CN111118350B - Ce-Mg-N composite treated GH4065 nickel-based high-temperature alloy and preparation process thereof - Google Patents
Ce-Mg-N composite treated GH4065 nickel-based high-temperature alloy and preparation process thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 100
- 239000000956 alloy Substances 0.000 title claims abstract description 100
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- 230000001681 protective effect Effects 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 230000006698 induction Effects 0.000 claims abstract description 19
- 238000003723 Smelting Methods 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 239000010936 titanium Substances 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 239000002893 slag Substances 0.000 claims description 18
- 239000011777 magnesium Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 238000005242 forging Methods 0.000 claims description 12
- 239000010955 niobium Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910000601 superalloy Inorganic materials 0.000 claims description 8
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 4
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 16
- 230000004584 weight gain Effects 0.000 abstract description 5
- 235000019786 weight gain Nutrition 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 2
- 239000000306 component Substances 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 15
- 238000005260 corrosion Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 238000005275 alloying Methods 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
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- 238000005728 strengthening Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
Abstract
The invention relates to the technical field of metal materials, in particular to a GH4065 nickel-based high-temperature alloy subjected to Ce-Mg-N composite treatment and a preparation process thereof. The alloy comprises the following components in percentage by mass: less than or equal to 0.02%, Co: 12.80% -13.20%, Cr: 15.80% -16.20%, W: 3.80% -4.20%, Mo: 3.80-4.20%, Al: 2.20% -2.40%, Ti: 3.80% -4.00%, Nb: 0.60-0.80%, Fe: 0.90% -1.10%, Ce: 0.005-0.03%, Mg: 0.002% -0.006%, N: 0.1 to 0.4 percent of Ni and a small amount of impurity elements such as O, S and the like. The preparation process of the alloy comprises a vacuum induction furnace and N2Smelting in a protective atmosphere electroslag remelting furnace, and then performing thermal processing and heat treatment. Compared with the common GH4065 alloy, the GH4065 alloy prepared by the Ce-Mg-N composite treatment through the process has the advantages that the oxidation weight gain rate is obviously reduced under the high-temperature condition, the oxidation resistance is obviously improved, in addition, the high-temperature tensile strength and the yield strength are also improved to a certain degree, and the advantages are more obvious when the temperature is relatively high.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a GH4065 nickel-based high-temperature alloy subjected to Ce-Mg-N composite treatment and a preparation process thereof.
Background
The turbine disk is one of the core components of an aircraft engine, and the performance level of the turbine disk plays a decisive role in improving the reliability, the service life and the like of the engine. With the continuous improvement of the thrust-weight ratio of the advanced aircraft turbine engine, the requirements on the temperature bearing capacity and the mechanical property of key hot end rotating parts such as a deformed high-temperature alloy turbine disc, a high-pressure compressor disc and the like are improved, and the service temperature is increased from 650 ℃ to 700 ℃ and even more than 750 ℃. The maximum service temperature of the traditional wrought superalloy IN718 with the largest consumption of turbine disks at home and abroad is 650 ℃, and the service temperature of the next generation IN718Plus alloy is close to 700 ℃. For the aeroengine turbine disc with the service temperature of above 700 ℃, the aeroengine turbine disc is generally prepared by a high-cost powder metallurgy process, mainly because the improvement of the performance of the deformed high-temperature alloy is mainly caused by the improvement of the alloying degree, and the segregation of the alloy elements of the cast ingot is aggravated, and the hot workability is deteriorated.
In recent years, with the continuous improvement of the smelting process, the hot working technology and the large-scale equipment capability of the high-temperature alloy, the capability of preparing the high-alloying deformation high-temperature alloy by adopting the casting and forging process at home and abroad is greatly improved, for example, the service temperature of Ren é 65 alloy of American ATI company can reach 740 ℃, and the high-alloying deformation high-temperature alloy is applied to key components such as turbine disks, compressor disks and the like of new generation LEAP series aeroengines. The GH4065 alloy developed in recent years in China has the use temperature of 750 ℃, has the performance equivalent to that of a second generation powder disk Ren 88DT, and is regarded as a deformed turbine disk material which is mainly developed in the future in China, but if the working temperature is further increased to be more than 800 ℃, the working environment of the turbine disk is more complicated, the requirements on the aspects of high-temperature mechanical property, oxidation resistance, corrosion resistance and the like are correspondingly improved, and the conventional GH4065 alloy cannot meet the requirements.
