on the surface of the skin, causing allergies. This process can be described as the nickel-containing material in the long-term contact with human skin, the role of human sweat accelerates the corrosion process of the material.
  • the European Union issued the Directive CE Directive 94/27/EEC, commonly known as The Nickel Directive, which imposes stricter requirements on the production of daily necessities, pointing out the materials implanted in the human body (implant materials).
  • the nickel mass fraction should not exceed 0.05%, and the alloy used for the manufacture of jewelry, watches, rings, bracelets and other products that have been in contact with human skin for a long time, the amount of nickel permeates into the skin per week.
  • the maximum limit should be more than 0.5 ⁇ g./cm 2 .
  • Foreign manufacturers, especially the EU countries have responded very positively to the nickel directive.
  • the Nickel Directive was incorporated into English law.
  • argon-oxygen decarburization refining A0D
  • vacuum oxygen decarburization V0D
  • Refining technology can be economically decarbonized, and it is easy to reduce the carbon content to below 0.03% by weight, which greatly reduces the occurrence of sensitization.
  • Ultra-low carbon austenitic stainless steel has gradually replaced Nb- and Ti-based stainless steels with its excellent corrosion resistance and comprehensive properties.
  • the reduction in carbon causes the strength of the austenitic stainless steel to decrease.
  • the role of nitrogen in stainless steel has begun to be valued.
  • nitrogen can increase strength in stainless steel, and later it has been found to have a beneficial effect on the corrosion resistance of steel.
  • the main factor that hinders the widespread use of nitrogen as an alloying element is the problem of nitrogen addition.
  • Nitrogen solubility is very low at atmospheric pressure and it is very difficult to add. Due to the small amount of addition, its beneficial effect on steel is not obvious.
  • nitrogen has an adverse effect on impact toughness and plasticity, which further hinders people's attention to the application of nitrogen.
  • T is the temperature and fN is the activation coefficient of nitrogen, which is affected by the alloying elements, wherein Cr, Mn, Mo, Nb reduce the activation coefficient value.
  • high-nitrogen steel smelting technologies have been developed abroad, including plasma smelting, pressurized induction furnace smelting, pressurized electroslag remelting smelting, powder metallurgy, and high-pressure nitrogen under normal pressure using advanced computer alloy design methods. Smelting of steel, etc.
  • the main trends in the development of high nitrogen steel are: (1) High strength and high toughness steel. This type of steel mainly utilizes the contribution of N to the mechanical properties of steel. By appropriate metallurgical process and proper alloy design, N is greatly dissolved in steel, and a stainless steel with ultra-high strength and super high toughness is developed. Some results have shown that this is another way to study ultra-high strength steel.
  • Ultrahigh-strength steels having a yield strength exceeding 2000 MPa in a solid solution state and a strength exceeding 3600 MPa in a cold deformation state have been studied.
  • the stainless steel material studied in this patent mainly utilizes the contribution of N to the corrosion resistance, completely replaces the nickel element in stainless steel with N, and studies the high-nitrogen stainless steel which is completely free of nickel on the basis, which fundamentally solves the human contact.
  • Nickel allergy problems in stainless steel applied on the product and saving nickel metal resources are improved, and the hardness of the material is greater than that of the original ultra-low carbon austenitic stainless steel.
  • Nitrogen has a solid solution strengthening effect, which not only improves the strength, toughness and creep resistance of steel, but also improves Abrasion resistance and improved corrosion resistance.
  • a steel containing more than 0.08% of nitrogen in a steel having a matrix of ferrite and a nitrogen containing 0.4% or more of a steel having austenite in the matrix is referred to as a high-nitrogen steel.
  • Nitrogen is more soluble in carbon in the austenitic phase of stainless steel than carbon, and has the effect of retarding the precipitation of carbides, and at the same time effectively improves the strength and corrosion resistance of steel.
  • the development of stainless steel with nickel instead of nickel can improve the corrosion resistance and strength by high-nitriding of stainless steel, stabilize the austenite phase and replace nickel, and obtain effects in terms of quality and cost.
  • the smelting of high-nitrogen stainless steel faces two major problems, namely how to obtain a high content of nitrogen in the molten state, and how to ensure that the nitrogen is dissolved in the solidification process, rather than the free state.
  • the main measures taken are: designing a reasonable alloy composition; adopting a suitable process route; selecting an appropriate nitrogen carrier.
  • the high-nitrogen steel smelting technology mainly adopts a smelting method in which a solid nitrogen-containing material is added to molten steel to alloy the steel, alloying with gaseous nitrogen or combining the two methods.
  • the high-nitrogen steel has a serious cold work hardening process during the processing (the steel is processed at normal temperature or below the crystallization temperature to produce strong plastic deformation, causing the lattice to be distorted, distorted, grain Producing shear, slip, grain elongation, significantly increasing hardness, reducing plasticity and impact toughness, known as cold work hardening), traditional stainless steel blank stamping methods and machining methods are not suitable for high nitrogen steel; High-nitrogen steel has a problem of high mechanical processing due to its high hardness. Summary of the invention
  • the stainless steel material is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen. Since it does not contain nickel, it does not cause nickel allergy when it comes into contact with the human body, and also avoids the use of nickel which is short of resources, is a kind of strength, A new type of austenitic stainless steel with excellent toughness.
  • the second technical problem to be solved by the present invention is to provide a method for smelting high-nitrogen steel in a pressurized induction furnace in view of the difficulty in smelting the above nitrogen-containing stainless steel in the prior art and the fact that the proportion of nitrogen in the stainless steel does not meet the design requirements.
  • the obvious feature of this method is the application of solid nitrogen-containing materials and gaseous nitrogen alloying nitrogen-enriching method to smelt high-nitrogen steel, so that the composition control is accurate and the nitrogen recovery rate is over 99%; Using a number of research, experiments, and verification smelting methods, the nitrogen content of high-nitrogen steel can be controlled within the design requirements to meet the design requirements.
  • the third technical problem to be solved by the present invention is that the above-mentioned high-nitrogen steel of the prior art has a serious cold work hardening phenomenon in the process of processing, and the conventional stainless steel blank stamping method is not suitable for high-nitrogen steel forming.
  • the problem is to provide a method for stamping high nitrogen steel blanks.
  • the fourth technical problem to be solved by the present invention is that the above-mentioned high-nitrogen steel has a severe cold hardening phenomenon in the process of processing, and the conventional mechanical processing method is not suitable for high-nitrogen steel and high-nitrogen steel. There is a defect that machining is difficult due to large hardness, and a mechanical processing method of high-nitrogen steel is provided.
  • the method for producing a stainless steel material of the present invention comprises a method of smelting high-nitrogen steel by a pressurized induction furnace, a method of stamping a high-nitrogen steel blank, and a machining method of high-nitrogen steel.
  • the austenite is a high temperature variant of iron having a face-centered cubic crystal structure, generally thermodynamically stable between 740 ° C and 1538 ° C, and contains from 0 to a maximum of 2.1 wt% of carbon in solid solution form. 1153 ° C)
  • austenitic steels all steels with a face-centered cubic lattice are called austenitic steels.
  • the tempering time is greater than 0. 5 hours
  • the holding time is greater than 0.55 hours
  • the holding time is greater than 0. 5 hours.
  • the solution temperature of the solution treatment is increased to between 1080-1120 ° C, the holding time is 1.0 hour, and the oil quenching is rapidly cooled. Under this circumstance, the cold work hardening phenomenon in the processing of high nitrogen steel is obviously suppressed.
  • the face-centered cubic lattice in high-nitrogen steel is basically stable, the composition of the high-nitrogen steel is more evenly distributed, and the material properties of the material can be recovered in time, which is advantageous for pressing the blank with high-nitrogen steel; the machining of the high-nitrogen steel of the invention
  • the suitable milling and turning processing methods and processing parameters are studied, which can overcome the problem of high hardness of high nitrogen steel due to high hardness. Steel is precision machined.
  • the traditional 316L appearance parts are usually solution treated at 900 ° C for half an hour.
  • high nitrogen steel will precipitate a large amount of nitride at 850-95 CTC, resulting in material composition and corrosion resistance. It is damaged, so the solution treatment temperature must reach above 1050 °C;
  • the technical solution adopted by the present invention to solve one of the technical problems is: constructing a stainless steel material,
  • the stainless steel material is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen, and the stainless steel material contains the following components by weight:
  • the stainless steel material of the present invention is used for parts of a product that is in direct contact with the human body.
  • the technical solution adopted by the present invention to solve the second technical problem is to construct a method for smelting high-nitrogen steel in a pressurized induction furnace, which is smelted by a pressurized induction smelting furnace, comprising the following steps:
  • the limit nitrogen value of the target steel under normal pressure is calculated by the following formula (1) and formula (2), and the limit nitrogen value is multiplied by the correction value to obtain the smelting preparation.
  • the actual weight percentage of the nitrogen content in the charge, the correction value is between 0.7 and 0.9;
  • P is the standard atmospheric pressure
  • S3 evacuate the smelting chamber of the pressure induction furnace.
  • the vacuum degree is less than 15Pa
  • the power supply starts to heat the smelting material.
  • the initial power is 40KW, and the power is gradually increased. After the molten pool occurs, the power is maintained and controlled. Avoid splashing;
  • the activity of nitrogen in the molten steel is calculated according to formula (1) and formula (2) according to the composition and nitrogen content requirements of different target steel species. Coefficient, saturation solubility, nitrogen filling pressure and nitrogen addition alloy addition.
  • the deoxidizing agent in the step S7 is bismuth carbon or deoxidized aluminum.
  • the technical solution adopted by the present invention to solve the third technical problem is to construct a stamping method for a high-nitrogen steel blank for stamping a high-nitrogen steel blank in a blank stamping apparatus, comprising the following steps:
  • a mold having a Rockwell hardness HRC of 60-70 and an impact toughness value of 55-120 J/cm 2 after tempering is used, and the mold is assembled to the blank stamping apparatus;
  • S2.2 After performing the operation of S2.1 to the set number of times, perform a solution treatment, solid solution Reason: The holding temperature is increased to between 1080-1120 ° C, the holding time is 1 hour, and the oil quenching is rapidly cooled; S2. 3: The operation of S2. 1 and S2. 2 is carried out to press into a high nitrogen steel blank.
  • the mold is a mold having a Rockwell hardness HRC of 62-64 and a impact toughness value of 60-90 J/cm 2 after tempering.
  • the holding time in the step S1. 1 is 0. 5-0. 75 hours.
  • the number of times of performing the operation of S2.1 in the step S2. 2 is 4-7 times.
  • the holding time in the step S2. 2 is 1-2 hours, and the oil quenching is rapidly cooled.
  • the high-nitrogen steel is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen, wherein the mass percentage of the nitrogen content is between 0.40% and 75%.
  • the technical solution adopted by the present invention to solve the fourth technical problem is to construct a mechanical processing method for high-nitrogen steel, comprising the following steps:
  • a tool with a Rockwell hardness HRA greater than 95 and a flexural strength ⁇ greater than 2 GPa is used;
  • the machine tool is used to mill the high-nitrogen steel.
