A high-performance stainless steel ultrafine wire and its manufacturing method

Abstract

The present invention discloses a high-performance stainless steel ultrafine wire and a method for manufacturing the same. The high-performance 1Cr13 alloy ultrafine wire comprises the following chemical components by weight: C 0.12-0.15%, Si ≤ 0.50%, Mn ≤ 0.60%, P ≤ 0.025%, S ≤ 0.025%, Cr 12.3-12.5%, Ni ≤ 0.75%, Mo 0.13-0.15%, Al ≤ 0.05%, Cu ≤ 0.50%, Sn ≤ 0.05%, N ≤ 0.18%, and the balance is Fe. The mass percentages of C, N, Ni, Mn, and Cr satisfy the following relationship: 2.04% ≤ (C+N) / Cr ≤ 2.06%, and 6.32% ≤ (Mn+Ni) / Cr ≤ 6.35%. The ultrafine wire provided by the present invention exhibits excellent room-temperature tensile properties and meets the mechanical property requirements for rods specified in the U.S. standard AMS5611B.

Description

Technical Field

[0001] The embodiments of the present invention relate to the technical field of metal materials, and specifically to a high-performance stainless steel ultrafine wire and a manufacturing method thereof, and more specifically to a high-performance 1Cr13 alloy ultrafine wire and a manufacturing method thereof. Background Art

[0002] 1Cr13 is a martensitic stainless steel. According to national standards, the alloy's chemical composition by weight (wt%) is as follows: C: 0.08-0.15, Si ≤ 1.0, Mn ≤ 1.0, P ≤ 0.040, S ≤ 0.030, Cr: 11.5-13.5, Ni ≤ 0.60, Fe: the balance. This alloy, after quenching and tempering, exhibits a good balance of strength, ductility, and toughness. It offers excellent corrosion resistance in mildly corrosive media up to 30°C and stable oxidation resistance below 700°C. This alloy is suitable for components operating in corrosive media and requiring moderate strength and high toughness. It is currently widely used in various industries, particularly in the aerospace, automotive, and petrochemical industries.

[0003] The American standard AMS 5611B (STEELBARS, FORGINGS, TUBING, AND RINGS, CORROSION AND MODERATE HEAT RESISTANT 12Cr Ferrite Controlled, Consumable Electrode Melted) stipulates that the chemical composition of the alloy is as follows by weight (Wt-%): C: 0.12-0.15, Si≤0.50, Mn≤0.60, P≤0.025, S≤0.025, Cr: 11.5-12.5, Ni≤0.75, Mo≤0.20, Al≤0.05, Cu≤0.50, Sn≤0.05, N≤0.18, Fe: balance. Cut a Φ12.5mm test bar from the large product, and then quench the test bar (945±5℃, keep warm for 1±0.1h, air cool) + temper twice (315±5℃, keep warm for 2±0.25h, air cool) and the mechanical properties should meet R p0.2 ≥1000MPa, R m ≥1240MPa, A≥10%, Z≥30%.

[0004] At present, aero-engines have put forward higher mechanical property requirements for 1Cr13 alloy ultrafine wire (below Φ3mm), especially requiring that the room temperature tensile properties of 1Cr13 alloy with specifications of Φ0.09~Φ0.99mm can reach the mechanical property level of bars in the American standard AMS5611B.

[0005] CN 102618706A discloses a method for replacing quenching and tempering treatment of 1Cr13 steel after cold drawing. The specification of 1Cr13 steel cold drawn material in the document is Φ12.9mm~Φ41.6mm, which is not an ultra-fine wire material, and the room temperature tensile properties of 1Cr13 steel after cold drawing and tempering treatment cannot reach R p0.2 ≥1000MPa, R m ≥1240MPa, A≥10%, Z≥30% performance level.

[0006] CN114752741 A discloses a method for improving the mechanical properties of 12Cr13 martensitic stainless steel. After the 12Cr13 martensitic stainless steel is heat-treated at 900-1000°C, it is rapidly cooled to room temperature by water quenching and quenching. After the pretreatment is completed, the quenched 12Cr13 martensitic stainless steel is cold-rolled at room temperature, and the reduction is controlled at 15-30%. After the processing is completed, the cold-deformed 12Cr13 martensitic stainless steel is tempered, thereby improving the mechanical properties of 12Cr13 martensitic stainless steel. The morphology of the 12Cr13 alloy sample in this document is a strip, and ultrafine wire is not mentioned. At the same time, the room temperature tensile properties of the alloy after the coordinated treatment of cold rolling deformation, quenching and tempering processes cannot reach R p0.2 ≥1000MPa, R m ≥1240MPa, A≥10%, Z≥30% performance level. Summary of the Invention

[0007] To this end, an embodiment of the present invention provides a high-performance 1Cr13 alloy ultrafine wire and a manufacturing method thereof. The 1Cr13 alloy ultrafine wire has excellent room temperature tensile properties. When its specification is Φ0.09~Φ0.99mm, it can meet the mechanical property requirements of bars in the American standard AMS 5611B.