The Ce element has active chemical property, is very easy to combine with O, S element in the alloy after being added into the high-temperature alloy, has very strong deoxidation and desulfurization effects, simultaneously, a proper amount of the Ce element can deteriorate the variety of inclusions in the alloy, improve the distribution of the inclusions and reduce the harm of the inclusions, and in addition, the Ce element can play a role in alloying when being dissolved into the alloy, and has different degrees of influences on the aspects of mechanical property, oxidation resistance, corrosion resistance and the like of the high-temperature alloy.
The Mg element has similar action effect with the Ce element and also has very strong effects of deoxidation, desulfurization and inclusion modification, and in addition, researches show that the Mg element can also improve the hot workability of the high-temperature alloy and improve the creep resistance of the high-temperature alloy.
The N element can obviously improve the corrosion resistance of the alloy, particularly the local corrosion resistance, such as intergranular corrosion resistance, pitting corrosion resistance, crevice corrosion resistance and the like, can also form AlN and TiN with Al and Ti elements in the high-temperature alloy, and has good strengthening effect on the high-temperature performance of the alloy if the size and the distribution of the nitride can be controlled.
Disclosure of Invention
The invention aims to provide a GH4065 alloy subjected to Ce-Mg-N composite treatment and a preparation process thereof, and by means of the characteristics of elements Ce, Mg and N, the high-temperature mechanical property, the oxidation resistance, the corrosion resistance and the like of the GH4065 alloy are further improved, so that the use temperature of the GH4065 alloy is increased, and the use field of the GH4065 alloy is expanded.
In order to achieve the purpose, the invention adopts the following technical scheme:
(1) on the basis of GH4065 alloy, redesigned composition. Specifically, Ce, Mg and N are added into the alloy, and the content of Al and Ti in the alloy is adjusted.
The high-temperature alloy has the following characteristics:
the alloy elements comprise C, Co, Cr, W, Mo, Al, Ti, Nb, Fe, Ce, Mg, N, Ni and the like.
According to mass percent, C: less than or equal to 0.02%, Co: 12.80% -13.20%, Cr: 15.80% -16.20%, W: 3.80% -4.20%, Mo: 3.80-4.20%, Al: 2.20% -2.40%, Ti: 3.80% -4.00%, Nb: 0.60-0.80%, Fe: 0.90% -1.10%, Ce: 0.005-0.03%, Mg: 0.002% -0.006%, N: 0.1 to 0.4 percent of Ni and a small amount of impurity elements such as O, S and the like.
The effect of the element Ce in the alloy is firstly deoxidation, desulfurization and deterioration of the inclusion, if the adding amount is too small, the effect of the element Ce cannot be reflected, if the adding amount is too large, the size of the inclusion is obviously increased, and the excessive element Ce also cannot be completely dissolved in the alloy, which is equivalent to the introduction of foreign inclusion, so that the performance of the alloy is deteriorated. Meanwhile, a proper amount of Ce element can improve the density and the adhesiveness of the oxide film on the surface of the alloy and prevent the oxide film from peeling off,further, the oxidation resistance of the alloy is improved, but if the element Ce is excessive, the oxidation resistance of the alloy deteriorates and the oxidation weight gain rate of the alloy increases. In addition, after the Ce element is added, the Ce element is easy to be partially gathered at the position of a grain boundary in the solidification process of the alloy, so that the function of pinning the grain boundary is achieved, the high-temperature mechanical property of the high-temperature alloy is enhanced, and the difficulty of hot working of the high-temperature alloy is also influenced. When the hot working temperature is lower, the pinning effect is more obvious, so can increase the degree of difficulty of hot working to a certain extent, when the hot working temperature is higher, Ce atomic kinetic energy increases, and thermal vibration aggravates, weakens the pinning effect to the grain boundary, so can weaken to hot workability's influence. Specifically, the content of Ce element can be-0.003%<wCe-T.O×280/48<0.005 percent, and considering the fluctuation of the content range of T.O in the alloy, the content range of Ce element can be controlled between 0.005 percent and 0.03 percent.
