CN114134428B - Nickel-saving iron-based high-temperature alloy for engine valve and manufacturing method thereof - Google Patents
Nickel-saving iron-based high-temperature alloy for engine valve and manufacturing method thereof Download PDFInfo
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Abstract
The invention provides a nickel-saving Fe-Ni-Cr-based high-temperature alloy. The selected components comprise the following components in percentage by mass: c:0.071-0.092%, mn:0.18 to 0.50 percent of Cr, 15.15 to 15.99 percent of Cr, 0.4 to 1.0 percent of Mo, 1.69 to 2.00 percent of Al, 2.00 to 2.19 percent of Ti, 0.45 to 0.75 percent of Nb, less than or equal to 0.3 percent of V, 27.35 to 29.98 percent of Ni, 0.002 to 0.007 percent of B, 0.005 to 0.013 percent of Zr, less than or equal to 0.02 percent of S, less than or equal to 0.02 percent of P, and the balance of Fe and inevitable impurities; wherein the contents of C, cr, mo, al, ti and Nb must satisfy: ni critical ＝10×(‑7.85‑15.7×C％+0.285×Cr％‑0.003×Mo％‑0.258×Al％+3.05×Ti％+2.25×Nb％) 1.584 Less than or equal to 25.0 percent, thus avoiding the formation of a blocky Laves phase in the liquid phase in the solidification process. The solidus temperature of the material is 1160-1178 ℃, the starting precipitation temperature of the Laves phase is 930-946 ℃, and the over-burning phenomenon in the manufacturing process is avoided. The nickel-saving Fe-Ni-Cr-based high-temperature alloy manufactured by the invention has better high-temperature performance than nickel-based alloys Inconel751 and NiCr20TiAl, and has unobvious strength and plasticity change at room temperature to 650 ℃, so that the nickel-saving Fe-Ni-Cr-based high-temperature alloy can replace the nickel-based alloys Inconel751 and NiCr20TiAl to produce engine valves, thereby reducing the cost.
Description
Technical Field
The invention relates to the technical field of iron-based high-temperature alloys, in particular to an engine valve material with excellent performance and a manufacturing method thereof.
Background
With the improvement of the requirements of people on the emission of the tail gas of the automobile engine, in order to reduce the emission of the tail gas containing harmful substances and improve the efficiency of the engine, the mechanical impact, the thermal load and the abrupt change of the temperature born by the engine valve, particularly the exhaust valve are strong, the working environment and the high temperature are more severe and higher, even reach more than 800 ℃, and therefore, the material for processing the exhaust valve also gradually adopts nickel-based high-temperature alloy or iron-based high-temperature alloy to replace the prior higher-end austenite heat-resistant steel such as 21-4NWNb, 61Cr21Mn10Mo1V1Nb1N and the like. The nickel-base superalloys currently used primarily for the manufacture of exhaust valves are Inconel751 and Nimonic 80A. The alloy content of the two products is high, particularly the content of nickel exceeds 70%, so the cost of the produced valve is very high. As the technology is continuously improved, the lead content in oil products used by an engine is greatly reduced, and the strict requirements of the automobile industry on cost are strict, people change the gas valve alloy for producing the gas valve from nickel-based high-temperature alloy to iron-based high-temperature alloy with low nickel content (20-40%), and successively invent more gas valve materials.
The main alloy elements of patent CN200910028928.X nickel-saving type valve alloy material comprise (by weight) C not more than 0.07%, ni30.00-34.00%, cr13.0-16.0%, mo0.60-0.80%, ti2.20-3.00%, al1.20-2.00% and Nb0.40-0.70%.
The main alloy elements of patent CN201210175284.9 'a valve alloy material and a manufacturing method thereof' comprise, by weight, less than or equal to 0.07% of C, 27-32% of Ni, 20-28% of Cr, 0.5-1.8% of Nb0.20-2.35% of Ti, 0.5-1.5% of Al, 0.01-0.20% of Zrs, and 0.20-0.50% of V.
The main alloy elements of patent CN201310349567.5, a high-strength nickel-saving gas valve steel and a preparation method thereof, comprise, by weight, 0.01-0.25% of C, 18.0-28.0% of Ni, 16.0-24.0% of Cr16, 18.0-28.0% of Ni, 0.5-2.5% of Al, 1.5-3.5% of Ti and 0.5-2.5% of Nb0.5.