[0008] In order to achieve the above objectives, the embodiments of the present invention provide the following technical solutions:

[0009] According to a first aspect of an embodiment of the present invention, the present invention provides a high-performance 1Cr13 alloy ultrafine wire, consisting of the following chemical components in weight percentage: C 0.12-0.15%, Si≤0.50%, Mn≤0.60%, P≤0.025%, S≤0.025%, Cr 12.3-12.5%, Ni≤0.75%, Mo 0.13-0.15%, Al≤0.05%, Cu≤0.50%, Sn≤0.05%, N≤0.18%, Fe balance; wherein the mass percentages of C, N, Ni, Mn and Cr satisfy the following relationship: 2.04%≤(C+N) / Cr≤2.06%, 6.32%≤(Mn+Ni) / Cr≤6.35%.

[0010] In order to solve the technical problem that the mechanical properties of ultrafine wire cannot reach the mechanical properties of rods in the American standard AMS 5611B, the present invention is based on the 1Cr13 alloy composition, fully considering the interaction between the added alloying elements and the matrix Fe, as well as the interaction between the alloying elements. Research and development found that the above chemical composition, under the above specific dosage ratio, the elements play the greatest synergistic role, which can significantly improve the room temperature tensile properties of 1Cr13 martensitic stainless steel ultrafine wire, meeting R p0.2 ≥1000MPa, R m ≥1240MPa, A≥10%, Z≥30%, reaching the mechanical property level of bars in the American standard AMS 5611B.

[0011] The chemical composition of martensitic stainless steel alloy is the basis for determining its mechanical properties. The functions of the main chemical components of the present invention are as follows:

[0012] ① Chromium: Adding Cr to Fe-based alloys can reduce the austenite phase area, improve the hardenability and wear resistance of the alloy, and improve the corrosion resistance and oxidation resistance. In addition, Cr is a medium carbide forming element, and the carbide M 23 C6 can strengthen the grain boundaries and improve the overall performance of the alloy.

[0013] ② Molybdenum: Adding a certain amount of Mo to Fe-based alloys can cause severe lattice distortion and a strong solid solution strengthening effect due to the Mo atomic radius, which is 9-12% larger than that of Fe. Mo is also a strong carbide former, and the resulting carbides (MC) refine the grains, improving the alloy's overall properties. Mo also enhances the alloy's corrosion resistance.

[0014] ③ Carbon and Nitrogen: The primary strengthening mechanism of 1Cr13 alloy steel is the formation of a certain amount of lath martensite during quenching. Martensite is a supersaturated solid solution of carbon in α-Fe. Carbon is a primary element in iron-based alloys and also a primary carbide-forming element. Carbides formed at the end of melting and solidification and during heat treatment refine grains, reducing crack and cavity initiation and propagation, thereby improving the alloy's strength and ductility. Furthermore, nitrogen plays a similar role to carbon in alloy steels.

[0015] ④ Manganese and Nickel: Adding a certain amount of Mn and Ni to iron-based alloys expands the austenite phase, which negatively impacts the alloy's strength but improves its plasticity. Furthermore, manganese is a good deoxidizer and desulfurizer, significantly improving the alloy's processing and overall mechanical properties. Ni also enhances the alloy's hardenability.

[0016] Furthermore, the specification of the ultrafine wire is Φ0.09~Φ0.99mm.

[0017] According to a second aspect of an embodiment of the present invention, the present invention provides a method for manufacturing the high-performance 1Cr13 alloy ultrafine wire as described above, comprising the following steps:

[0018] According to the alloy design ratio, Cr, Mo and Fe are smelted, then refined, and C, Mn, Ni and ferrochrome nitride are added. After the raw materials are fully melted, they are poured to obtain steel ingots;

[0019] The steel ingot is subjected to hot working, first annealing, drawing, second annealing, quenching, and two temperings in sequence to obtain the high-performance 1Cr13 alloy ultrafine wire; wherein the drawing parameters are: controlling the deformation of the finished product to be 88% to 98%.