The Mg element has the similar action to Ce in the alloy, and is mainly used for deoxidation, desulfurization and modification of inclusions. In addition, Mg element is dissolved in the alloy in a solid way, and the creep resistance and the hot working plasticity of the high-temperature alloy can be improved. Specifically, the content of Mg element can be controlled within the range of 0.002% -0.006%.
N element has been widely recognized as a harmful element in the past, so the content of N in the nickel-base superalloy is generally controlled to be less than 0.05%, so that the mechanical properties and the processability of the alloy are prevented from being adversely affected by precipitated nitrides. However, a great deal of research in recent years has revealed that when N is added as an alloying element and the N content of the alloy is controlled to a relatively high level, a large amount of nitrides distributed uniformly and dispersedly are likely to be produced, and these nitrides can avoid excessive growth of alloy grains, which is advantageous for improving the mechanical properties of the alloy. In addition, the N element can obviously improve the corrosion resistance of the alloy, particularly the local corrosion resistance, such as intergranular corrosion resistance, pitting corrosion resistance, crevice corrosion resistance and the like. Specifically, the content of the N element in the alloy can be controlled within the range of 0.1-0.4%.
In addition, after 0.1-0.4% of N element is added into the GH4065 alloy, part of Al and Ti elements can be combined with the N element to form uniformly dispersed nitride, so that the high-temperature performance of the alloy is further improved, and therefore, compared with the common GH4065 alloy, the content of the Al and Ti elements in the invention also needs to be correspondingly adjusted. Specifically, the content of Al element can be controlled within the range of 2.20-2.40%, and the content of Ti element can be controlled within the range of 3.80-4.00%.
(2) Aiming at the GH4065 alloy with the adjusted components, the preparation process is designed.
The preparation process of the invention has the whole process route of vacuum induction furnace + N2Smelting in a protective atmosphere electroslag remelting furnace, and then carrying out hot working and heat treatment on an electroslag remelted ingot, wherein the method specifically comprises the following steps:
step 1, vacuum induction furnace melting
1) Charging: adding metal cobalt, metal chromium, metal tungsten, metal molybdenum, metal niobium, industrial pure iron and a metal nickel plate into a crucible according to the alloy component ratio; graphite, metallic aluminum, metallic titanium and chromium nitride (Cr) are sequentially added into an external stock bin2N), rare earth magnesium alloy (according to mass percent: ce: 20% -50%, Mg: 5-30 percent of Ni and a small amount of impurity elements);
2) opening a power supply and a vacuum valve, and vacuumizing to less than or equal to 3Pa (so as to reduce air suction during heating of the furnace burden);
3) heating by power supply, closing the vacuum pump and introducing N2When the pressure reaches 20kPa, the melting period is carried out, no specific time requirement exists in the melting period, the furnace burden is ensured to be fully melted, the furnace burden is heated to be red at a lower power at the beginning, and then the furnace burden is heated and melted as soon as possible by using the maximum power under a certain vacuum degree;
4) after melting down, opening a vacuum pump, vacuumizing to below 10Pa, and refining for 20 min;
5) the vacuum pump is turned off and N is charged2Adding graphite, metal aluminum, metal titanium and chromium nitride into the bin when the pressure is 10 kPa;
6) deep thermocouple temperature measurement, power adjustment, adding rare earth magnesium alloy when the temperature reaches 1500-1550 ℃, and heat preservation for 5 min;
7) and (6) pouring.