The main alloy elements of patent CN201410370362.X, a nickel-saving type gas valve alloy and a preparation method thereof, comprise, by weight, 0.01-0.30% of C, 40.0-50.0% of Nis, 24.0-28.0% of Cr24, 0.7-2.5% of Als, 1.0-3.7% of Tis, 0.2-2.5% of Nbs, 0.2-1.2% of Mos and 0.05-0.5% of V.
CN201510176213.4, a low-nickel austenite gas valve alloy and a preparation method thereof, the main alloy elements comprise, by weight, 0.02-0.08% of C, 8.0-35.0% of Ni0, 12.0-17.0% of Cr12, 1.5-2.5% of Al, 2.5-3.5% of Ti, 0.05-0.2% of Y and 0.05-0.3% of Hf0.
The main alloy elements of patent CN201510250560.7 'an Ni-saving high-temperature resistant gas valve alloy' comprise, by weight, 0.03-0.08% of C, 34.0-36.0% of Ni, 16.0-16.5% of Cr16, 0.5-1.5% of Nb0, 2.3-2.9% of Ti, 1.5-2.2% of Al, 0.5-1.5% of Mo and 0.02-0.1% of ZrC.
The main alloy elements of patent CN201711343698.7, an improved valve stainless steel and a preparation method thereof, comprise, by weight, not more than 0.20% of C, 28.0-35.0% of Ni0, 12.5-16.5% of Cr12, 0.2-1.50% of Mo0, 1.4-2.4% of All, 2.0-3.50% of Ti2 and 0.15-0.20% of Nb0.15.
The main alloy elements of patent CN201911103173.5 'a low-cost high-performance gas valve alloy and a preparation method thereof' comprise, by weight, 0.05-0.15% of C, 25.0-30.0% of Ni0, 20.0-25.0% of Cr20, 0.6-1.6% of Al, 2.0-3.0% of Ti, 0.8-1.8% of Nb0, 0.1-0.4% of V, 0.01-0.05% of Zr0, and 0.01-0.03% of Ce0.01.
The main alloy elements of patent CN95108211.6 'a high-strength heat-resistant steel' are C0.02-0.2%, ni20-28%, cr17-23%, al0.7-2.0%, ti1.80-3.2%, nb0.7-2.0%, zr0.01-0.2% and Co0.1-3.0% by weight.
The main alloy elements of patent CN200510051398.2 'high-performance nickel-saving valve alloy material' are C0.043-0.10 wt%, ni40-50 wt%, cr18-25 wt%, nb0.5-1.5 wt%, ti1.8-2.8 wt%, al0.6-1.6 wt% and Zr0.02-0.3 wt%.
The main alloy elements of CN201610034401.8 microalloyed high-strength oxidation-resistant Fe-Ni alloy gas valve steel comprise, by weight, C0.02-0.1%, ni25.0-36.0%, cr14.0-20.0%, ti1.9-3.0%, al0.5-2.6%, mo0.7-1.2%, nb0.40-0.76%, and N0.01-0.1%.
The main alloy elements of patent CN201711437693.0 'A high-hardness alloy air valve and its preparation method' comprise, by weight, C0.03-0.10%, ni25.00-30.00%, cr21.00-25.00%, al0.70-3.00%, ti2.00-4.00%, nb0.80-3.00%, and V0.20-0.60%.
The main alloy elements of patent EP0657558A1 "iron-based superalloy" comprise, by weight, not more than 0.20% of C, 25.0-30.0% of Ni, 10-15% of Cr, 0.7-2.0% of Al, 2.5-4.0% of Ti, and 0.05-1.0% of Nbs.
The main alloy elements of the FE-NI-CR based high-temperature alloy, the engine valve and the woven mesh support for the exhaust catalyst in the patent US5660938 comprise, by weight, 0.01-0.15% of C, 30-49% of Ni, 13-18% of Cr, 1.6-3.0% of Al, 1.5-3.0% of Ti, less than or equal to 2.5% of Mo and less than or equal to 3% of W.
The main alloy elements of the patent US5951789 heat-resistant alloy for exhaust valve and the manufacturing method thereof comprise, by weight, 0.01-0.1% of C, 25-45% of Ni, 12-25% of Cr, 0.5-3.0% of Al, 3.5% or less of Ti, 0.2-2.0% of Nb0, 3% or less of W, 3% or less of Mo and 1% or less of V.