[0020] The study found that in the drawing step, by controlling the deformation of the ultra-fine finished wire to 88% to 98%, and combining the second annealing + quenching + two tempering processes, the ultra-fine wire has R p0.2 ≥1000MPa, R m Excellent mechanical properties of ≥1240MPa, A≥10%, Z≥30%.

[0021] Furthermore, the parameters of the hot working are: heating temperature of 1180-1200° C., holding time ≥ 2 h, and cooling method of slow cooling.

[0022] Furthermore, the parameters of the first annealing are: annealing temperature is 760° C.±10° C., holding time is ≥1 hour, and cooling method is air cooling.

[0023] Furthermore, the parameters of the second annealing are: annealing temperature is 760° C.±10° C., holding time is 0.5 to 10 minutes, and cooling method is air cooling.

[0024] Furthermore, the quenching parameters are: quenching temperature is 945±5°C, holding time is 1±0.1h, and cooling method is air cooling.

[0025] Furthermore, the parameters of the two temperings are: the tempering temperature is 315±5°C, the holding time is 2±0.25h, and the cooling method is air cooling.

[0026] Furthermore, the smelting is carried out under vacuum conditions at a smelting temperature of 1600-1650°C.

[0027] Furthermore, the refining temperature is 1630-1650° C., and argon is filled into the smelting furnace until the vacuum degree in the furnace is ≤0.5Pa.

[0028] In some specific embodiments, the method for manufacturing the high-performance 1Cr13 alloy ultrafine wire as described above comprises the following steps:

[0029] 1) Melting: Weigh Cr, Mo and Fe raw materials and place them in a crucible. Draw into a high vacuum state and set the melting temperature of the melting furnace to 1600-1650°C. After the raw materials are fully melted, continue heating for 5-10 minutes until the raw materials are completely melted.

[0030] 2) Refining: The solution temperature is controlled at 1630-1650°C, and argon is filled into the melting furnace until the vacuum degree in the furnace is ≤0.5Pa. After refining for 10 minutes, C, Mn, Ni and ferrochrome nitride are added. After the raw materials are fully melted, the temperature of the molten steel is adjusted to 1550-1580°C and then poured to obtain a steel ingot;

[0031] 3) Hot working: hot working the steel ingot into Φ8mm wire rod, wherein the heating temperature is 1180-1200℃, the holding time is ≥2h, and the cooling method is slow cooling;

[0032] 4) First annealing: anneal the Φ8mm wire rod after hot working at 760℃±10℃, with a holding time of ≥1 hour and air cooling;

[0033] 5) Drawing: The wire rod after the first annealing treatment is drawn and reduced in diameter using a wire drawing machine to a diameter of Φ0.09-Φ0.99 mm, and the deformation of the finished product is controlled to be 88%-98%;

[0034] 6) Second annealing: The ultra-fine wire of Φ0.09~Φ0.99mm is subjected to the second annealing treatment, the annealing temperature is 760℃±10℃, the annealing time is 0.5~10min, and the cooling method is air cooling;

[0035] 7) Quenching: After the second annealing, the Φ0.09-Φ0.99 mm ultrafine wire is quenched at 945±5°C, the holding time is 1±0.1h, and the cooling method is air cooling;

[0036] 8) Double tempering: The Φ0.09~Φ0.99mm ultrafine wire after quenching is tempered twice, the tempering system is 315±5℃, the holding time is 2±0.25h, and the cooling method is air cooling.

[0037] The embodiments of the present invention have the following advantages:

[0038] The room temperature tensile properties of the 1Cr13 alloy ultrafine wire provided by the present invention meet the requirements of the mechanical properties of bars in the American standard AMS5611B. At the same time, after aviation testing, it meets the use requirements of springs for aviation power plants, has excellent comprehensive performance, and meets the needs of actual equipment. DETAILED DESCRIPTION

[0039] The following describes the implementation of the present invention using specific embodiments. Those skilled in the art will readily understand the other advantages and benefits of the present invention from the disclosure herein. Obviously, the embodiments described are only a portion of the present invention, not all of it. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are intended to fall within the scope of protection of the present invention.

[0040] Example 1

[0041] This embodiment provides a high-performance 1Cr13 alloy ultrafine wire, the chemical composition of which is shown in Table 1.

[0042] Raw materials: pure iron, pure metallic chromium, pure electrolytic manganese, pure electrolytic nickel, pure carbon particles, pure ferrochromium nitride, pure molybdenum.