Step 2, N2Smelting in electroslag remelting furnace under protective atmosphere
1) Preparing slag charge: according to mass percent, CaF2：45％～55％，Al2O3：15％～25％，CaO：8％～12％，Ce2O3：8％～12％，MgO：4％～6％，TiO2: 4% -6%, Al powder: 0.04-0.06 percent, and the mass ratio of the slag charge to the alloy is 1: 10. It can be seen that the slag composition in the invention is greatly different from the slag composition of a common electroslag furnace. Firstly, 8 to 12 percent of Ce is added into slag charge2O34 to 6 percent of MgO and 4 to 6 percent of TiO2The main consideration is that Ce, Mg and Ti are active in chemical property, high in saturated vapor pressure and easy to oxidize and burn in the electroslag remelting process. In addition, the invention leads 0.04 to 0.06 percent of Al in the slag charge2O3The Al powder is replaced by the Al powder and has two main functions, on one hand, the Al powder is used as a deoxidizer to remove oxygen brought in during slag adding so as to ensure the purity of the alloy, and on the other hand, the Al powder can emit a large amount of heat during oxidation reaction so as to be beneficial to rapidly melting slag, so that the slag and the alloy are separated thoroughly in the initial stage of electroslag remelting, the quality of the bottom of an electroslag ingot is ensured, and the production rhythm can be accelerated.
2) Consumable electrode preparation: firstly, cutting off a central shrinkage cavity at the end part of a vacuum induction melting cast ingot, then carrying out homogenization treatment on the cast ingot at high temperature, and then forging the cast ingot by using a quick forging machine so as to eliminate the defects of loose shrinkage cavity and the like in the cast ingot and further ensure the quality of a consumable electrode.
3) Vacuumizing: before remelting starts, the protective cover of the electroslag remelting furnace needs to be sealed, then the protective cover is vacuumized to be less than or equal to 3Pa, so that the burning loss of alloy elements such as Ce, Mg, Ti and the like caused by the reaction of oxygen in the protective cover and alloy in the remelting process is avoided, and oxide inclusions in the ingot are increased.
4) Charging N2: after the vacuum pumping is finished, filling high-purity N into the protective cover2，N2The pressure is controlled to be about 0.1 MPa. Is charged into N2Is mainly composed ofThe purpose is to prevent the loss of dissolved nitrogen element in the alloy after remelting, further protect the alloy liquid and prevent the residual oxygen in the protective cover from influencing the alloy components.
5) Remelting: the remelting process is basically consistent with the remelting process of the common GH4065 alloy.
It is to be noted that the smelting process of the invention adopts a vacuum induction furnace + N2The smelting in the protective atmosphere electroslag remelting furnace is different from the smelting in a common vacuum induction furnace, an electroslag remelting furnace and a vacuum consumable electrode furnace, and is mainly based on the following considerations.
Firstly, the saturated vapor pressure of Ce, Mg and N elements is very high, and the elements are very easy to enter gas phase under the vacuum condition, so that the alloy described in the patent is not suitable to be smelted by adopting a vacuum consumable furnace, but N is used2The electroslag remelting in the protective atmosphere is used as the final smelting process, and part of Ce is added into the remelting slag2O3、MgO。
In addition, for the smelting process of the vacuum induction furnace, the electroslag remelting furnace and the vacuum consumable electrode furnace, the vacuum induction furnace mainly has the function of producing ingots with the content of alloy elements meeting the requirement, the electroslag remelting furnace mainly has the function of removing harmful impurity elements and non-metallic inclusions in metal and purifying the metal to obtain ingots with uniform and compact solidification structures, the vacuum consumable electrode furnace mainly has the function of removing gas elements such as O, H, N and the like and certain volatile impurity elements in the metal, meanwhile, the other reason for selecting the vacuum consumable electrode furnace is that the ingot defects of the vacuum induction furnace are more, and when the vacuum consumable electrode furnace is directly used as a consumable electrode for electroslag remelting, the process fluctuation is larger, and the defects are easy to appear. However, in N2In the protective atmosphere electroslag remelting process, the gas phase partial pressure of gas elements such as H, O and other volatile impurity elements except N is approximately 0, so that the gas elements can be effectively removed, and the main function of the vacuum consumable electrode furnace is played. As for the problem of large process fluctuation when a vacuum induction furnace ingot is directly used as a consumable electrode for electroslag remelting, the central shrinkage cavity of the ingot is cut off, then the ingot is subjected to homogenization treatment at high temperature, and then a quick forging machine is used for forging to eliminate the loose shrinkage cavity in the ingot, so that the loose shrinkage cavity is removedHigh ingot quality.