  • the cutting speed Vc is between 60 and 100 m/min, the speed n is between 3000 and 5000 r/min, and the feed per blade fz is between 0. 02-0. 04-0. 4mm;
  • the feed rate F is between 200 and 600 mm/min, and the amount of the knife is between 0. 03-0. 4mm;
  • the machine has the following processing parameters for turning high-nitrogen steel:
  • the speed n is between 700 and 1000 r/min, and the feed per fr is between 0. 02-0. 04 mm/r, the amount of the knife is between 0 02-0. 3mm; until high-nitrogen steel is processed into parts that meet the design requirements;
  • the emulsion is a mass fraction of 3-6% of the emulsion
  • the pH of the emulsion is between 9. 0-9.
  • the refractive index of the emulsion is between 1-3, and it is a rust preventive emulsion.
  • the method for implementing the stainless steel material of the present invention and its smelting, blank stamping, and machining has the following beneficial effects:
  • the stainless steel material is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen. When exposed to human body, nickel allergy is not caused, and nickel which is short of resources is avoided, which is a new type of strength and toughness. Stainless steel.
  • the obvious feature of this method is the application of solid nitrogen-containing materials and gaseous nitrogen two alloying nitrogen-enriching methods to smelt high-nitrogen steel, so that the composition control is accurate, and the nitrogen recovery rate is over 99%.
  • the smelting method can control the nitrogen content of high-nitrogen steel within the design requirements, meet the design requirements, achieve accurate composition control, high nitrogen yield and stable effect; the invention can make the nitrogen yield reach 99 More than %, especially smelting up to 0.7% of high-nitrogen steel becomes a reality, and is suitable for mass-smelting nitrogen content of 0.4%-0. 75% of special steel, making mass production for contact with human body Nickel stainless steel is possible.
  • the high nitrogen steel is subjected to cyclic blanking, stress relief annealing, and solution treatment.
  • the holding temperature of the stress relief annealing is between 1050-1100 ° C and the holding time is 0.5 hours, and the holding temperature of the solution treatment is increased to Between 1080-1120 ° C, holding time of 1 hour, and oil quenching and rapid cooling, in this case, the cold work hardening phenomenon in the processing of high nitrogen steel is obviously suppressed, and the face centered cubic lattice in high nitrogen steel Basically stable, the distribution of components in high-nitrogen steel is more uniform, the material properties of the material can be restored in time, which is beneficial to the pressing of high-nitrogen steel.
  • the Rockwell hardness HRC after tempering is between 60-70, and The die with the impact toughness value of 55-120 J/cm 2 can be pressed for the blank, which can overcome the problem that the general die has poor stamping effect on the blank stamping of the high-nitrogen steel.
  • the stainless steel material is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen, and the stainless steel material contains the following components by weight:
  • the stainless steel material is preferably used for parts of products that are in direct contact with the human body, such as the watch strap, case, and bottom cover of the watch.
  • the stainless steel material can also be used in mechanical equipment, building materials, industrial materials, and the like.
  • pressurized induction smelting furnace smelting production of a pressurized induction furnace: North Electric Furnace Plant; model: ZG-0.05T, including the following steps:
  • the limit nitrogen value of the target steel under normal pressure is calculated by the following formula (1) and formula (2), and the limit nitrogen value is multiplied by the correction value to obtain the smelting preparation.
  • the actual weight percentage of the nitrogen content in the charge, the correction value is between 0.7 and 0.9;
  • the smelting materials are prepared, and the smelting materials are cleaned and filled into the finished smelting materials.
  • the steels here do not refer to the high-nitrogen steel of the final product, but the smelting of high-nitrogen steel.
  • the main steel in the process does not contain N, for example, steel can be, but is not limited to, 13Cr21Mnl6N (non-standard steel number);
  • S3 evacuate the smelting chamber of the pressure induction furnace.
  • the vacuum degree is less than 15Pa
  • the power is sent to heat the smelting material.
  • the initial power is 40KW, and the power is gradually increased. After the molten pool occurs, the power is maintained and controlled to avoid splashing.
  • the activity coefficient, saturation solubility, nitrogen filling pressure and nitrogen addition alloy addition amount of nitrogen in molten steel are calculated according to formula (1) and formula (2).
  • the deoxidizing agent in the step S7 is bismuth carbon, deoxidized aluminum (commonly used carbon and aluminum).
  • the high-nitrogen steel refers to a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen, and the components thereof are referred to the above-mentioned "stainless steel material”.
  • the advantage of the pressurized induction furnace is that the pressurized gas is pressurized to facilitate nitrogen absorption.
  • stamping method for high nitrogen steel blank For stamping of high nitrogen steel blanks in blank stamping equipment, the stamping method comprises the following steps:
  • a mold having a Rockwell hardness HRC of 60-70 and an impact toughness value of 55-120 J/cm 2 after tempering is used, and the mold is assembled to the blank stamping apparatus;
  • S2. 2 After the operation of S2. 1 is performed to the set number of times, a solution treatment is carried out, and the solution treatment is carried out: the holding temperature is increased to between 1080-1120 ° C, the holding time is 1 hour, and the oil quenching is rapidly cooled;
  • S2. 3 Cycling the operations of S2. 1 and S2. 2 to stamping into high nitrogen steel blanks.
  • the mold is a mold having a Rockwell hardness HRC of 62-64 and a impact toughness value of 60-90 J/cm 2 after tempering; the holding time in the step S2.1 is between 0. 5-0. 75 ⁇ ; The number of times of the operation of S2. 1 in the step S2. 2 is 4-7 times; the holding time in the step S2. 2 is 1-2 hours; 5 ⁇ The nitrogen content of the nickel-containing nickel-based Cr-Mn-N austenitic stainless steel, wherein the mass percentage of the nitrogen content is between 0. 4-0.
  • the machining method comprises the following steps:
  • a tool with a Rockwell hardness HRA greater than 95 and a flexural strength ⁇ greater than 2 GPa is used;
  • Milling machinery uses the following machining parameters to mill high-nitrogen steel: cutting speed Vc is 60-100 m/min, speed n is 3000-5000 r/min, feed per blade fz is 0 02-0. 4mm; 02-0. 4mm; 02-0. 4mm;
  • the machine is equipped with the following processing parameters for turning high-nitrogen steel:
  • the speed n is between 700 and 1000 r/min, and the feed per fr is between 0. 02-0. 04 mm/r, the amount of AP is between 0 02-0. 3mm; until high-nitrogen steel is processed into parts that meet the design requirements;
  • the cooling liquid is used for milling and turning, and the coolant is an emulsion having a mass fraction of 3-6%, and the pH of the emulsion is between 9.0 and 9.5.
  • Manufacturer of emulsion Shenzhen Keward Technology Co., Ltd.; Model: H537.
  • the emulsion has a refractive index of 1-3 and is a rust preventive emulsion.
  • the stainless steel material is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen, and the stainless steel material contains the following components by weight:
  • the stainless steel material is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen, and the stainless steel material contains the following components by weight:
  • the stainless steel material is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen, and the stainless steel material contains the following components by weight:
  • the stainless steel material is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen, and the stainless steel material contains the following components by weight:
  • the stainless steel material is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen, and the stainless steel material contains the following components by weight:
  • Example 6 The stainless steel material is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen, and the stainless steel material contains the following components by weight
  • the stainless steel material is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen, and the stainless steel material contains the following components by weight
  • the stainless steel material is a Cr-Mn-N austenitic stainless steel in which nickel is replaced by nitrogen, and the stainless steel material contains the following components by weight
  • the steel grade is 13Cr21Mnl6N (non-standard steel grade), and the composition control range and smelting control target are shown in Table 1.
  • the nitrogen gas pressure value required to make the saturated solubility of nitrogen greater than 0.7% at the temperature of 1873K is calculated, wherein the nitrogen content of manganese nitride is 5.95%.
  • Nitrogen recovery rate reaches 99%
  • the steel grade is 13Cr22Mnl7N (non-standard steel grade), and the composition control range and smelting control target are shown in Table 3.
  • the nitrogen content of chromium nitride is 4.42%.
  • the specific steps are as follows:
  • (1) Put pure iron, metallic chromium, ferroniobium, ferrovanadium, and niobium carbon into the furnace.
  • Manganese nitride, silicon, carbon, deoxidized aluminum, boron iron, chromium iron nitride, and deoxidizer are loaded into the silo.
  • Antimony carbon and deoxidized aluminum are deoxidizers.
  • the nitrogen recovery rate reaches 99.9.
  • the activity coefficient, saturation solubility, nitrogen filling pressure and nitrogen addition alloy of nitrogen in molten steel are calculated according to formula (1) and formula (2). the amount.
  • the equipment adopts 50-300t hydraulic press, and the stress-relieving annealing strip furnace is protected by nitrogen atmosphere. 1050 ° C, each holding time 0. 6 hours, in the solution treatment vacuum quenching furnace insulation temperature 1120 ° C, each holding time 1. 1 hour, the mold material used for the compact is DC53 (HRC64, impact toughness 70 J /cm 2 ) , The steel grade used for the sheet is 13Cr21Mnl6N (non-standard steel grade), the measured hardness is HV270, and the composition is shown in Table 5.
  • the material When roughing, the material has a large cold deformation and a cold work hardening (increased by more than 10 HV per press). It must be softened once (the hardness can approach the initial value after softening), and solid solution after every 4 rounds. Treatment to completely soften the material and restore the material's structural properties.
  • the hardness of the mold material preferably must reach HRC 62-64 and the impact toughness value reaches 60-90 J/cm 2 .
  • HRC62 impact toughness value of 60
  • HRC64 impact toughness value of 90
  • HRC63 impact toughness value of 80.
  • a mold having a Rockwell hardness HRC of 60 and a impact toughness value of 55 J/cm 2 after tempering treatment was used, and the mold was assembled to a blank pressing apparatus.
  • S2. 2 Cycling After S2. 1 operation to 4 times, a solution treatment is carried out, and solution treatment is carried out: the holding temperature is increased to 1080 ° C, the holding time is 1 hour, and the oil quenching is rapidly cooled.
  • S2. 3 Cycling the S2. 1 and S2. 2 operations 3 times to punch into a high-nitrogen steel blank, that is, performing the S2.1 and S2.2 operations one time in this step, and repeating the operation three times. Such an operation.
  • a mold having a Rockwell hardness HRC of 70 and a impact toughness value of 120 J/cm 2 after tempering treatment was used, and the mold was assembled to a blank stamping apparatus.
  • S2. 3 Cycling S2. 1 and S2. 2 operations 7 times to stamping into high nitrogen steel blanks.
  • a mold having a Rockwell hardness HRC of 62 and a impact toughness value of 60 J/cm 2 after tempering treatment was used, and the mold was assembled to a blank stamping apparatus.
  • S2. 1 For the high-nitrogen steel blank, the high-nitrogen steel after the blank is re-stressed once after the blank is re-stressed, and the stress is annealed.
  • the holding temperature is 1070 ° C, and the holding time is 0.6 hours.