[0043] The method for manufacturing the high-performance 1Cr13 alloy ultrafine wire of this embodiment includes the following steps:

[0044] Melting: Weigh the raw materials according to the designed composition ratio, put pure metal chromium, pure molybdenum and pure iron into the crucible, evacuate to a high vacuum state, and the melting temperature is 1600-1650℃. After the raw materials are completely melted, continue heating for about 5 minutes until the raw materials are completely melted;

[0045] Refining: The solution temperature is controlled at 1630-1650℃, and argon is filled into the furnace until the vacuum degree in the furnace is ≤0.5Pa. After refining for 10 minutes, pure carbon particles, pure electrolytic manganese, pure electrolytic nickel and pure ferrochrome nitride are added. After the small materials are completely melted, the temperature of the molten steel is adjusted to 1550-1580℃ and then poured to obtain a steel ingot.

[0046] Hot processing: hot processing the steel ingot into Φ8mm wire rod, wherein the heating temperature is 1180~1200℃, the holding time is ≥2h, and the cooling method is slow cooling;

[0047] First annealing: anneal the Φ8mm wire rod after hot working at 760℃±10℃, with a holding time of ≥1 hour and air cooling;

[0048] Drawing: The annealed wire rod is drawn and reduced to a diameter of Φ0.09-Φ0.99mm using a wire drawing machine, with the deformation of the finished product controlled at 88%-98%;

[0049] Second annealing: annealing of ultra-fine wires with a diameter of Φ0.09 to Φ0.99 mm, at a temperature of 760°C ± 10°C, for a time of 0.5 to 10 minutes, with air cooling as the cooling method;

[0050] Quenching: quench the annealed Φ0.09~Φ0.99mm ultra-fine wire at 945±5℃, keep warm for 1±0.1h, and use air cooling as the cooling method;

[0051] Double tempering: The Φ0.09~Φ0.99mm ultrafine wire after quenching is tempered twice, the tempering system is 315±5℃, the heat preservation is 2±0.25h, and the cooling method is air cooling to obtain 1Cr13 alloy ultrafine wire with a specification of Φ0.09~Φ0.99mm.

[0052] Table 1 Chemical composition of the alloy in Example 1 (Wt-%)

[0053] C Si Mn Cr Ni Mo N P S Al Cu Sn Fe 0.142 <0.1 0.29 12.32 0.49 0.14 0.11 <0.025 0.0014 <0.05 <0.05 <0.05 Balance

[0054] The room temperature tensile properties (R p0.2 、R m , A and Z) were tested, and the results are shown in Table 2.

[0055] Table 2 Room temperature tensile properties of 1Cr13 alloy Φ0.90 mm ultrafine wire in Example 1

[0056]

[0057]

[0058] The results show that the room temperature tensile properties (R p0.2 、R m , A and Z) have reached the mechanical property level of the bar in the American standard AMS 5611B.

[0059] Example 2

[0060] This embodiment provides a high-performance 1Cr13 alloy ultrafine wire, which differs from Example 1 in that the weight percentages of the chemical components are different.

[0061] The chemical composition of the alloy of this embodiment is shown in Table 3, and the room temperature tensile property test results are shown in Table 4.

[0062] Table 3 Chemical composition of the alloy in Example 2 (Wt-%)

[0063] C Si Mn Cr Ni Mo N P S Al Cu Sn Fe 0.144 <0.1 0.27 12.34 0.51 0.15 0.11 <0.025 0.0012 <0.05 <0.05 <0.05 Balance

[0064] Table 4 Room temperature tensile properties of 1Cr13 alloy Φ0.30 mm ultrafine wire in Example 2

[0065]

[0066] The results show that the room temperature tensile properties (R p0.2 、R m , A and Z) have reached the mechanical property level of the bar in the American standard AMS 5611B.

[0067] Example 3

[0068] This embodiment provides a high-performance 1Cr13 alloy ultrafine wire, which differs from Example 1 in that the weight percentages of the chemical components are different.

[0069] The chemical composition of the alloy of this embodiment is shown in Table 5, and the room temperature tensile property test results are shown in Table 6.

[0070] Table 5 Chemical composition of the alloy in Example 3 (Wt-%)

[0071] C Si Mn Cr Ni Mo N P S Al Cu Sn Fe 0.126 <0.1 0.54 12.46 0.25 0.14 0.13 <0.025 0.0012 <0.05 <0.05 <0.05 Balance

[0072] Table 6 Room temperature tensile properties of 1Cr13 alloy Φ0.30 mm ultrafine wire in Example 3

[0073]

[0074] The results show that the room temperature tensile properties (R p0.2 、R m , A and Z) have reached the mechanical property level of the bar in the American standard AMS 5611B.

[0075] Comparative Example 1

[0076] This comparative example provides an alloy ultrafine wire, which differs from Example 1 in that the weight percentages of the chemical components are different.