By examining the characteristics of the solidus temperature and the Laves phase dissolution temperature of the Fe — Ni — Cr-based high-temperature alloy for valve fabrication in these patents, it was found that the solidus temperature and the Laves phase precipitation start temperature vary greatly within the ranges of the respective compositions provided. The solidus temperature of some materials is lower, even lower than the ordinary forging or hot rolling temperature, and because the thermal conductivity of the materials is poor, the materials are easy to cause the phenomenon of overburning in the rapid deformation process of forging or hot rolling and the like, so that core cracks exist and the materials are scrapped. Some Laves phases begin to precipitate at a temperature higher than the solidus temperature, and large Laves phases are formed in the obtained structure, which adversely affects the properties of the material.
Therefore, in order to avoid the overheating and overburning phenomenon of the alloy material caused by the temperature rise exceeding the solidus line in the rapid thermal deformation production process, the solidus line temperature must be higher than the forging or hot rolling temperature of the conventional Fe-Ni-Cr-based high-temperature alloy by about 50-100 ℃; meanwhile, the Laves phase is not formed in the solidification process, so that the generation of the blocky Laves phase is avoided. For these two reasons, it is necessary to design a nickel-saving Fe-Ni-Cr-based superalloy, which not only avoids the above two problems, but also produces engine exhaust valves with performance equivalent to Inconel751 and Nimonic 80A.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a nickel-saving Fe-Ni-Cr-based high-temperature alloy. The invention also aims to provide a method for manufacturing the nickel-saving Fe-Ni-Cr-based high-temperature alloy.
The invention has the technical scheme that the nickel-saving iron-based high-temperature alloy for the engine valve is a nickel-saving Fe-Ni-Cr-based high-temperature alloy and comprises the following components in percentage by mass:
c:0.071-0.092%, mn:0.18 to 0.50 percent of Cr, 15.15 to 15.99 percent of Cr, 0.4 to 1.0 percent of Mo, 1.69 to 2.00 percent of Al, 2.00 to 2.19 percent of Ti, 0.45 to 0.75 percent of Nb, less than or equal to 0.3 percent of V, 27.35 to 29.98 percent of Ni, 0.002 to 0.007 percent of B, 0.005 to 0.013 percent of Zr, less than or equal to 0.02 percent of S, less than or equal to 0.02 percent of P, and the balance of Fe and inevitable impurities;
wherein the contents of C, cr, mo, al, ti and Nb meet the following requirements:
Ni critical ＝10×(-7.85-15.7×C％+0.285×Cr％-0.003×Mo％-0.258×Al％+3.05×Ti％+2.25 ×Nb％) 1.584 ≤25.0％。
this avoids the formation of a lumpy Laves phase in the liquid phase during solidification. The formula definition is the innovation point of the invention and is mainly used for defining whether the Laves phase appears above the solidus in the phase diagram of the steel grade of the invention. If this value is outside the Ni range of the steel grade, the steel grade is less likely to exhibit a bulk Laves phase. If still in the Ni range, a massive Laves phase may appear, which may affect the use of the steel grade.
According to the nickel-saving iron-based high-temperature alloy for the engine valve, the solidus temperature of the material is 1160-1178 ℃, and the initial precipitation temperature of the Laves phase is 930-946 ℃.
The main design idea of the invention is as follows:
carbon mainly forms carbide with elements such as Ti, nb, cr, V and the like in the alloy to improve the mechanical property, strengthen the grain boundary, prevent the granular discontinuous carbide precipitated in the grain boundary from sliding along the grain and expanding cracks in the deformation process, prolong the service life and improve the lasting plasticity and the toughness of the alloy. In the present invention, ni is considered critical A requirement of ≦ 25.0%, the C content is defined in the range of 0.071 to 0.092%.
Manganese functions as an austenite forming element and also functions as a deoxidizer in the alloy for smelting, but it easily segregates to grain boundaries, weakens the bonding force of the grain boundaries, and remarkably reduces the permanent strength, so that the Mn content is defined in the range of 0.18 to 0.50% in the present invention.
The chromium has the function of improving the heat strength, creep resistance, high-temperature oxidation resistance and high-temperature gas corrosion resistance of the alloy. An excess will promote the formation of detrimental phases in the alloy, and therefore the Cr content is defined in the range of 15.15-15.99% in the present invention.
Molybdenum is added into the alloy to mainly improve the heat resistance and the lasting plasticity of the alloy and improve the notch sensitivity, while excessive molybdenum is easy to increase the initial precipitation temperature of the Laves phase and promote the formation of harmful phases in the alloy, so the content of Mo is defined to be in the range of 0.4-1.0 percent in the invention.