  • S2. 2 After the S2. 1 operation is carried out to 5 times, a solution treatment is carried out, and the solution treatment is carried out: the holding temperature is increased to 1100 ° C, the holding time is 1 hour, and the oil quenching is rapidly cooled.
  • S2. 3 Cycling S2. 1 and S2. 2 operations 5 times to stamping into high nitrogen steel blanks.
  • a mold having a Rockwell hardness HRC of 64 and a impact toughness value of 90 J/cm 2 after tempering treatment was used, and the mold was assembled to a blank stamping apparatus.
  • S2. 2 After the S2. 1 operation is carried out to 5 times, a solution treatment is carried out, and the solution treatment is carried out: the holding temperature is increased to 1090 ° C, the holding time is 1. 1 hour, and the oil quenching is rapidly cooled.
  • S2. 3 Cycling S2. 1 and S2. 2 operations 2 times to stamping into high nitrogen steel blanks.
  • a mold having a Rockwell hardness HRC of 63 after tempering treatment and an impact toughness value of 80 J/cm 2 was used, and the mold was assembled to a blank stamping apparatus.
  • S2. 2 Cycling After S2. 1 operation to 6 times, a solution treatment is carried out, and solution treatment is carried out: the holding temperature is increased to 11 10 ° C, the holding time is 1 hour, and the oil quenching is rapidly cooled.
  • S2. 3 Cycling S2. 1 and S2. 2 operations 6 times to stamping into high nitrogen steel blanks.
  • the maximum speed is 15000r/min
  • the coolant is semi-synthetic cutting fluid H537
  • the milling cutter used is UKK: KEC0304 carbide milling cutter.
  • the turning tool used is MBN25 (boron nitride insert).
  • the turning process parameters are as shown in Table 7, the turning process can be carried out normally.
  • the method includes the following steps:
  • a mold having a Rockwell hardness of HRA of 96 and a bending strength of ⁇ of 2. lGPa is selected;
  • the machine tool uses the following processing parameters to mill the high-nitrogen steel: the cutting speed Vc is 55.6 m / min, the speed n is 3000 r / min, the feed rate per blade fz is 0. 01mm / z, the feed speed F is 01 ⁇ ; The amount of the knife is 0. 03 mm;
  • the machine tool is 0. 05mm/r, the amount of the feed is 0. 05mm;
  • the coolant is used for milling and turning, and the coolant is an emulsion having a mass fraction of 5%.
  • the r value of the emulsion is 9.0.
  • the emulsion has a refractive index of 2 and is a rust preventive emulsion.
  • the method includes the following steps:
  • the machine tool uses the following processing parameters to mill the high-nitrogen steel:
  • the cutting speed Vc is 94. 2 m/min, the speed n is 5000 r/min, the feed per tooth fz is 0. 02 mm/z, the feed rate F 2 ⁇ ;
  • the amount of the knife is 0.2 mm;
  • the machine tool uses the following processing parameters for the turning of the high-nitrogen steel: the speed n is 1000 r / min, the feed per revolution fr is 0. 04 ⁇ / r, the amount of the knife Ap is 0. 3 ⁇ ;
  • the coolant is used for milling and turning, and the coolant is an emulsion with a mass fraction of 3%.
  • the r value of the emulsion is 9.5.
  • the emulsion has a refractive index of 3 and is a rust preventive emulsion.
  • the method includes the following steps:
  • a mold having a Rockwell hardness of HRA of 96 and a bending strength of ⁇ of 2. 5 GPa is selected;
  • the mechanical equipment uses the following processing parameters to mill high-nitrogen steel: cutting speed Vc is 66m/min, speed n is 3500 r/min, feed per tooth fz is 0. 015 mm/z, feed rate F is 211 mm / mm n, the amount of eating Ap is 0. 09 mm;
  • the machine tool has the following processing parameters for the turning of the high-nitrogen steel: the speed n is 800 r / min, the feed per fr is 0. 039 mm / r, the amount of the knife Ap is 0. 18mm;
  • the coolant is used for milling and turning, and the coolant is an emulsion of 6% by mass.
  • the r value of the emulsion is 9.2.
  • the emulsion has a refractive index of 1, and is a rust preventive emulsion.
  • the nitrogen gas pressure value required to make the saturated solubility of nitrogen greater than 0.7% at a temperature of 1873K is calculated, wherein the nitrogen content of manganese nitride is 5.95%.
  • the pumping chamber of the pressurized induction furnace is evacuated, and when the degree of vacuum is less than 15 Pa, the electric heating furnace is started, and the power is 40 kW, which is gradually increased.
  • a mold having a Rockwell hardness HRC of 63 and a impact toughness value of 90 J/cm 2 after tempering treatment was used, and the mold was assembled to a blank stamping apparatus.
  • S2. 2 Cycling After S2. 1 operation to 5 times, a solution treatment is carried out, and solution treatment is carried out: the holding temperature is increased to 1090 ° C, and the holding time is 1. 1 hour.