Finally, vacuum induction furnace + N2Compared with the smelting of a vacuum induction furnace, an electroslag remelting furnace and a vacuum consumable electrode furnace, the smelting of the protective atmosphere electroslag remelting furnace obviously reduces the production cost.
Step 3, hot working and heat treatment
In the patent, the hot working and heat treatment process of the GH4065 alloy after the Ce-Mg-N composite treatment is not particularly required, and the hot working and heat treatment process commonly used for the GH4065 alloy can be directly adopted. Namely homogenizing at high temperature, forging and cogging, and then performing standard heat treatment (1080 ℃ multiplied by 4h, air cooling, 760 ℃ multiplied by 8h, air cooling).
Detailed Description
The following examples are given to illustrate specific embodiments of the present invention, but the present invention is not limited to the following examples.
Example 1
The GH4065 alloy of the embodiment is not treated with Ce-Mg-N, and the contents of Al and Ti elements are not adjusted, mainly serving as a control experiment. The chemical components of the material comprise the following components in percentage by mass: c: less than or equal to 0.02%, Co: 12.80% -13.20%, Cr: 15.80% -16.20%, W: 3.80% -4.20%, Mo: 3.80-4.20%, Al: 2.00% -2.20%, Ti: 3.60% -3.80%, Nb: 0.60-0.80%, Fe: 0.90 to 1.10 percent of Ni and the balance of Ni.
The preparation method of example 1 comprises the following steps:
(1) vacuum induction furnace melting
1) Charging: adding metal cobalt, metal chromium, metal tungsten, metal molybdenum, metal niobium, industrial pure iron and metal nickel plates into a crucible according to the alloy component ratio in the embodiment 1; graphite, metallic aluminum and metallic titanium are sequentially added into an external bin.
2) Opening a power supply and a vacuum valve, and vacuumizing to less than or equal to 3 Pa;
3) heating by electricity, closing the vacuum pump, introducing Ar to 20kPa, and entering a melting period;
4) after melting down, opening a vacuum pump, vacuumizing to below 10Pa, and refining for 20 min;
5) closing the vacuum pump, charging Ar to 10kPa, and adding graphite, metal aluminum and metal titanium in the storage bin;
6) measuring the temperature, adjusting the power, and keeping the temperature for 5min when the temperature reaches 1500-1550 ℃;
7) and (6) pouring.
(2) Melting in Ar protective atmosphere electroslag remelting furnace
1) Preparing slag charge: according to mass percent, CaF2：59％，Al2O3：23.95％，CaO：12％，Ce2O3：0，MgO：0，TiO2: 5%, Al powder: 0.05 percent, and the mass ratio of the slag to the alloy is 1: 10.
2) Consumable electrode preparation: and cutting off the central shrinkage cavity at the end part of the vacuum induction melting cast ingot, and homogenizing and forging the cast ingot.
3) Vacuumizing: before remelting, sealing the protective cover of the electroslag remelting furnace, and vacuumizing to less than or equal to 3 Pa.
4) And (3) Ar filling: after the vacuum pumping is finished, high-purity Ar is filled into the protective cover, and the Ar pressure is controlled to be 0.1 MPa.
5) Remelting: the remelting process is basically consistent with the remelting process of the common GH4065 alloy.
(3) Hot working and heat treatment
Adopting the common hot processing and heat treatment process of GH4065 alloy, namely homogenizing at high temperature, forging and cogging, and then performing standard heat treatment (1080 ℃ for 4h, air cooling, 760 ℃ for 8h, air cooling).