The addition of aluminum and titanium is primarily to form a gamma prime precipitation strengthening phase with nickel. If the Al content is too high, an excessive amount of intermetallic compounds of aluminum may be generated, resulting in a doubling of the processing difficulty. Too high Ti promotes the formation of a bulk Laves phase, so the Al content is defined in the range of 1.69-2.00% in the present invention; the Ti content is defined in the range of 2.00-2.19%.
The addition of nickel makes the alloy obtain a gamma matrix with a face-centered cubic structure, and forms a gamma' phase precipitation strengthening phase with Al, ti, nb and other elements. Also from the viewpoint of alloy cost, the present invention defines the Ni content in the range of 27.35 to 29.98%.
The niobium is added, and the main purpose is to form carbide with carbon to improve the heat strength of the alloy, and also to form a gamma' phase precipitation strengthening phase with the action of Ni element to improve the high-temperature strength. Since niobium is relatively expensive and too much may also cause the formation of a bulk Laves phase, the present invention defines the Nb content in the range of 0.45-0.75%.
The vanadium is added, the main purposes are to form carbide, refine alloy grains, improve the plasticity of the hot working process, improve the hot strength of the alloy and be beneficial to improving the notch sensitivity. In view of the fact that vanadium is expensive, the present invention defines the V content in the range of 0.3% or less.
The zirconium element is added, and the main purposes are to improve the endurance life of the alloy, reduce the creep rate and improve the endurance notch sensitivity. Meanwhile, the thermoplasticity and hot workability of the alloy are improved through the grain boundary strengthening effect of zirconium. The present invention defines the Zr content in the range of 0.005 to 0.013%.
The boron element is added, and the grain boundary strengthening effect is mainly utilized to refine grains and improve the thermoplasticity of the alloy. When the amount of boride is too large, boride having a low melting point is easily produced, and hot workability is deteriorated. Therefore, the present invention defines the B content in the range of 0.002 to 0.007%.
The invention also provides a method for manufacturing the nickel-saving iron-based high-temperature alloy for the engine valve,
the method comprises the following steps: non-vacuum induction melting, electroslag remelting, forging and cogging, wire rolling, solid solution and silvering;
1) Non-vacuum induction melting
Adopting non-vacuum induction melting, selecting slag charge proportioning: caO CaF 2 30-40; the white slag time is more than 15 minutes; tapping temperature: casting an electrode bar at 1530-1590 ℃;
2) Electroslag remelting
Carrying out electroslag remelting on the electrode rod smelted by the non-vacuum induction furnace; selecting five-element slag system CaF2: al 2 O 3 :CaO:MgO: TiO 2 15-25; the melting speed in the electroslag process is controlled to be 3.0-6.0kg/min; obtaining an electroslag ingot;
3) Forging and cogging
Cogging the electroslag ingot by adopting a rapid radial forging combined cogging process or a direct radial forging cogging process, wherein the forging temperature range is 1100-1140 ℃; the forging temperature is more than or equal to 1000 ℃, and the finish forging temperature is more than or equal to 850 ℃ to obtain a rolled blank;
4) Wire rod rolling
Putting the rolled blank into a heating furnace of a wire rolling production line; controlling the temperature of a soaking section of the heating furnace at 1110 +/-10 ℃, and tapping and rolling after the temperature of the soaking section reaches the temperature; the finishing temperature is less than or equal to 950 ℃.
According to the method for preparing the nickel-saving iron-based high-temperature alloy for the engine valve, the slag amount is preferably added in the step 1) according to the specification of a non-vacuum induction furnace, and the range of the slag amount is 10-20 kg/ton.
Considering that the nickel-saving Fe-Ni-Cr-based high-temperature alloy contains high content of Ti element and is easy to lose, a quinary slag system CaF is selected 2 :Al 2 O 3 :CaO:MgO:TiO 2 ＝60-70:15-25:8-12:3-6:3-10。
Preferably, the slag system of five elements CaF 2 :Al 2 O 3 :CaO:MgO:TiO 2 ＝60-70:15-25:8-12:3-6:3-5。
Covering slag early in the smelting process (within 5-15 minutes after melting), and reducing air suction. According to the method for manufacturing the nickel-saving iron-based high-temperature alloy for the engine valve, the electrode rod with the diameter phi of 360-400mm is cast in the step 1).
According to the method for manufacturing the nickel-saving iron-based high-temperature alloy for the engine valve, the electroslag ingot in the step 2) is preferably 400-450mm in diameter.
According to the method for manufacturing the nickel-saving iron-based high-temperature alloy for the engine valve, the cross-sectional dimension of the rolled blank in the step 3) is preferably as follows: 140-160 (+ 5, -7). Times.140-160 (+ 5, -7) mm 2 (ii) a Length: 8000-10000 mm.