  • the solution treatment is preferably an oil quenching treatment, and in other embodiments, a water quenching treatment may also be employed.
  • S2. 3 Cycling S2. 1 and S2. 2 operations 2 times to stamping into high nitrogen steel blanks.
  • Machining includes the following steps:
  • a mold having a Rockwell hardness of HRA of 96 and a bending strength of ⁇ of 2. 5 GPa is selected;
  • the mechanical equipment uses the following processing parameters to mill high-nitrogen steel: cutting speed Vc is 66m/min, speed n is 3500 r/min, feed per tooth fz is 0. 015 mm/z, feed rate F is 211 mm / mm n, the amount of eating Ap is 0. 09 mm;
  • the machine tool uses the following processing parameters for the turning of the high-nitrogen steel: the speed n is 800 r / min, the feed per revolution fr is 0. 039 mm / r, the amount of the knife Ap is 0. 18mm;
  • coolant is used for milling and turning, and the coolant is an emulsion with a mass fraction of 6%. 2 ⁇
  • the pH of the emulsion was 9.2.
  • the emulsion has a refractive index of 2 and is a rust preventive emulsion.

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Abstract

一种不锈钢材料及其制造方法,该不锈钢材料是以氮取代镍的Cr-Mn-N奥氏体不锈钢。制造方法包括:冶炼方法、坯件冲压方法、机械加工方法。冶炼方法主要是以固体含氮物料和气态氮两种合金化增氮方法来冶炼高氮钢。坯件冲压方法主要是循环进行冲坯、热处理、固溶处理,控制保温温度与保温时间,模具选用主要参考硬度值和冲击韧性值。机械加工主要是控制铣削和车削的合适的加工参数。该不锈钢材料的冶炼方法适于批量冶炼含氮量0.4-0.75wt%的高氮钢;坯件冲压方法抑制了高氮钢加工过程的冷作硬化现象,利于坯件冲压;机械加工方法克服了高氮钢因为硬度大而加工难度大的问题。

Description

说 明 书 一种不锈钢材料及其制造方法 技术领域
本发明涉及不锈钢及冶炼、加工方法, 更具体地说, 涉及一种不锈钢材料 及其制造方法。 背景技术
1、 使用高氮钢的意义
不锈钢是不易生锈的钢,不锈钢的不锈性和耐蚀性是由于其表面上富铬氧 化膜(钝化膜)而形成。 由于不锈钢具有优异的耐蚀性、 成型性、 相容性以及 在很宽温度范围内的强韧性等系列特点, 在重工业、 轻工业、 生活用品行业以 及建筑装饰等行业中以其优异特性取得广泛的应用, 不仅是功能性材料, 也是 现代结构材料。 不锈钢具有寿命周期长、 成本低的优势, 可 100%回收再利用, 也是不会造成环境污染(无铅、无聚氯乙烯、无环境荷尔蒙)的绿色环保材料。 不锈钢自 20世纪发明以来是当今唯一的产量和需求持续上升 (世界年均增长 率 6%) 的金属材料, 由于技术的更新与进步, 成本的降低, 不锈钢的产量不 断提升。
不锈钢材料大量应用于与人体接触的产品, 如手表、 首饰、 医疗器械、 人 体器官植入等,这些领域所用不锈钢牌号主要为 SUS 304 (06Crl9Ni lO )和 SUS 316L (022Crl7Ni l2Mo2 ), 但是这两类材料镍含量均超过 8%。 近年来的研究表 明,镍在长期接触人体时可能会有溶出而对人体造成危害, 主要体现在镍对皮 肤的过敏反应以及镍可能致癌的影响,即含镍金属材料用于制造接触人体皮肤 的物品,会诱发过敏反应,而在人体内使用含镍金属材料时,可能会诱发疾病。
含镍金属制品 (包括镀层)与人体皮肤长期直接接触,有些人会在接触部位 造成不同程度的皮肤损害, 轻微的有发红、 搔痒, 严重的会红肿、 溃烂等, 这 种现象称之为镍过敏。 在日常生活中, 人们经常接触含镍金属制品 (如手表、 首饰等), 因此引起皮肤过敏的病例屡见不鲜。 对镍引起皮肤过敏机理的研究 表明, 金属不会直接与人体皮肤发生不良反应,皮肤在长期与含镍制品直接接 触中,吸收含镍材料中释放的镍离子,与皮肤黏膜上皮蛋白结合,滞留于表皮, 导致皮肤表面出现湿疹等病理变化, 引起过敏。这个过程可以描述为含镍材料 在与人体皮肤长期接触过程中, 人体汗液的作用加速了材料的腐蚀过程。
镍对人体产生的致敏反应和致癌影响,日益引起世界医学界和材料界的重 视。各国对日用和医用金属材料中的镍含量限制越来越严格,标准规定中所允 许的最高镍含量也越来越低。 自 20世纪 80年代开始就有标准规定,将镍质量 分数大于 1%的合金划入致癌物质和皮肤过敏物质范畴, 并要求在产品质量证 明书中附带说明可能对人体产生有害后果的"安全证书"。 1994年,通过的 ISO 6871-2-1994国际标准警告:镍质量分数大于 1%的口腔矫形合金, 属人体不能 耐受的 "危险等级"合金。 1999年 7月, 欧盟发布了指导性法规 CE Direct ive 94/27/EEC, 即俗称镍指令 (The Nickel Directive) , 对日用品生产用材的规 定更加苛刻, 指出植入人体内的材料 (植入材料、矫形假牙等)中, 镍质量分数 不应超过 0. 05%, 而用于制造长期接触人体皮肤的首饰、 手表、 戒指、 手镯等 产品的合金, 镍含量则以每周渗入皮肤的量不应超过 0. 5 μ g./cm2为最高限量。 国外厂商特别是欧盟国家对镍指令反应非常积极。 2000年 1月 20日, 镍指令 纳入英国法律。 2000年 7月 21日, 德国禁止生产和进口与皮肤长期接触的含 镍成分时款配饰。 2002 年, 我国首饰行业制定并颁布了强制性技术标准 GB 11887— 2002《首饰贵金属的规定及命名方法》, 其中明确规定: 首饰与人体皮 肤长期接触部分的镍释放量每周必须小于 0. 5 μ g/cm2, 并于 2005年确立了首 饰镍释放量的测定标准。 2007 年起, 我国钟表行业正在制定强制性技术标准 《直接接触人体皮肤的手表元件中有害物质限量的规定》, 其中也规定了与人 体皮肤长期接触部分的镍释放量要求。现有与人体接触产品的不锈钢虽然其耐 腐蚀性能较好, 但均存在着镍释放量超标的潜在风险。 因此, 为了避免在与人 体接触不锈钢产品的镍释放超标问题,研究低镍乃至无镍的奥氏体不锈钢及其 加工技术势在必行。
另外, 从资源角度分析, 我国是一个缺少镍、 铬资源的国家, 中国镍资源 储量为 670万吨, 硫化铜镍矿约占总储量的 91%, 其余为氧化矿。 世界各国在 争夺镍铬资源开发控制权方面竞争激烈,因此镍铬资源供应是我国发展不锈钢 生产的重要限制因素, 且近年来镍原料价格高涨,相对使得镍铬系不锈钢成本 偏高, 因此发展低镍乃至无镍不锈钢具有重要的战略意义。
2、 相关技术的发展
低镍或无镍的奥氏体不锈钢的发展经过了几个阶段,是伴随着奥氏体不锈 钢的发展而不断进度的。奥氏体不锈钢自二十世纪二十年代初发明以来,得到 了迅猛的发展。 目前, 奥氏体不锈钢已发展成不锈钢中最重要的钢类, 其生产 量和使用量约占不锈钢总产量及用量的 60%以上。
随着冶炼技术的发展,氩一氧脱碳精炼法(A0D)和真空吹氧脱碳法(V0D) 开始作为商品化的大生产应用到不锈钢的生产工艺上。用精炼技术可经济地脱 碳, 并易于将碳含量降至 0. 03wt%以下, 大大减少了敏化现象的发生。 超低碳 奥氏体不锈钢以其优异的耐蚀性和综合性能, 逐渐取代了含 Nb、 Ti类不锈钢。 然而碳的降低, 使得奥氏体不锈钢的强度下降。 为弥补降碳引起的强度不足, 氮在不锈钢中的作用开始为人们所重视。从二十世纪二十年代开始, 人们发现 在不锈钢中氮可以提高强度, 后来又陆续发现其对钢的耐蚀性能有有益的影 响。 但氮作为合金化元素使用的最早报道是在 1938年。 阻碍氮作为合金元素 广泛使用的主要因素首先是氮的加入问题。在大气压强下氮溶解度非常低, 加 入非常困难。 由于加入量很小, 因此其对钢的有利作用不明显。 此外, 在某些 合金钢中, 氮在冲击韧性、 塑性等方面存在不利影响, 进一步阻碍了人们对氮 的应用的重视。
二十世纪五十年代, 由于当时不锈钢中贵重元素镍资源的奇缺,促使了人 们对铬镍锰氮和铬锰氮奥氏体不锈钢的广泛研究。 这种研究的结果, 导致了 Cr-Mn-Ni-N不锈钢系列即 200系的诞生。 钢中的 N含量集中在 0. 10〜0. 25% 范围内。 到六十年代, 由于 A0D炉外精炼技术的工业应用, 使得氮的加入和控 制问题得到了一定程度的解决。对含氮不锈钢的进一步研究使得氮在不锈钢中 的有益作用越来越多地为人们所认识。 当时, 研究者已经认识到, 氮在显著提 高不锈钢的力学性能的同时,还提高钢的耐腐蚀性能,特别是耐局部腐蚀性能 如耐晶间腐蚀、 点腐蚀和缝隙腐蚀等。
但是,受冶炼条件等因素的限制, 当时氮在不锈钢中的溶解度仍然处于较 低的水平。 随着加压冶金技术的发展, 氮可以以较大含量固溶于钢中, 并因此 对钢的性能带来了更大的影响。氮在钢中的作用再次被人们所广泛关注。工业 对高氮钢寄予了很大的兴趣。
氮在铁合金中的溶解度关系为:
logN=-293/T-l. 16-logfN+0. 51ogPN2
式中 T为温度, fN为氮的活化系数, 受合金元素影响, 其中 Cr、 Mn、 Mo、 Nb降低其活化系数值。
目前, 国外已开发了多种高氮钢的冶炼技术, 包括等离子冶炼、加压感应 炉冶炼、加压电渣重熔冶炼、粉末冶金以及利用先进的计算机合金设计方法进 行的常压下高氮钢的冶炼等。 高氮钢发展的主要趋势有: (1 )高强高韧钢。此 类钢主要利用 N对钢力学性能的贡献, 通过适当的冶金工艺和恰当的合金设 计, 将 N极大地固溶于钢中, 从而研制出超高强度、 超高韧性的不锈钢。 部分 成果已表明, 这是研究超高强度钢的又一途径。 已经研究出固溶状态下屈服强 度超过 2000MPa, 冷变形状态下强度超过 3600MPa的超高强度钢。 (2 ) 以耐蚀 性能为主的综合性能优异的不锈钢。 此类钢主要利用 N对钢的耐蚀性能的贡 献, 并兼顾 N在力学性能上的影响, 针对特殊的服役环境, 研究出一系列新型 超级不锈钢。 (3 ) 以节约资源、 降低成本为主要目的的经济型不锈钢。此类钢 利用 N对钢组织的影响, 部分或全部替代贵重金属镍, 使得钢在较低的原料成 本下仍保持奥氏体组织,从而在性能上兼顾奥氏体钢的特点和 N对钢性能的作 用, 进一步扩大了不锈钢的使用。