It should be noted that, since this example is a control experiment and the addition of Ce, Mg and N elements needs to be avoided, the protective gas introduced during the melting process of the vacuum induction furnace and the electroslag remelting furnace is not N2And is Ar. In addition, Ce in electroslag remelting slag2O3And the addition of MgO is set to be 0, and the addition of the main components in the slag is increased in proportion.
Example 2
The GH4065 alloy of this example was Ce-Mg-N treated and the contents of Al and Ti elements were adjusted. The chemical components of the material comprise the following components in percentage by mass: c: less than or equal to 0.02%, Co: 12.80% -13.20%, Cr: 15.80% -16.20%, W: 3.80% -4.20%, Mo: 3.80-4.20%, Al: 2.20% -2.40%, Ti: 3.80% -4.00%, Nb: 0.60-0.80%, Fe: 0.90% -1.10%, Ce: 0.005-0.015%, Mg: 0.002% -0.004%, N: 0.1 to 0.25 percent of Ni and the balance of Ni.
The preparation method of example 2 comprises the following steps:
(1) vacuum induction furnace melting
1) Charging: adding metal cobalt, metal chromium, metal tungsten, metal molybdenum, metal niobium, industrial pure iron and metal nickel plates into a crucible according to the alloy component ratio in the embodiment 2; graphite, metallic aluminum, metallic titanium and chromium nitride (Cr) are sequentially added into an external stock bin2N), rare earth magnesium alloy (according to mass percent: ce: 40%, Mg: 20%, Ni: 40%).
2) Opening a power supply and a vacuum valve, and vacuumizing to less than or equal to 3 Pa;
3) heating by power supply, closing the vacuum pump and introducing N2Reaching 20kPa, entering a melting period;
4) after melting down, opening a vacuum pump, vacuumizing to below 10Pa, and refining for 20 min;
5) the vacuum pump is turned off and N is charged2Adding graphite, metal aluminum, metal titanium and chromium nitride into the bin when the pressure is 10 kPa;
6) measuring the temperature, adjusting the power, adding the rare earth magnesium alloy when the temperature reaches 1500-1550 ℃, and keeping the temperature for 5 min;
7) and (6) pouring.
(2)N2Smelting in electroslag remelting furnace under protective atmosphere
1) Preparing slag charge: according to mass percent, CaF2：50％，Al2O3：19.95％，CaO：10％，Ce2O3：10％，MgO：5％，TiO2: 5%, Al powder: 0.05 percent, and the mass ratio of the slag to the alloy is 1: 10.
2) Consumable electrode preparation: and cutting off the central shrinkage cavity at the end part of the vacuum induction melting cast ingot, and homogenizing and forging the cast ingot.
3) Vacuumizing: before remelting, sealing the protective cover of the electroslag remelting furnace, and vacuumizing to less than or equal to 3 Pa.
4) Charging N2: after the vacuum pumping is finished, filling high-purity N into the protective cover2，N2The pressure is controlled at 0.1 MPa.
5) Remelting: the remelting process is basically consistent with the remelting process of the common GH4065 alloy.
(3) Hot working and heat treatment
Adopting the common hot processing and heat treatment process of GH4065 alloy, namely homogenizing at high temperature, forging and cogging, and then performing standard heat treatment (1080 ℃ for 4h, air cooling, 760 ℃ for 8h, air cooling).
Example 3
The GH4065 alloy of this example was Ce-Mg-N treated and the contents of Al and Ti elements were adjusted. The chemical components of the material comprise the following components in percentage by mass: c: less than or equal to 0.02%, Co: 12.80% -13.20%, Cr: 15.80% -16.20%, W: 3.80% -4.20%, Mo: 3.80-4.20%, Al: 2.20% -2.40%, Ti: 3.80% -4.00%, Nb: 0.60-0.80%, Fe: 0.90% -1.10%, Ce: 0.015% -0.025%, Mg: 0.004-0.006%, N: 0.25 to 0.4 percent of Ni and the balance of Ni.