According to the method for manufacturing the nickel-saving iron-based high-temperature alloy for the engine valve, the heat preservation time in the step 4) is preferably 30-70 minutes.
Further, the temperature is preserved for 40-60 minutes in the step 4).
According to the method for manufacturing the nickel-saving iron-based high-temperature alloy for the engine valve, the rolling speed in the step 4) is preferably less than or equal to 23m/s.
The material not only has the solidus temperature which is about 50-60 ℃ higher than the forging or hot rolling temperature (1100-1120 ℃) of the conventional Fe-Ni-Cr-based high-temperature alloy, but also has the initial precipitation temperature of a Laves phase which is lower than the solidus temperature, and simultaneously has the performance which is equivalent to that of the nickel-based high-temperature alloy Inconel751 and Nimonic 80A.
Compared with the existing alloy, the invention has the following beneficial effects:
the nickel-saving Fe-Ni-Cr-based high-temperature alloy with higher solidus temperature is obtained through reasonable alloy component design, the hot-workable temperature range of the material is expanded, the overburning phenomenon caused by poor heat conductivity in the hot-workable process is avoided, and the generation of large Laves harmful phases in the solidification process of the material is also avoided, so that the structure is improved, the performance is improved, and the problems of difficult processing and high rejection rate of the iron-based high-temperature alloy are solved.
Detailed Description
Example 1:
the nickel-saving Fe-Ni-Cr-based high-temperature alloy comprises the following components in percentage by mass: 0.090% of C, 0.48% of Mn, 15.96% of Cr, 0.98% of Mo, 1.95% of Al, 2.15% of Ti, 0.73% of Nb, 0.28% of V, 29.95% of Ni, 0.006% of B, 0.012% of Zr, 0.001% of S, 0.014% of P, and the balance Fe and inevitable impurities. Ni critical 16.15%, solidus temperature T Fixing device At 1183.09 deg.C, and a Laves phase precipitation temperature T Lav It was 865.66 ℃. The manufacturing process comprises the following steps: non-vacuum induction melting and electric heatingSlag remelting, forging and cogging, wire rolling, solid solution and silver bright processing.
1) Non-vacuum induction melting
Adopting non-vacuum induction melting, selecting slag charge proportioning: caO CaF 2 = 65. The amount of slag added is 15 kg/ton according to the specification of the non-vacuum induction furnace. The slag is covered early in the smelting process (within 10 minutes after melting), and air suction is reduced. The white slag time must be greater than 15 minutes. Tapping temperature: 1540 deg.C. And casting the electrode bar with the size of 360mm phi.
2) Electroslag remelting
And carrying out electroslag remelting on the electrode rod smelted by the non-vacuum induction furnace. Considering that the nickel-saving Fe-Ni-Cr-based high-temperature alloy contains high content of Ti element and is easy to lose, a five-element slag system CaF is selected 2 :Al 2 O 3 :CaO:MgO: TiO 2 10. The melting speed in the electroslag process is controlled to be 5.0kg/min. Obtaining an electroslag ingot with the diameter of 420 mm.
3) Forging and cogging
The electroslag ingot with the diameter of 420mm of the nickel-saving Fe-Ni-Cr-based high-temperature alloy is cogging by adopting a rapid radial forging combined cogging process or a direct radial forging cogging process. The forging heating temperature range is 1110 ℃. The open forging temperature is 1050 ℃, and the finish forging temperature is 860 ℃. Obtaining the section size: 140 (+ 5, -7) X140 (+ 5, -7) mm 2 (ii) a Length: 8300mm rolled blank.
4) Wire rod rolling
And putting the rolled blank into a heating furnace of a wire rolling production line. The temperature of the soaking section of the heating furnace is controlled at 1110 +/-10 ℃, and tapping and rolling are carried out after the temperature of the soaking section reaches 45 minutes. The rolling speed is 20m/s, and the finishing temperature is 930 ℃.
After subsequent solution heat treatment, the material has no overburning phenomenon and does not have massive Laves phase.
Example 2:
the nickel-saving Fe-Ni-Cr-based high-temperature alloy comprises the following components in percentage by mass: 0.075% of C, 0.20% of Mn, 15.16% of Cr, 0.42% of Mo, 1.72% of Al, 2.05% of Ti, 0.47% of Nb, 0.05% of V, 27.40% of Ni, 0.003% of B, 0.007% of Zr, 0.002% of S, 0.015% of P and the balance of Fe and inevitable impurities. N is a radical of hydrogeni critical 11.82%, solidus temperature T Fixing device The temperature is 1187.69 ℃, and the precipitation temperature T of the Laves phase Lav The temperature was 910.39 ℃. The manufacturing process comprises the following steps: non-vacuum induction melting, electroslag remelting, forging and cogging, wire rolling, solid solution and bright silver processing.