本专利研究的不锈钢材料, 主要是利用 N对耐蚀性能的贡献, 以 N完全 替代不锈钢中的镍元素,研究出在基础上完全不含镍元素的高氮不锈钢, 从根 本上解决在于人体接触产品上应用的不锈钢的镍过敏问题, 并节约镍金属资 源。 同时, 通过 N 的加入, 提高材料硬度和耐磨性能, 材料硬度大于原有超 低碳奥氏体不锈钢。
氮元素有固溶强化作用, 不仅可以提高钢材强度、 韧性、 蠕变抗力, 提高 耐磨性, 而且能改善其耐蚀性。 基体为铁素体的钢中含有 0.08%以上的氮和基 体为奥氏体的钢中含有 0.4%以上的氮的钢称为高氮钢。 氮在不锈钢的奥氏体 相中比碳容易固溶, 并有延缓碳化物析出的效果, 同时能有效地改善钢的强度 和耐蚀性。 以氮替代镍的不锈钢研制, 可以通过不锈钢高氮化来提高耐蚀性和 强度, 使奥氏体相稳定并取代镍, 在质量和成本方面获得效果。 高氮不锈钢的 冶炼主要面临两个问题, 即如何在熔化状态获得高含量氮, 以及怎样保证在凝 固过程中使氮处于溶解状态, 而不是游离态。 为获得高含氮量, 所采取的主要 措施有: 设计合理的合金成分; 采取合适的工艺路线; 选择适当的氮载体。 当 前高氮钢冶炼技术主要采用向熔融钢液加入固体含氮材料使钢合金化、采用气 态氮的合金化或两种方式结合的冶炼方法。
综上,可以看到,现有技术存在人体接触含镍的不锈钢会产生镍过敏问题; 同时, 在冶炼含氮不锈钢时, 存在冶炼困难、 不锈钢中氮的添加比例达不到设 计要求的技术难题。
同时,相对于传统的不锈钢,高氮钢在加工产生过程中存在较严重的冷作 硬化现象(钢材在常温或在结晶温度以下的加工产生强烈的塑性变形, 使晶格 扭曲、 畸变, 晶粒产生剪切、 滑移, 晶粒被拉长, 显著提高硬度, 降低塑性和 冲击韧性, 称为冷作硬化), 传统的不锈钢的坯件冲压方法及机械加工方法不 适用于高氮钢; 并且高氮钢存在因硬度大故机械加工难度大的问题。 发明内容
本发明要解决的技术问题之一在于,针对现有技术的上述人体接触含镍的 不锈钢会产生镍过敏问题, 提供一种不锈钢材料。该不锈钢材料是以氮取代镍 的 Cr-Mn-N奥氏体不锈钢, 由于不含镍, 与人体接触时不会产生镍过敏问题, 同时也避免了使用资源短缺的镍,是一种强度、韧性优异的新型奥氏体不锈钢。
本发明要解决的技术问题之二在于,针对现有技术的上述含氮不锈钢冶炼 困难、不锈钢中氮的添加比例达不到设计要求的缺陷, 提供一种加压感应炉冶 炼高氮钢的方法。该方法明显的特点是应用固体含氮物料和气态氮两种合金化 增氮方法来冶炼高氮钢, 从而使成分控制准确, 氮回收率达到 99%以上; 同时 采用多次研究、 实验、验证的冶炼方法, 可以将高氮钢的氮含量控制在设计要 求的范围内, 满足设计要求。
本发明要解决的技术问题之三在于,针对现有技术的上述高氮钢在加工产 生过程中存在较严重的冷作硬化现象、传统的不锈钢的坯件冲压方法不适用于 高氮钢成形的问题, 提供一种高氮钢坯件冲压的方法。
本发明要解决的技术问题之四在于,针对现有技术的上述高氮钢在加工产 生过程中存在较严重的冷作硬化现象、 传统的机械加工方法不适用于高氮钢、 及高氮钢存在因硬度大故机械加工难度大的缺陷,提供一种高氮钢的机械加工 方法。
本发明的不锈钢材料的制造方法包括:加压感应炉冶炼高氮钢的方法、高 氮钢坯件冲压的方法、 高氮钢的机械加工方法。
奥氏体是具有面心立方晶体结构的铁的高温变体, 一般在 740°C和 1538 °C之间热力学稳定,并以固溶形式含有从 0到最大 2. 1重量%的碳 (在 1153°C ), 通常来讲,所有具有面心立方晶格的钢都称为奥氏体钢。本发明经研究、实验, 发现高氮钢经循环冲坯、 去应力退火、 固溶处理, 在此过程中, 去应力退火的 保温温度介于 1050-1100°C、 保温时间大于 0. 5小时, 固溶处理的保温温度增 加至介于 1080-1120°C、保温时间 1. 0小时, 且油淬快速冷却, 在此情况下, 高氮钢加工过程中的冷作硬化现象明显被抑制,同时高氮钢中的面心立方晶格 基本稳定, 高氮钢中的成分分布更加均匀, 材料的组织性能可以及时恢复, 利 于用高氮钢压制坯件; 本发明的高氮钢的机械加工方法中,针对高氮钢的硬度 大、加工难度大的问题,研究出合适的铣削加工及车削加工的方法及加工参数, 可以克服高氮钢因硬度大故加工难度大的问题, 对高氮钢进行精密加工。
传统手表用 316L外观件通常固溶处理的温度在 900°C, 保温半小时, 而 高氮钢由于冶炼工艺的特殊性, 在 850-95CTC时会大量析出氮化物导致材料成 分、 耐腐蚀等性能受到破坏, 故其固溶处理温度必须达到 1050°C以上; 多次 实验表明在 1100°C左右保温 1小时后高氮钢由于前期的冲压所出现的耐腐蚀、 光泽度等都能得到优化。
本发明解决其技术问题之一所采用的技术方案是: 构造一种不锈钢材料, 该不锈钢材料是以氮取代镍的 Cr-Mn-N奥氏体不锈钢,该不锈钢材料包含以下 重量百分比的组分:
Cr: 18-22%;
Mn: 14-17%;
N: 0.4-0.75%;
C: 小于 0.15%。
在本发明所述的不锈钢材料中,该不锈钢材料用于与人体直接接触的产品 的零件。
本发明解决其技术问题之二所采用的技术方案是:构造一种加压感应炉冶 炼高氮钢的方法, 利用加压感应冶炼炉熔炼, 包括如下步骤:
S1: 依据目标钢种的元素成分, 通过下述的公式(1)及公式(2)计算出 目标钢种在常压下的极限氮含量值,该极限氮含量值乘以修正值得到冶炼配制 炉料中氮含量的实际加入重量百分比, 该修正值介于 0.7-0.9;
公式 (1):
Figure imgf000009_0001
式中 为 分压, P为标准大气压;
公式 (2):
lg = {-164i»[Cr] + 8.33ί»[Μ] -33.2ί»[Μο] -134ί»[Μκ] +1.68i»[Cr]2 -1.83ί»[Μ]2 -2.78ί»[Μο]2 +8.82ί»[Μκ]2
+ (1.6ω[Νί] + 1.2ω[Μο] + 2Λ6ω[Μη])ω[ϋΓ] + (-0.26ω[Μο]+0.09ω[Μη])ω[Νί] } τ + {0.0415«[ ] +
0 019«[M] + 0 064«[Mo] + 0 35«[MK]-0 006«[Cr]2+0 01«[M]2-0 013i»[Mo]2-0.0056iB[MK + (― 0.009ί»[Μ] - 0.0005ί»[Μο] - 0.0005«[ ])«[0] + (0.0003ί»[Μο] + 0.0007ί»[Μκ])ίΒ[Μ] } + 0.13i»[C] + 0.06ί»[Λ·] + 0.046ί»[Ρ] + 0.007 «[5] + 0Μω[ΑΙ] - 0.9ω[Τί] - 0Λω[Υ] - 0.003«[^] - 0.12ω[0] 式中 为钢液中氮的活度系数; 为合金元素 m的质量分数%;
S2: 按钢种所含元素的要求配制冶炼物料, 清理坩埚, 装入配制完成的冶
S3: 对加压感应炉熔炼室进行抽空, 真空度小于 15Pa时开始送电以加热 冶炼物料, 起始功率为 40KW, 逐步增大功率, 出现熔池后, 维持并控制功率, 避免喷溅;
S4: 炉料化清后调低功率至 15-20KW, 进入精炼, 精炼 30-40分钟, 真空 度 5Pa, 脱离 0、 H元素;
S5: 气体氮合金化: 开启制氮机, 充入氮气, 炉内压力至少调节至充氮压 力, 提高氮在钢液中的饱和溶解度;
S6: 合金化: 由加料口分步加入提高气体分压的冶炼原料、 及按照 S1中 氮含量的实际加入重量百分比计算得到的氮化铬铁、 氮化锰或其它增氮合金, 以提高合金收得率;
S7: 加入脱氧剂, 控制钢液温度比熔点高 100~150°C, 带电浇入锭模中, 降温;
S8: 放气, 破空, 打开炉盖取出锭模, 制成高氮钢。
在本发明所述的加压感应炉冶炼高氮钢的方法中,根据不同目标钢种的成 分和氮含量要求, 依据公式 (1) 和公式 (2) 计算出氮在钢液中的活度系数、 饱和溶解度、 充氮压力和增氮合金加入量。
在本发明所述的加压感应炉冶炼高氮钢的方法中, 所述步骤 S5采用气体 氮 合 金 化 方 法 , 氮 气 纯 度 99% , 充 氮 压 力 由 公 式 : lg/¼ =2x(lg[%N]-lg^+lg/ e)结合公式 (2) 计算得出。
在本发明所述的加压感应炉冶炼高氮钢的方法中, 步骤 S7中的脱氧剂为 坩埚碳、 脱氧铝。
本发明解决其技术问题之三所采用的技术方案是:构造一种高氮钢坯件的 冲压方法, 用于在坯件冲压设备中高氮钢坯件的冲压, 包括以下步骤:
S1: 选择模具
选用经回火处理后洛氏硬度 HRC介于 60-70 、 且冲击韧性值介于 55-120 J/cm2的模具, 将所述模具装配于坯件冲压设备;
S2: 热处理
S2.1: 对高氮钢冲坯, 每冲坯一次后对冲坯后的高氮钢去应力退火一次, 去应力退火: 保温温度介于 1050-1100°C, 保温时间 0.5小时;
S2.2: 循环进行 S2.1的操作至设定次数后, 进行一次固溶处理, 固溶处 理: 保温温度增加至介于 1080-1120°C, 保温时间 1小时, 油淬快速冷却; S2. 3: 循环进行 S2. 1和 S2. 2的操作至冲压成高氮钢坯件。
在本发明所述的高氮钢坯件的冲压方法中,所述模具为经回火处理后洛氏 硬度 HRC介于 62-64 、 且冲击韧性值介于 60-90 J/cm2的模具。
在本发明所述的高氮钢坯件的冲压方法中, 所述步骤 S2. 1中的保温时间 介于 0. 5-0. 75小时。
在本发明所述的高氮钢坯件的冲压方法中, 所述步骤 S2. 2 中循环进行 S2. 1的操作的设定次数为 4-7次。
在本发明所述的高氮钢坯件的冲压方法中, 所述步骤 S2. 2中的保温时间 为 1-2小时, 油淬快速冷却。
在本发明所述的高氮钢坯件的冲压方法中, 高氮钢为以氮取代镍的 Cr-Mn-N奥氏体不锈钢, 其中氮含量的质量百分比介于 0. 4_0. 75 %。
本发明解决其技术问题之四所采用的技术方案是:构造一种高氮钢的机械 加工方法, 包括以下步骤:
S1 : 选择刀具
选用洛氏硬度 HRA大于 95, 抗弯强度 δ大于 2GPa的刀具;
S2 : 加工
S2. 1: 铣削
机械设备采用以下加工参数对高氮钢进行铣削:切削速度 Vc介于 60-100 m/min, 转速 n介于 3000-5000 r/min, 每刃进给量 f z介于 0. 02-0. 04mm/z , 进给速度 F介于 200-600mm/min, 吃刀量 Ap介于 0. 03-0. 4mm;
S2. 2 : 车削
机械设备采用以下加工参数对高氮钢进行车削: 转速 n 介于 700-1000 r/min, 每转进给量 fr介于 0. 02-0. 04 mm/r, 吃刀量 Ap介于 0. 02-0. 3mm; 直至把高氮钢加工成符合设计要求的零件;