The preparation process of example 3 is completely identical to that of example 2.
The specific components of the samples obtained in examples 1 to 3 were measured, and the results are shown in Table 1.
TABLE 1 specific components (wt,%) of the samples obtained in examples 1 to 3
High temperature oxidation is a type of metal corrosion caused by the reaction of a metal material with oxygen at high temperatures to form an oxide. Under the condition of high temperature, the alloy has higher oxidation resistance only by generating a complete and compact oxide film with good adhesion with a matrix on the surface. The service temperature of the GH4065 alloy is 750 ℃ or even higher, so the oxidation resistance at the service temperature is one of the important performance indexes. In view of the above, the patent tests the static oxidation behavior of the samples obtained in examples 1 to 3 at 700 ℃ to 850 ℃ according to HB5228-2000, detects the oxidation condition of the samples by a weight gain method, takes 3 parallel samples from each group of samples and calculates the average value thereof, and the final detection result is shown in Table 2.
TABLE 2 average oxidation weight gain (K, g.m) at 700 deg.C to 850 deg.C for the samples obtained in examples 1 to 3-2·h-1)
In addition, the patent tests the high-temperature tensile properties of the samples obtained in examples 1-3 at 750 ℃ and 800 ℃ according to GB/T4338-2006, 3 parallel samples are taken from each group of samples, the average value of the samples is calculated, and the final detection result is shown in Table 3.
TABLE 3 tensile Properties at 750 ℃ and 800 ℃ of the samples obtained in examples 1 to 3
The detection results in table 2 show that when the GH4065 alloy is compositely treated by Ce-Mg-N and the contents of Ce, Mg and N are controlled within a reasonable range, the oxidation weight gain rate of the alloy under high temperature conditions is significantly reduced, which indicates that the high temperature oxidation resistance of the alloy is significantly improved, mainly because a proper amount of Ce improves the density and adhesion of an oxide film on the surface of the alloy, and a proper amount of N improves the local corrosion resistance of the alloy.
The detection results in table 3 show that after a proper amount of Ce, Mg and N elements are added, the high-temperature tensile strength and yield strength of the alloy are improved to a certain extent, and the advantages are more obvious when the temperature is relatively high. The main reasons are that Ce element is eccentrically pinned at a crystal boundary, TiN and AlN are uniformly dispersed and precipitated, and Mg element improves the creep resistance and thermoplasticity of the alloy.
Claims (7)
1. A preparation process of GH4065 nickel-based high-temperature alloy subjected to Ce-Mg-N composite treatment is characterized by comprising the following steps of: the alloy comprises the following components in percentage by mass: less than or equal to 0.02%, Co: 12.80% -13.20%, Cr: 15.80% -16.20%, W: 3.80% -4.20%, Mo: 3.80-4.20%, Al: 2.20% -2.40%, Ti: 3.80% -4.00%, Nb: 0.60-0.80%, Fe: 0.90% -1.10%, Ce: 0.005-0.03%, Mg: 0.002% -0.006%, N: 0.1-0.4 percent, and the balance of Ni and a small amount of impurity elements such as O, S and the like;
the preparation process comprises the following steps:
(1) vacuum induction furnace melting
1) Charging: adding metal cobalt, metal chromium, metal tungsten, metal molybdenum, metal niobium, industrial pure iron and a metal nickel plate into a crucible according to the alloy component ratio; graphite, metal aluminum, metal titanium, chromium nitride and rare earth magnesium alloy are sequentially added into an external storage bin, wherein the rare earth magnesium alloy comprises the following components in percentage by mass: 20% -50%, Mg: 5-30 percent of Ni and a small amount of impurity elements;
2) opening a power supply and a vacuum valve, and vacuumizing to less than or equal to 3 Pa;