1) Non-vacuum induction melting
Adopting non-vacuum induction melting, selecting slag charge proportion: caF is CaO 2 = 64. The amount of slag added is 16 kg/ton according to the specification of the non-vacuum induction furnace. The slag is covered early in the smelting process (within 10 minutes after melting), and the air suction is reduced. The white slag time must be greater than 15 minutes. Tapping temperature: 1550 ℃. And casting the electrode bar with the size of 360mm phi.
5) Electroslag remelting
And carrying out electroslag remelting on the electrode rod smelted by the non-vacuum induction furnace. Considering that the nickel-saving Fe-Ni-Cr-based high-temperature alloy contains high content of Ti element and is easy to lose, a quinary slag system CaF is selected 2 :Al 2 O 3 :CaO:MgO: TiO 2 10. The melting speed in the electroslag process is controlled to be 5.2kg/min. Obtaining an electroslag ingot with phi of 420 mm.
6) Forging and cogging
The electroslag ingot with the diameter of 420mm of the nickel-saving Fe-Ni-Cr-based high-temperature alloy is cogging by adopting a rapid radial forging combined cogging process or a direct radial forging cogging process. The forging heating temperature was 1100 ℃. The open forging temperature is 1050 ℃, and the finish forging temperature is 850 ℃. Obtaining the section size: 140 (+ 5, -7) x 140 (+ 5, -7) mm 2 (ii) a Length: 8500mm rolled blank.
7) Wire rod rolling
And putting the rolled blank into a heating furnace of a wire rolling production line. The temperature of the soaking section of the heating furnace is controlled to be 1110 +/-10 ℃, and after the temperature of the soaking section reaches the temperature, the temperature is preserved for 50 minutes, and then tapping and rolling are carried out. The rolling speed is 19.5m/s, and the finishing temperature is 920 ℃.
After subsequent solution heat treatment, the material has no overburning phenomenon and does not have massive Laves phase.
Example 3:
the nickel-saving Fe-Ni-Cr-based high-temperature alloy comprises the following components in percentage by mass: c0.080%0.35% of Mn, 15.75% of Cr, 0.70% of Mo, 1.85% of Al, 2.15% of Ti, 0.60% of Nb, 0.15% of V, 28.30% of Ni, 0.004% of B, 0.009% of Zr, 0.001% of S, 0.014% of P and the balance of Fe and inevitable impurities. Ni critical 18.50%, solidus temperature T Fixing device The temperature is 1167.14 ℃, and the Laves phase precipitation temperature T Lav The temperature was 954.18 ℃. The manufacturing process comprises the following steps: non-vacuum induction melting, electroslag remelting, forging and cogging, wire rolling, solid solution and bright silver processing.
1) Non-vacuum induction melting
Adopting non-vacuum induction melting, selecting slag charge proportion: caF is CaO 2 = 65. The amount of slag added is 16 kg/ton according to the specification of the non-vacuum induction furnace. The slag is covered early in the smelting process, and the air suction is reduced. The white slag time must be greater than 15 minutes. Tapping temperature: 1550 ℃. And casting the electrode bar with the size of 360mm phi.
8) Electroslag remelting
And carrying out electroslag remelting on the electrode rod smelted by the non-vacuum induction furnace. Considering that the nickel-saving Fe-Ni-Cr-based high-temperature alloy contains high content of Ti element and is easy to lose, a five-element slag system CaF is selected 2 :Al 2 O 3 :CaO:MgO: TiO 2 10. The melting speed in the electroslag process is controlled to be 5.1kg/min. Obtaining an electroslag ingot with the diameter of 420 mm.
9) Forging and cogging
The electroslag ingot with the diameter of 420mm of the nickel-saving Fe-Ni-Cr-based high-temperature alloy is cogging by adopting a rapid radial forging combined cogging process or a direct radial forging cogging process. The forging heating temperature was 1110 ℃. The open forging temperature is 1050 ℃, and the finish forging temperature is 850 ℃. Obtaining the section size: 140 (+ 5, -7) X140 (+ 5, -7) mm 2 (ii) a Length: 8500mm billet.