其中, 铣削及车削时采用冷却液, 冷却液为质量分数为 3-6%的乳化液, 所述乳化液的 PH值介于 9. 0-9. 5。
在本发明所述的高氮钢的机械加工方法中, 所述乳化液的折光系数介于 1-3, 且为防锈乳化液。
实施本发明的不锈钢材料及其冶炼、坯件冲压、机械加工的方法, 具有以 下有益效果:
1、 不锈钢材料
该不锈钢材料是以氮取代镍的 Cr-Mn-N奥氏体不锈钢, 人体接触时, 不 会产生镍过敏问题, 同时也避免了使用资源短缺的镍, 是一种强度、 韧性优异 的新型奥氏体不锈钢。
2、 加压感应炉冶炼高氮钢的方法
该方法明显的特点是应用固体含氮物料和气态氮两种合金化增氮方法来 冶炼高氮钢, 从而使成分控制准确, 氮回收率达到 99%以上; 同时采用多次研 究、实验、验证的冶炼方法,可以将高氮钢的氮含量控制在设计要求的范围内, 满足设计要求, 达到成分控制准确, 氮收得率高且稳定的效果; 本发明可使氮 的收得率达到 99%以上, 尤其是冶炼高达 0. 7%的高氮钢成为现实, 并适用于大 批量冶炼含氮量 0. 4%-0. 75%的特殊钢, 使批量生产用于与人体接触的无镍不 锈钢成为可能。
3、 高氮钢坯件冲压的方法
高氮钢经循环冲坯、 去应力退火、 固溶处理, 在此过程中, 去应力退火的 保温温度介于 1050-1100°C、 保温时间 0. 5小时, 固溶处理的保温温度增加 至介于 1080-1120°C、 保温时间 1小时, 且油淬快速冷却, 在此情况下, 高 氮钢加工过程中的冷作硬化现象明显被抑制,同时高氮钢中的面心立方晶格基 本稳定, 高氮钢中的成分分布更加均匀, 材料的组织性能可以及时恢复, 利于 对高氮钢进行坯件的压制; 同时选用经回火处理后洛氏硬度 HRC介于 60-70 、 且冲击韧性值介于 55-120 J/cm2的模具进行坯件的压制, 可以克服一般的模 具对高氮钢进行坯件冲压时冲压效果较差的问题。
4、 高氮钢的机械加工方法
本发明的高氮钢的机械加工方法中,针对高氮钢的硬度大、加工难度大的 问题,研究出合适的铣削加工及车削加工的方法及加工参数, 可以克服高氮钢 因硬度大故加工难度大的问题, 利于对高氮钢进行精密加工。 具体实施方式
为了对本发明的技术特征、 目的和效果有更加清楚的理解,现以具体实施 方式对本发明进行举例说明。
不锈钢材料:
该不锈钢材料是以氮取代镍的 Cr-Mn-N奥氏体不锈钢,该不锈钢材料包含 以下重量百分比的组分:
Cr: 18-22 %;
Mn: 14-17 %;
N: 0.4-0.75 %;
C: 小于 0.15%。
该不锈钢材料优选用于与人体直接接触的产品的零件,如手表的表带、表 壳和底盖等。 当然, 在其它的实施例中, 该不锈钢材料也可以用于机械设备、 建筑用材料、 工业材料等。
一种加压感应炉冶炼高氮钢的方法:
利用加压感应冶炼炉熔炼 (加压感应炉的生产产家: 北方电炉厂; 型号: ZG-0.05T), 包括如下步骤:
S1: 依据目标钢种的元素成分, 通过下述的公式(1)及公式(2)计算出 目标钢种在常压下的极限氮含量值,该极限氮含量值乘以修正值得到冶炼配制 炉料中氮含量的实际加入重量百分比, 该修正值介于 0.7-0.9;
公式 (1):
Figure imgf000013_0001
公式 (2):
lg = {-164i»[Cr] + 8.33ί»[Μ] -33.2ί»[Μο] -134ί»[Μκ] +1.68i»[Cr]2 -1.83ί»[Μ]2 -2.78ί»[Μο]2 +8.82ί»[Μκ]2
+ (1.6ω[Νί] + 1.2ω[Μο] + 2Λ6ω[Μη])ω[ϋΓ] + (-0.26ω[Μο]+0.09ω[Μη])ω[Νί] } τ + {0.0415«[ ] +
0 019«[M] + 0 064«[Mo] + 0 35«[MK]-0 006«[Cr]2+0 01«[M]2-0 013i»[Mo]2-0.0056iB[MK + (― 0.009ί»[Μ] - 0.0005ί»[Μο] - 0.0005«[ ])«[0] + (0.0003ί»[Μο] + 0.0007ί»[Μκ])ίΒ[Μ] } + 0.13i»[C] + 0.06ί»[Λ·] + 0.046ί»[Ρ] + 0.007 «[5] + 0Μω[ΑΙ] - 0.9ω[Τί] - 0Λω[Υ] - 0.003«[^] - 0.12ω[0] 式中 Λ 为钢液中氮的活度系数; 为合金元素 m的质量分数%;
S2 : 按钢种所含元素的要求配制冶炼物料, 清理坩埚, 装入配制完成的冶 炼物料; 需要说明的是, 此处的钢种并不是指最终制品高氮钢, 而是高氮钢冶 炼过程中的主体钢, 不包含 N, 例如钢种可以但不限于是 13Cr21Mnl6N (非标 准钢号);
S3: 对加压感应炉熔炼室进行抽空, 真空度小于 15Pa时开始送电以加热 冶炼物料, 起始功率为 40KW, 逐步增大功率, 出现熔池后, 维持并控制功率, 避免喷溅;
S4: 炉料化清后调低功率 15-20KW, 进入精炼, 精炼 30-40分钟, 真空度 5Pa, 脱离 0、 H元素;
S5 : 气体氮合金化: 开启制氮机, 充入氮气, 炉内压力至少调节至充氮压 力, 提高氮在钢液中的饱和溶解度;
S6 : 合金化: 由加料口分步加入提高气体分压的冶炼原料、 及按照 S1中 氮含量的实际加入重量百分比计算得到的氮化铬铁、 氮化锰或其它增氮合金, 以提高合金收得率;
S7 : 加入脱氧剂, 控制钢液温度比熔点高 100~150°C, 带电浇入锭模中, 降温;
S8 : 放气, 破空, 打开炉盖取出锭模, 制成高氮钢。
根据不同目标钢种的成分和氮含量要求, 根据公式(1 )和公式(2 )计算 出氮在钢液中的活度系数、 饱和溶解度、 充氮压力和增氮合金加入量。
所述步骤 S5 采用气态渗氮方法, 氮气纯度 99%, 充氮压力由公式: lg /¼ = 2x (lg[%N] -lg ^ +lg O结合公式 (2 ) 计算得出。
步骤 S7中的脱氧剂为坩埚碳、脱氧铝(工业常用碳及铝)。本实施例的方 法中,高氮钢是指以氮取代镍的 Cr-Mn-N奥氏体不锈钢,其成分参照上述的 "不 锈钢材料"。
加压感应炉的优点在于充入气体加压后利于氮气吸收。
高氮钢坯件的冲压方法 用于在坯件冲压设备中高氮钢坯件的冲压, 该冲压方法包括以下步骤:
S1 : 选择模具
选用经回火处理后洛氏硬度 HRC介于 60-70 、 且冲击韧性值介于 55-120 J/cm2的模具, 将所述模具装配于坯件冲压设备;
S2 : 热处理
S2. 1: 对高氮钢冲坯, 每冲坯一次后对冲坯后的高氮钢去应力退火一次, 去应力退火: 保温温度介于 1050-1100°C, 保温时间 0. 5小时;
S2. 2 : 循环进行 S2. 1的操作至设定次数后, 进行一次固溶处理, 固溶处 理: 保温温度增加至介于 1080-1120°C, 保温时间 1小时, 油淬快速冷却;
S2. 3: 循环进行 S2. 1和 S2. 2的操作至冲压成高氮钢坯件。
优选地, 所述模具为经回火处理后洛氏硬度 HRC介于 62-64 、 且冲击韧 性值介于 60-90 J/cm2的模具; 所述步骤 S2. 1中的保温时间介于 0. 5-0. 75小 时; 所述步骤 S2. 2中循环进行 S2. 1 的操作的设定次数为 4-7次; 所述步骤 S2. 2中的保温时间为 1-2小时; 高氮钢为以氮取代镍的 Cr-Mn-N奥氏体不锈 钢, 其中氮含量的质量百分比介于 0. 4-0. 75 %。
一种高氮钢的机械加工方法
该机械加工方法包括以下步骤:
S1 : 选择刀具
选用洛氏硬度 HRA大于 95, 抗弯强度 δ大于 2GPa的刀具;
S2 : 加工
S2. 1: 铣削机械设备采用以下加工参数对高氮钢进行铣削: 切削速度 Vc 介于 60-100 m/min , 转速 n 介于 3000-5000 r/min , 每刃进给量 fz 介于 0. 02-0. 04mm/z , 进给速度 F 介于 200-600mm/min, 吃刀量 AP 介于 0. 03- 0. 4mm;
S2. 2 : 车削
机械设备采用以下加工参数对高氮钢进行车削: 转速 n 介于 700-1000 r/min, 每转进给量 fr介于 0. 02-0. 04 mm/r, 吃刀量 AP介于 0. 02-0. 3mm; 直至把高氮钢加工成符合设计要求的零件; 其中, 铣削及车削时采用冷却液, 冷却液为质量分数为 3-6%的乳化液, 所述乳化液的 PH值介于 9.0-9.5。 乳化液的生产厂家: 深圳市科沃德科技有 限公司; 型号: H537。
所述乳化液的折光系数介于 1-3, 且为防锈乳化液。
不锈钢材料的实施例:
实施例 1
该不锈钢材料是以氮取代镍的 Cr-Mn-N奥氏体不锈钢,该不锈钢材料包含 以下重量百分比的组分:
Cr: 18%; Mn: 14%; N: 0.4%; C: 0.1%。
实施例 2
该不锈钢材料是以氮取代镍的 Cr-Mn-N奥氏体不锈钢,该不锈钢材料包含 以下重量百分比的组分:
Cr: 22%; Mn: 17%; N: 0.75%; C: 0.12%。
实施例 3
该不锈钢材料是以氮取代镍的 Cr-Mn-N奥氏体不锈钢,该不锈钢材料包含 以下重量百分比的组分:
Cr: 18 %; Mn: 14 %; N: 0.4 %; C: 0.1%; S: 0.02 %; P: 0.025 %; Si: 0.8 %; Cu: 0.2 %; Al: 0.01 %; 以及 Fe。
实施例 4
该不锈钢材料是以氮取代镍的 Cr-Mn-N奥氏体不锈钢,该不锈钢材料包含 以下重量百分比的组分:
Cr: 22 %; Mn: 17 %; N: 0.75 %; C: 0.12%; S: 0.01 %; P: 0.015 %; Si: 0.1%; Cu: 0.2 %; Al: 0.012 %; 以及 Fe。
实施例 5
该不锈钢材料是以氮取代镍的 Cr-Mn-N奥氏体不锈钢,该不锈钢材料包含 以下重量百分比的组分:
Cr: 21 %; Mn: 16 %; N: 0.6%; C: 0.13%。
实施例 6 该不锈钢材料是以氮取代镍的 Cr-Mn-N奥氏体不锈钢,该不锈钢材料包含 以下重量百分比的组分
Cr: 21%; Mn: 16%; N: 0.5%; C: 0.13%; S: 0.002%; P: 0.006%。
实施例 6
该不锈钢材料是以氮取代镍的 Cr-Mn-N奥氏体不锈钢,该不锈钢材料包含 以下重量百分比的组分
Cr: 21%; Mn: 16% ; N: 0.5%; C: 0.13%; S: 0.002%; P: 0.006%; Si: 0.7%; Cu: 无; A1: 无 ; 以及 Fe。
实施例 7
该不锈钢材料是以氮取代镍的 Cr-Mn-N奥氏体不锈钢,该不锈钢材料包含 以下重量百分比的组分
Cr: 20.6%; Mn: 15.79%; 0.46%; C: 0.13%; S: 0.003%; P: 0.007%; Si: 0.72%; Cu: 无; Al: 无; 0.0014%; 以及 Fe。
加压感应炉冶炼高氮钢的方法的实施例:
实施例 8
设备采用 50Kg加压感应熔炼炉, 极限真空度为 6.67X10— 2Pa, 电源功率 为 160KW,频率为 2500Hz,装炉量为 43Kg。钢种为 13Cr21Mnl6N (非标准钢号), 成分控制范围及冶炼控制目标见表 1。