[0077] The chemical composition of the alloy of this embodiment is shown in Table 7, and the test results of the room temperature tensile properties are shown in Table 8.

[0078] Table 7 Chemical composition of the alloy in Comparative Example 1 (Wt-%)

[0079] C Si Mn Cr Ni Mo N P S Al Cu Sn Fe 0.132 <0.1 0.26 12.42 0.28 0.14 0.10 <0.025 0.0012 <0.05 <0.05 <0.05 Balance

[0080] Table 8 Room temperature tensile properties of Φ0.30 mm ultrafine wire in comparative example 1

[0081]

[0082] The results show that the room temperature tensile properties (R p0.2 、R m , A and Z) do not reach the mechanical property level of the bar in the American standard AMS 5611B.

[0083] Comparative Example 2

[0084] This comparative example provides an alloy ultrafine wire, which differs from Example 1 in that the weight percentage of Cr is 12.14%, and the weight percentages of other chemical components are the same as those in Example 1.

[0085] The test results of mechanical properties are shown in Table 9.

[0086] Table 9 Room temperature tensile properties of Φ0.30 mm ultrafine wire in comparative example 2

[0087]

[0088] The results show that the room temperature tensile properties (R p0.2 、R m , A and Z) do not reach the mechanical property level of the bar in the American standard AMS 5611B.

[0089] Although the present invention has been described in detail above using general descriptions and specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made thereto. Therefore, such modifications and improvements, without departing from the spirit of the present invention, are intended to be within the scope of protection claimed herein.

Claims

1. A high-performance 1Cr13 alloy ultrafine wire, characterized in that: The ultrafine wire is composed of the following chemical components in weight percentage: C 0.12-0.15%, Si≤0.50%, Mn≤0.60%, P≤0.025%, S≤0.025%, Cr 12.3-12.5%, Ni≤0.75%, Mo 0.13-0.15%, Al≤0.05%, Cu≤0.50%, Sn≤0.05%, N≤0.18%, and Fe as the balance; wherein the mass percentages of C, N, Ni, Mn and Cr satisfy the following relationship: 2.04%≤(C+N) / Cr≤2.06%, 6.32%≤(Mn+Ni) / Cr≤6.35%; and the specification of the ultrafine wire is Φ0.09-Φ0.99 mm.

2. The method for manufacturing high-performance 1Cr13 alloy ultrafine wire according to claim 1, characterized in that: The steps include: According to the alloy design ratio, Cr, Mo and Fe are smelted, then refined, and C, Mn, Ni and ferrochrome nitride are added. After the raw materials are fully melted, they are poured to obtain steel ingots; The steel ingot is subjected to hot working, first annealing, drawing, second annealing, quenching, and two temperings in sequence to obtain the high-performance 1Cr13 alloy ultrafine wire; The drawing parameters are as follows: controlling the deformation of the finished product to be 88% to 98%.

3. The method for manufacturing high-performance 1Cr13 alloy ultrafine wire according to claim 2, characterized in that: The parameters of the hot working are: heating temperature of 1180-1200° C., holding time of ≥2 hours, and slow cooling.

4. The method for manufacturing high-performance 1Cr13 alloy ultrafine wire according to claim 2, characterized in that: The parameters of the first annealing are: annealing temperature is 760°C ± 10°C, holding time is ≥ 1 hour, and cooling method is air cooling.

5. The method for manufacturing high-performance 1Cr13 alloy ultrafine wire according to claim 2, characterized in that: The parameters of the second annealing are: annealing temperature is 760° C.±10° C., holding time is 0.5 to 10 minutes, and cooling method is air cooling.

6. The method for manufacturing high-performance 1Cr13 alloy ultrafine wire according to claim 2, characterized in that: The quenching parameters are as follows: quenching temperature is 945±5°C, holding time is 1±0.1h, and cooling method is air cooling.

7. The method for manufacturing high-performance 1Cr13 alloy ultrafine wire according to claim 2, characterized in that: The parameters of the two tempering processes are as follows: the tempering temperature is 315±5° C., the holding time is 2±0.25 h, and the cooling method is air cooling.

8. The method for manufacturing high-performance 1Cr13 alloy ultrafine wire according to claim 2, characterized in that: The smelting is carried out under vacuum conditions at a smelting temperature of 1600-1650°C.

9. The method for manufacturing high-performance 1Cr13 alloy ultrafine wire according to claim 2, characterized in that: The refining temperature is 1630-1650° C., and argon gas is filled into the smelting furnace until the vacuum degree in the furnace is ≤0.5 Pa.

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