10 ) wire rod rolling
And putting the rolled blank into a heating furnace of a wire rolling production line. The temperature of the soaking section of the heating furnace is controlled to be 1110 +/-10 ℃, and after the temperature of the soaking section reaches the temperature, the temperature is kept for 45 minutes, and then tapping and rolling are carried out. The rolling speed is 20m/s, and the finishing temperature is 930 ℃.
After subsequent solution heat treatment, the material has no overburning phenomenon and does not have massive Laves phase.
Example 4:
the nickel-saving Fe-Ni-Cr-based high-temperature alloy comprises the following components in percentage by mass: 0.085 percent of C, 0.40 percent of Mn, 15.60 percent of Cr, 0.50 percent of Mo, 1.80 percent of Al, 2.10 percent of Ti, 0.50 percent of Nb, 0.15 percent of V, 28.00 percent of Ni, 0.005 percent of B, 0.008 percent of Zr, 0.001 percent of S, 0.015 percent of P and the balance of Fe and inevitable impurities. Ni critical 13.56% solidus temperature T Fixing device At 1188.01 deg.C, and a Laves phase precipitation temperature T Lav The temperature was 898.41 ℃. The manufacturing process comprises the following steps: non-vacuum induction melting, electroslag remelting, forging and cogging, wire rolling, solid solution and bright silver processing.
1) Non-vacuum induction melting
Adopting non-vacuum induction melting, selecting slag charge proportioning: caF is CaO 2 = 64. The amount of slag added is 16 kg/ton according to the specification of the non-vacuum induction furnace. The slag is covered early in the smelting process (within 9 minutes after melting), and air suction is reduced. The white slag time must be greater than 15 minutes. Tapping temperature: 1552 deg.C. And casting the electrode bar with the size of 360mm phi.
2) Electroslag remelting
And carrying out electroslag remelting on the electrode rod smelted by the non-vacuum induction furnace. Considering that the nickel-saving Fe-Ni-Cr-based high-temperature alloy contains high content of Ti element and is easy to lose, a five-element slag system CaF is selected 2 :Al 2 O 3 :CaO:MgO: TiO 2 = 21.5. The melting speed in the electroslag process is controlled to be 5.0kg/min. Thus obtaining an electroslag ingot with the diameter phi of 425 mm.
3) Forging and cogging
The electroslag ingot with the diameter of 425mm of the nickel-saving Fe-Ni-Cr-based high-temperature alloy is cogging by adopting a rapid radial forging combined cogging process or a direct radial forging cogging process. The forging heating temperature was 1110 ℃. The open forging temperature is 1050 ℃, and the finish forging temperature is 850 ℃. Obtaining the section size: 140 (+ 5, -7) X140 (+ 5, -7) mm 2 (ii) a Length: 8600 mm.
4) Wire rod rolling
And putting the rolled blank into a heating furnace of a wire rod rolling production line. The temperature of the soaking section of the heating furnace is controlled to be 1110 +/-20 ℃, and after the temperature of the soaking section reaches the temperature, the temperature is kept for 50 minutes, and then tapping and rolling are carried out. The rolling speed is 20.5m/s, and the finishing temperature is 925 ℃.
After the subsequent solution heat treatment, the material has no overburning phenomenon and does not have a massive Laves phase.
The results of the high temperature transient tensile properties and the durability properties obtained are shown in Table 1. The alloy has the advantages that the strength and the plasticity of the alloy are not obviously changed between room temperature and 650 ℃, the strength is obviously reduced and the plasticity is obviously improved after the temperature exceeds 700 ℃, and even the superplasticity phenomenon exists at higher temperature. The endurance of the alloy is improved significantly with the duration of the reduction of the stress. Generally, the high-temperature performance of the nickel-saving Fe-Ni-Cr-based high-temperature alloy manufactured by the invention is superior to that of nickel-based alloys Inconel751 and NiCr20TiAl.
The nickel-saving Fe-Ni-Cr-based high-temperature alloy manufactured by the invention has better high-temperature performance than that of nickel-based alloys Inconel751 and NiCr20TiAl, and has unobvious strength and plasticity change at room temperature to 650 ℃, so that the nickel-saving Fe-Ni-Cr-based high-temperature alloy can replace the nickel-based alloys Inconel751 and NiCr20TiAl to produce engine valves, thereby reducing the cost.