13Cr21Mnl6N成分控制范围及控制目标
Figure imgf000017_0001
按公式 g 2 g( /P0)- τ- - , 通过计算可得温度 1873K时要使氮的饱 和溶解度大于 0.7%需要的充氮气压力值, 其中氮化锰含氮量 5.95%
具体步骤如下:
(1)将纯铁、 金属铬、 钼、 坩埚碳装入炉内。 氮化锰、 锰、 脱氧剂装入料 仓。 (2)对加压感应炉熔炼室进行抽空, 真空度小于 15Pa时开始送电加热炉 料, 功率 40KW, 逐步增大。
(3) 炉料化清出现熔池后, 控制功率, 避免喷溅, 真空度逐步降低。
(4) 调低功率至 15KW, 进入精炼, 精炼 30Min, 真空度 5Pa, 脱离的 0、 H元素。
(5) 合金化: 由加料口分步加入部分脱氧剂、 Cu。
(6)气体氮合金化: 开启制氮机, 充入氮气 2-3分钟, 调节炉内压力至所 需的压力值, 提高氮在钢液中的饱和溶解度。
(7) 加入 MnN合金。
(8) 加入最终脱氧剂, 控制钢液温度比熔点高 10(T150°C, 为避免注温下 降和氧化膜混入注流中, 带电浇入锭模, 降温 5min。
(9) 放气, 破空, 打开炉盖取出锭模, 以备进行后序热处理。
表 2: 成品钢的化学成分 (%)
Figure imgf000018_0002
氮回收率达到 99%
实施例 9
设备采用 50Kg加压感应熔炼炉, 极限真空度为 6.67X10— 2Pa, 电源功率 为 160KW,频率为 2500Hz,装炉量为 43Kg。钢种为 13Cr22Mnl7N (非标准钢号), 成分控制范围及冶炼控制目标见表 3。
表 3: 13Cr22Mnl7N成分控制范围及控制目标
Figure imgf000018_0003
Figure imgf000018_0001
氮化铬铁含氮量 4.42% 具体步骤如下:
(1) 将纯铁、 金属铬、 铌铁、 钒铁、 坩埚碳装入炉内。 氮化锰、 硅、 碳、 脱氧铝、 硼铁、 氮化铬铁、 脱氧剂装入料仓。 坩埚碳、 脱氧铝为脱氧剂。
(2) 对加压感应炉熔炼室进行抽空, 真空度小于 15Pa时开始送电加热炉 料, 功率 40KW, 逐步增大。
(3)炉料化清出现熔池后, 维持并控制功率,避免喷溅, 真空度逐步降低。
(4) 调低功率至 20KW, 进入精炼, 精炼 30分钟, 真空度 5Pa, 脱离 0、 H元素。 (5) 合金化: 由加料口分步加入部分脱氧剂、 Si。
(6)气体氮合金化: 开启制氮机, 充入氮气 2-3分钟, 调节炉内压力至充 氮压力或者稍大于充氮压力, 提高氮在钢液中的饱和溶解度。
(7) 加入 FeB、 FeCrN、 MnN。 提高气体分压的冶炼物料此处指 FeB。
(8)加入最终脱氧剂, 控制钢液温度比熔点高 100~150°C, 为避免注温下 降和氧化膜混入注流中, 带电浇入锭模, 降温 5分钟。
(9) 放气, 破空, 打开炉盖取出锭模, 以备进行后序热处理。
表 4: 成品钢的化学成分 (wt%)
Figure imgf000019_0001
氮回收率达到 99.9 根据不同目标钢种的成分和氮含量要求, 依据公式(1)和公式(2)计 算出氮在钢液中的活度系数、 饱和溶解度、 充氮压力和增氮合金加入量。
进一步地讲: 所述步骤 S5采用气态渗氮方法, 氮气纯度 99%, 充氮压 力由公式: lg =2x(lg [ ] -Ig^+lgO结合公式 (2) 计算得出。 高氮钢坯件的冲压方法的实施例:
实施例 10
设备采用 50-300t液压机, 去应力退火条带炉采用氮气气氛保护,保温温 度 1050°C, 每次保温时间 0. 6小时, 固溶处理中真空淬火炉保温温度 1120°C, 每次保温时间 1. 1小时,压坯所用模具材料为 DC53(HRC64,冲击韧性 70 J/cm2) , 板材所用钢号为 13Cr21Mnl6N (非标准钢号), 实测硬度 HV270, 成分见表 5。
表 5: 高氮钢的化学成分 (wt %)
Figure imgf000020_0001
具体流程:
使用喷枪加热软化板材—— >下料成壳坯—— >开耳—— >冲孔 粗磨—— >粗压一每 1次一〉条带炉软化一 -循环 4次一〉固溶处理(直至尺寸 基本成型) —— >粗铲—— >精磨—— >精压—— >精铲—— >修孔
粗压时, 材料的尺寸冷变形较大, 冷作硬化较严重 (每压一次 HV增加 10 以上), 必须压一次软化一次(软化后硬度能接近初始值), 每 4轮过后进行一 次固溶处理以彻底软化材料, 恢复材料组织性能。
模具材料的硬度优选必须达到 HRC62-64, 冲击韧性值达到 60-90 J/cm2。 如 HRC62 , 冲击韧性值 60; 或 HRC64, 冲击韧性值 90; 或 HRC63 , 冲击韧性值 80。
实施例 11
S1 : 选择模具
选用经回火处理后洛氏硬度 HRC为 60、且冲击韧性值为 55 J/cm2的模具, 将所述模具装配于坯件压制设备。
S2 : 热处理
S2. 1: 对高氮钢冲坯, 每冲坯一次后对冲坯后的高氮钢去应力退火一次, 去应力退火: 保温温度为 1050°C, 保温时间为 0. 6小时。
S2. 2 : 循环进行 S2. 1的操作至 4次后, 进行一次固溶处理, 固溶处理: 保温温度增加至 1080°C, 保温时间 1小时, 油淬快速冷却。
S2. 3 : 循环进行 S2. 1和 S2. 2的操作 3次至冲压成高氮钢坯件, 即依次 进行一次 S2. 1和 S2. 2的操作为本步骤的 1次操作,重复进行 3次这样的操作。
其它与实施例 10相同, 不再赘述。 实施例 12
SI : 选择模具
选用经回火处理后洛氏硬度 HRC为 70 、 且冲击韧性值为 120 J/cm2的模 具, 将所述模具装配于坯件冲压设备。
S2 : 热处理
S2. 1: 对高氮钢冲坯, 每冲坯一次后对冲坯后的高氮钢去应力退火一次, 去应力退火: 保温温度为 1100°C, 保温时间为 0. 75小时。
S2. 2 : 循环进行 S2. 1的操作至 5次后, 进行一次固溶处理, 固溶处理: 保温温度增加至 1120°C, 保温时间 1. 2小时, 油淬快速冷却。
S2. 3: 循环进行 S2. 1和 S2. 2的操作 7次至冲压成高氮钢坯件。
其它与实施例 10相同, 不再赘述。
实施例 13
S1 : 选择模具
选用经回火处理后洛氏硬度 HRC为 62、且冲击韧性值为 60 J/cm2的模具, 将所述模具装配于坯件冲压设备。
S2 : 热处理
S2. 1 :对高氮钢冲坯,每冲坯一次后对冲坯后的高氮钢去应力退货火一次, 去应力退火: 保温温度为 1070°C, 保温时间为 0. 6小时。
S2. 2 : 循环进行 S2. 1的操作至 5次后, 进行一次固溶处理, 固溶处理: 保温温度增加至 1100°C, 保温时间 1小时, 油淬快速冷却。
S2. 3: 循环进行 S2. 1和 S2. 2的操作 5次至冲压成高氮钢坯件。
其它与实施例 10相同, 不再赘述。
实施例 14
S1 : 选择模具
选用经回火处理后洛氏硬度 HRC为 64、且冲击韧性值为 90 J/cm2的模具, 将所述模具装配于坯件冲压设备。
S2 : 热处理
S2. 1: 对高氮钢冲坯, 每冲坯一次后对冲坯后的高氮钢去应力退火一次, 去应力退火: 保温温度为 1080°C, 保温时间为 0. 6小时。
S2. 2 : 循环进行 S2. 1的操作至 5次后, 进行一次固溶处理, 固溶处理: 保温温度增加至 1090°C, 保温时间 1. 1小时, 油淬快速冷却。
S2. 3: 循环进行 S2. 1和 S2. 2的操作 2次至冲压成高氮钢坯件。
其它与实施例 10相同, 不再赘述。
实施例 15
S1 : 选择模具
选用经回火处理后洛氏硬度 HRC为 63、且冲击韧性值为 80 J/cm2的模具, 将所述模具装配于坯件冲压设备。
S2 : 热处理
S2. 1: 对高氮钢冲坯, 每冲坯一次后对冲坯后的高氮钢去应力退火一次, 去应力退火: 保温温度为 1090°C, 保温时间为 0. 7小时。
S2. 2 : 循环进行 S2. 1的操作至 6次后, 进行一次固溶处理, 固溶处理: 保温温度增加至 11 10°C, 保温时间 1小时, 油淬快速冷却。
S2. 3: 循环进行 S2. 1和 S2. 2的操作 6次至冲压成高氮钢坯件。
其它与实施例 10相同, 不再赘述。
高氮钢的机械加工方法的实施例:
实施例 16
使用 PCV-30 加工中心, 最高转速 15000r/min, 冷却液为半合成切削液 H537;所用铣刀为 UKK : KEC0304硬质合金铣刀,当切削工艺参数如表 6所示时, 铣削加工可正常进行; 所用车刀为 MBN25 (氮化硼刀片), 当车削工艺参数如表 7所示时, 车削加工可正常进行。
表 6 : 铣削工艺参数
材料 切削参数 (刀具 D6.0四刃铣刀)
切削速度 转速 每刃进给量 /进给速度 吃刀量 Ap (mm) Vc (m/min) n(r/min) fz(mm/z ) 1 F(mm/min)
高氮钢 粗 65 3450 0.015/207 0.30
精 90 4800 0.015/288 0.03 表 7 : 车削工艺参数
Figure imgf000023_0001
实施例 17
高氮钢的机械加工方法。
该方法包括以下步骤:
S1 : 选择模具
选用洛氏硬度 HRA为 96, 抗弯强度 δ为 2. lGPa的模具;
S2 : 加工
S2. 1: 铣削
机械设备采用以下加工参数对高氮钢进行铣削: 切削速度 Vc 为 56. 5 m/min, 转速 n 为 3000 r/min, 每刃进给量 fz为 0. 01mm/z , 进给速度 F为 120mm/min, 吃刀量 Ap为 0. 03 mm;
S2. 2: 车削
机械设备采用以下加工参数对高氮钢进行车削: 转速 n为 700 r/min, 每 转进给量 fr为 0. 02 mm/r, 吃刀量 AP为 0. 05mm;
直至把高氮钢加工成符合设计要求的零件;
其中, 铣削及车削时采用冷却液, 冷却液为质量分数为 5%的乳化液, 所 述乳化液的 ra值为 9. 0。 所述乳化液的折光系数为 2, 且为防锈乳化液。
实施例 18
该方法包括以下步骤:
S1 : 选择模具
选用洛氏硬度 HRA为 95. 5, 抗弯强度 δ为 2. 3GPa的模具;
S2 : 加工
S2. 1: 铣削 机械设备采用以下加工参数对高氮钢进行铣削: 切削速度 Vc 为 94. 2 m/min, 转速 n 为 5000 r/min, 每齿进给量 fz为 0. 02 mm/z , 进给速度 F 为 400mm/min, 吃刀量 Ap为 0. 2 mm;
S2. 2: 车削
机械设备采用以下加工参数对高氮钢进行车削: 转速 n为 1000 r/min, 每转进给量 fr为 0. 04匪 /r, 吃刀量 Ap为 0. 3匪;
直至把高氮钢加工成符合设计要求的零件;
其中, 铣削及车削时采用冷却液, 冷却液为质量分数为 3%的乳化液, 所 述乳化液的 ra值为 9. 5。 所述乳化液的折光系数为 3, 且为防锈乳化液。
实施例 19
该方法包括以下步骤:
S1 : 选择模具
选用洛氏硬度 HRA为 96, 抗弯强度 δ为 2. 5GPa的模具;
S2 : 加工
S2. 1: 铣削时的加工参数
机械设备采用以下加工参数对高氮钢进行铣削: 切削速度 Vc 为 66m/min, 转速 n为 3500 r/min, 每齿进给量 fz为 0. 015 mm/z, 进给速度 F 为 211 mm/mi n, 吃刀量 Ap为 0. 09 mm;
S2. 2 : 车削时的加工参数
机械设备采用以下加工参数对高氮钢进行车削: 转速 n为 800 r/min, 每 转进给量 fr为 0. 039 mm/r, 吃刀量 Ap为 0. 18mm;
直至把高氮钢加工成符合设计要求的零件;
其中, 铣削及车削时采用冷却液, 冷却液为质量分数为 6%的乳化液, 所 述乳化液的 ra值为 9. 2。 所述乳化液的折光系数为 1, 且为防锈乳化液。
整体实施例:
实施例 20
设备采用 50Kg加压感应熔炼炉, 极限真空度为 6. 67 X 10— 2Pa, 电源功 率为 160KW, 频率为 2500Hz , 装炉量为 43Kg。钢种为 13Cr21Mnl6N (非标准钢 号), 成分控制范围及冶炼控制目标见表 8。
13Cr21Mnl6N成分控制范围及控制目标
Figure imgf000025_0001
按公式 g 2 g(0)- τ- - , 通过计算可得温度 1873K时要使氮的饱 和溶解度大于 0.7%需要的充氮气压力值, 其中氮化锰含氮量 5.95%
具体步骤如下:
(1)将纯铁、 金属铬、 钼、 坩埚碳装入炉内。 氮化锰、 锰、 脱氧剂装入料 仓。
(2)对加压感应炉熔炼室进行抽空, 真空度小于 15Pa时开始送电加热炉 料, 功率 40KW, 逐步增大。
(3) 炉料化清出现熔池后, 控制功率, 避免喷溅, 真空度逐步降低。
(4) 调低功率至 15KW, 进入精炼, 精炼 30Min, 真空度 5Pa, 脱离 0、 H 元素。
(5) 合金化: 由加料口分步加入部分脱氧剂、 Cu。
(6)气体氮合金化: 开启制氮机, 充入氮气 2-3分钟, 调节炉内压力至所 需的压力值, 提高氮在钢液中的饱和溶解度。
(7) 加入 MnN合金。
(8) 加入最终脱氧剂, 控制钢液温度比熔点高 10(T150°C, 为避免注温下 降和氧化膜混入注流中, 带电浇入锭模, 降温 5min。
(9) 放气, 破空, 打开炉盖取出锭模, 以备进行后序热处理。
表 9: 高氮钢的化学成分 (wt%)
Figure imgf000025_0002
回收率达到 99% 通过上述方法, 得到如表 9所示的所含元素质量百分比的高氮钢。
对该高氮钢进行坯件冲压:
S1 : 选择模具
选用经回火处理后洛氏硬度 HRC为 63、 且冲击韧性值为 90 J/cm2的模 具, 将所述模具装配于坯件冲压设备。
S2 : 热处理
S2. 1 :对高氮钢冲坯,每冲坯一次后对冲坯后的高氮钢去应力退火一次, 去应力退火: 保温温度为 1080°C, 保温时间为 0. 6小时。
S2. 2 : 循环进行 S2. 1的操作至 5次后, 进行一次固溶处理, 固溶处理: 保温温度增加至 1090°C, 保温时间 1. 1小时。 固溶处理优选采用油淬处理, 在其它的实施例中, 也可以采用水淬处理。
S2. 3: 循环进行 S2. 1和 S2. 2的操作 2次至冲压成高氮钢坯件。
对制成的高氮钢坯件进行机械加工:
机械加工包括以下步骤:
S1 : 选择模具
选用洛氏硬度 HRA为 96, 抗弯强度 δ为 2. 5GPa的模具;
S2 : 加工
S2. 1: 铣削时的加工参数
机械设备采用以下加工参数对高氮钢进行铣削: 切削速度 Vc 为 66m/min, 转速 n为 3500 r/min, 每齿进给量 fz为 0. 015 mm/z, 进给速度 F 为 211 mm/mi n, 吃刀量 Ap为 0. 09 mm;
S2. 2 : 车削时的加工参数
机械设备采用以下加工参数对高氮钢进行车削: 转速 n为 800 r/min, 每转进给量 fr为 0. 039 mm/r, 吃刀量 Ap为 0. 18mm;
直至把高氮钢加工成符合设计要求的零件;
其中, 铣削及车削时采用冷却液, 冷却液为质量分数为 6%的乳化液, 所述乳化液的 PH值为 9. 2。 所述乳化液的折光系数为 2, 且为防锈乳化液。 上面对本发明的实施例进行了描述,但是本发明并不局限于上述的具体 施方式, 上述的具体实施方式仅仅是示意性的, 而不是限制性的, 本领域的 通技术人员在本发明的启示下,在不脱离本发明宗旨和权利要求所保护的范 情况下, 还可做出很多形式, 这些均属于本发明的保护之内。

Claims

权 利 要 求 书
1、一种不锈钢材料,其特征在于,该不锈钢材料是以氮取代镍的 Cr-Mn-N 奥氏体不锈钢, 该不锈钢材料包含以下重量百分比的组分:
Cr: 18-22%;
Mn: 14-17%;
N: 0.4-0.75%;
C: 小于 0.15%。
2、 根据权利要求 1所述的不锈钢材料, 其特征在于, 该不锈钢材料用于 与人体直接接触的产品的零件。
3、 一种加压感应炉冶炼高氮钢的方法, 利用加压感应冶炼炉熔炼, 其特 征在于, 包括如下步骤:
S1: 依据目标钢种的元素成分, 通过下述的公式(1)及公式(2)计算出 目标钢种在常压下的极限氮含量值,该极限氮含量值乘以修正值得到冶炼配制 炉料中氮含量的实际加入重量百分比, 该修正值介于 0.7-0.9;
公式 (1):
1.17—
Figure imgf000028_0001
式中 为氮气分压, P为标准大气压;
公式 (2):
lg = {-164i»[Cr] + 8.33ί»[Μ] -33.2ί»[Μο] -134ί»[Μκ] +1.68i»[Cr]2 -1.83ί»[Μ]2 -2.78ί»[Μο]2 +8.82ί»[Μκ]2
+ (1.6ω[Νί] + 1.2ω[Μο] + 2Λ6ω[Μη])ω[ϋΓ] + (-0.26ω[Μο]+0.09ω[Μη])ω[Νί] } /τ + {0.0415«[ ] +
0 019«[M] + 0 064«[Mo] + 0 35«[MK]-0 006«[Cr]2+0 01«[M]2-0 013i»[Mo]2-0.0056iB[MK + (― 0.009ί»[Μ] - 0.0005ί»[Μο] - 0.0005«[ ])«[0] + (0.0003ί»[Μο] + 0.0007ί»[Μκ])ίΒ[Μ] } + 0.13i»[C] + 0.06ί»[Λ·] + 0.046ί»[Ρ] + 0.007 «[5] + 0Μω[ΑΙ] - 0.9ω[Τί] - 0Λω[Υ] - 0.003«[^] - 0.12ω[0] 式中/ 为钢液中氮的活度系数; 为合金元素 m的质量分数%;
S2: 按钢种所含元素的要求配制冶炼物料, 清理坩埚, 装入配制完成的冶 炼物料; S3: 对加压感应炉熔炼室进行抽空, 真空度小于 15Pa时开始送电以加热 冶炼物料, 起始功率为 40KW, 逐步增大功率, 出现熔池后, 维持并控制功率, 避免喷溅;
S4: 炉料化清后调低功率至 15-20KW, 进入精炼, 精炼 30-40分钟, 真空 度 5Pa, 脱离 0、 H元素;
S5: 气体氮合金化: 开启制氮机, 充入氮气, 炉内压力至少调节至充氮压 力, 提高氮在钢液中的饱和溶解度;
S6: 合金化: 由加料口分步加入提高气体分压的冶炼原料、 及按照 S1中 氮含量的实际加入重量百分比计算得到的氮化铬铁、 氮化锰或其它增氮合金, 以提高合金收得率;
S7: 加入脱氧剂, 控制钢液温度比熔点高 100~150°C, 带电浇入锭模中, 降温;
S8: 放气, 破空, 打开炉盖取出锭模, 制成高氮钢。
4、 根据权利要求 3所述的加压感应炉冶炼高氮钢的方法, 其特征在于, 根据不同目标钢种的成分和氮含量要求, 依据公式(1)和公式(2)计算出氮 在钢液中的活度系数、 饱和溶解度、 充氮压力和增氮合金加入量。
5、 根据权利要求 4所述的加压感应炉冶炼高氮钢的方法, 其特征在于, 所述步骤 S5 采用气体氮合金化方法, 氮气纯度 99%, 充氮压力由公式: lg 2 =2x(lg[%N]-lg +lg/ e)结合公式 (2) 计算得出。
6、 根据权利要求 3所述的加压感应炉冶炼高氮钢的方法, 其特征在于, 步骤 S7中的脱氧剂为坩埚碳、 脱氧铝。
7、 一种高氮钢坯件的冲压方法, 用于在坯件冲压设备中高氮钢坯件的冲 压, 其特征在于, 包括以下步骤:
S1: 选择模具
选用经回火处理后洛氏硬度 HRC介于 60-70 、 且冲击韧性值介于 55-120 J/cm2的模具, 将所述模具装配于坯件冲压设备;
S2: 热处理
S2.1: 对高氮钢冲坯, 每冲坯一次后对冲坯后的高氮钢去应力退火一次, 去应力退火: 保温温度介于 1050-1100°C, 保温时间 0. 5小时;
S2. 2: 循环进行 S2. 1的操作至设定次数后, 进行一次固溶处理, 固溶处 理: 保温温度增加至介于 1080-1120°C, 保温时间 1小时, 油淬快速冷却; S2. 3: 循环进行 S2. 1和 S2. 2的操作至冲压成高氮钢坯件。
8、 根据权利要求 7所述的高氮钢坯件的冲压方法, 其特征在于, 所述模 具为经回火处理后洛氏硬度 HRC介于 62-64 、 且冲击韧性值介于 60-90 J/cm2 的模具。
9、 根据权利要求 7所述的高氮钢坯件的冲压方法, 其特征在于, 所述步 骤 S2. 1中的保温时间介于 0. 5-0. 75小时。
10、根据权利要求 7所述的高氮钢坯件的冲压方法, 其特征在于, 所述步 骤 S2. 2中循环进行 S2. 1的操作的设定次数为 4-7次。
11、根据权利要求 7所述的高氮钢坯件的冲压方法, 其特征在于, 所述步 骤 S2. 2中的保温时间为 1-2小时, 油淬快速冷却。
12、根据权利要求 7所述的高氮钢坯件的冲压方法, 其特征在于, 高氮钢 为以氮取代镍的 Cr-Mn-N 奥氏体不锈钢, 其中氮含量的质量百分比介于 0. 4-0. 75 %。
13、 一种高氮钢的机械加工方法, 其特征在于, 包括以下步骤:
S1 : 选择刀具
选用洛氏硬度 HRA大于 95, 抗弯强度 δ大于 2GPa的刀具;
S2 : 加工
S2. 1: 铣削
机械设备采用以下加工参数对高氮钢进行铣削:切削速度 Vc介于 60-100 m/min, 转速 n 介于 3000-5000 r/min每刃进给量 f z介于 0. 02-0. 04mm/z , 进给速度 F介于 200-600mm/min, 吃刀量 Ap介于 0. 03-0. 4mm;
S2. 2 : 车削
机械设备采用以下加工参数对高氮钢进行车削: 转速 n 介于 700-1000 r/min, 每转进给量 fr介于 0. 02-0. 04 mm/r, 吃刀量 Ap介于 0. 02-0. 3mm; 直至把高氮钢加工成符合设计要求的零件; 其中, 铣削及车削时采用冷却液, 冷却液为质量分数为 3-6%的乳化液, 所述乳化液的 PH值介于 9. 0-9. 5。
14、 根据权利要求 13所述的高氮钢的机械加工方法, 其特征在于, 所述 乳化液的折光系数介于 1-3, 且为防锈乳化液。
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