Claims (7)
1. A nickel-saving iron-based high-temperature alloy for engine valves is characterized in that: the nickel-saving iron-based high-temperature alloy is a nickel-saving Fe-Ni-Cr-based high-temperature alloy and comprises the following components in percentage by mass: c:0.071-0.092%, mn:0.18-0.50%, cr:15.15-15.99%, mo:0.4-1.0%, al:1.69-2.00%, ti:2.00-2.19%, nb:0.45-0.75%, V is less than or equal to 0.3%, ni:27.35-29.98%, B:0.002-0.007%, zr:0.005-0.013%, S is less than or equal to 0.02%, P is less than or equal to 0.02%, and the balance of Fe and inevitable impurities;
wherein the contents of C, cr, mo, al, ti and Nb meet the following requirements:
Ni critical =10×(-7.85-15.7×C%+0.285×Cr%-0.003×Mo%-0.258×Al%+3.05×Ti%+2.25×Nb%) 1.584 less than or equal to 25.0 percent; the solidus temperature of the high-temperature alloy material is 1160-1178 ℃, the initial precipitation temperature of the Laves phase is 930-946 ℃, and the nickel-saving iron-based high-temperature alloy for the engine valveThe preparation method of gold comprises the following steps: non-vacuum induction melting, electroslag remelting, forging and cogging, wire rolling, solid solution and bright silver processing.
2. The method for producing a nickel-saving iron-based superalloy for an engine valve according to claim 1, wherein the method comprises:
the method comprises the following steps: non-vacuum induction melting, electroslag remelting, forging and cogging, wire rolling, solid solution and bright silver processing;
1) Non-vacuum induction melting
Adopting non-vacuum induction melting, selecting slag charge proportion: caF is CaO 2 30-40; the white slag time is more than 15 minutes; tapping temperature: casting an electrode bar at 1530-1590 ℃;
2) Electroslag remelting
Carrying out electroslag remelting on the electrode rod smelted by the non-vacuum induction furnace; selecting five-element slag system CaF 2 :Al 2 O 3 :CaO:MgO: TiO 2 15-25; the melting speed in the electroslag process is controlled to be 3.0-6.0kg/min; obtaining an electroslag ingot;
3) Forging and cogging
Cogging the electroslag ingot by adopting a rapid radial forging combined cogging process or a direct radial forging cogging process, wherein the forging temperature range is 1100-1140 ℃; the open forging temperature is more than or equal to 1000 ℃, the finish forging temperature is more than or equal to 850 ℃ to obtain a rolled blank;
4) Wire rod rolling
Putting the rolled blank into a heating furnace of a wire rolling production line; controlling the temperature of a soaking section of the heating furnace at 1110 +/-10 ℃, and tapping and rolling after the temperature of the soaking section reaches the temperature; the finishing temperature is less than or equal to 950 ℃.
3. The method for manufacturing a nickel-saving iron-based high-temperature alloy for an engine valve according to claim 2, wherein: in the step 1), the amount of slag is added according to the specification of the non-vacuum induction furnace, and the range is 10-20 kg/ton.
4. The method for manufacturing the nickel-saving iron-based superalloy for an engine valve according to claim 2, wherein the method comprises: step 3) said rollingThe section size of the blank: 140-160 (+ 5, -7). Times.140-160 (+ 5, -7) mm 2 (ii) a Length: 8000-10000 mm.
5. The method for manufacturing the nickel-saving iron-based superalloy for an engine valve according to claim 2, wherein the method comprises: and 4) keeping the temperature for 30-70 minutes.
6. The method for manufacturing the nickel-saving iron-based superalloy for an engine valve according to claim 5, wherein the method comprises: and 4) preserving the heat for 40-60 minutes.
7. The method for manufacturing a nickel-saving iron-based high-temperature alloy for an engine valve according to claim 2, wherein: and 4) the rolling speed is less than or equal to 23m/s.
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| CN103451559A (en) * | 2012-05-31 | 2013-12-18 | 宝钢特种材料有限公司 | Gas valve alloy material and manufacturing method thereof |
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| JP4163055B2 (en) * | 2003-06-24 | 2008-10-08 | 日本精線株式会社 | Stainless steel wire for heat-resistant springs and heat-resistant spring products using the same |
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| CN101784687A (en) * | 2007-10-03 | 2010-07-21 | 住友金属工业株式会社 | Austenitic stainless steel |
| CN103014551A (en) * | 2011-09-22 | 2013-04-03 | 兴化市新迅达不锈钢标准件有限公司 | Novel high-temperature alloy heat-resistant stainless steel bolt and production process thereof |
| CN103451559A (en) * | 2012-05-31 | 2013-12-18 | 宝钢特种材料有限公司 | Gas valve alloy material and manufacturing method thereof |
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