3) heating by electricity, closing the vacuum pump, introducing N2 to 20kPa, and entering a melting period;
4) after melting down, opening a vacuum pump, vacuumizing to below 10Pa, and refining for 20 min;
5) closing the vacuum pump, charging N2-10 kPa, and adding the graphite, the metal aluminum, the metal titanium and the chromium nitride in a storage bin;
6) measuring the temperature, adjusting the power, adding the rare earth magnesium alloy when the temperature reaches 1500-1550 ℃, and keeping the temperature for 5 min;
7) pouring;
(2) smelting in an electroslag remelting furnace under N2 protective atmosphere
1) Preparing slag charge: according to mass percent, CaF2：45％～55％，Al2O3：15％～25％，CaO：8％～12％，Ce2O3：8％～12％，MgO：4％～6％，TiO2: 4% -6%, Al powder: 0.04-0.06 percent, and the mass ratio of slag charge to alloyIs 1: 10;
2) consumable electrode preparation: cutting off a central shrinkage cavity at the end part of the vacuum induction melting cast ingot, and carrying out homogenization and forging treatment on the cast ingot;
3) vacuumizing: before remelting, sealing the protective cover of the electroslag remelting furnace, and vacuumizing to less than or equal to 3 Pa;
4) charging N2: after the vacuum pumping is finished, filling high-purity N into the protective cover2，N2The pressure is controlled to be about 0.1 MPa;
5) remelting: the remelting process is consistent with the remelting process of the common GH4065 alloy;
(3) hot working and heat treatment
Adopting the common hot processing and heat treatment process of GH4065 alloy, namely homogenizing at high temperature, forging and cogging, and then performing standard heat treatment, wherein the heat treatment conditions are 1080 ℃ multiplied by 4h, air cooling, 760 ℃ multiplied by 8h, and air cooling.
2. The preparation process of the Ce-Mg-N composite treated GH4065 nickel-base superalloy according to claim 1, wherein the preparation process comprises the following steps: the content of the Ce element is 0.005-0.015 percent.
3. The preparation process of the Ce-Mg-N composite treated GH4065 nickel-base superalloy according to claim 1, wherein the preparation process comprises the following steps: the content of the Ce element is 0.015-0.025 percent.
4. The preparation process of the Ce-Mg-N composite treated GH4065 nickel-base superalloy according to claim 1, wherein the preparation process comprises the following steps: the content range of the Mg element is 0.002% -0.004%.
5. The preparation process of the Ce-Mg-N composite treated GH4065 nickel-base superalloy according to claim 1, wherein the preparation process comprises the following steps: the content range of the Mg element is 0.004-0.006 percent.
6. The preparation process of the Ce-Mg-N composite treated GH4065 nickel-base superalloy according to claim 1, wherein the preparation process comprises the following steps: the content range of the N element is 0.1-0.25%.
7. The preparation process of the Ce-Mg-N composite treated GH4065 nickel-base superalloy according to claim 1, wherein the preparation process comprises the following steps: the content range of the N element is 0.25-0.4%.
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| CN1079995A (en) * | 1993-01-06 | 1993-12-29 | 冶金工业部钢铁研究总院 | Heat and corrosion resistant cast nickel-base alloy |
| CN105821250A (en) * | 2015-01-06 | 2016-08-03 | 宝钢特钢有限公司 | High-strength nickel-base superalloy and manufacturing method thereof |
| JP2016216805A (en) * | 2015-05-26 | 2016-12-22 | 新日鐵住金株式会社 | Austenitic heat resistant alloy and heat and pressure resistant member |
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| CN1079995A (en) * | 1993-01-06 | 1993-12-29 | 冶金工业部钢铁研究总院 | Heat and corrosion resistant cast nickel-base alloy |
| CN105821250A (en) * | 2015-01-06 | 2016-08-03 | 宝钢特钢有限公司 | High-strength nickel-base superalloy and manufacturing method thereof |
| JP2016216805A (en) * | 2015-05-26 | 2016-12-22 | 新日鐵住金株式会社 | Austenitic heat resistant alloy and heat and pressure resistant member |
| CN110337500A (en) * | 2017-02-21 | 2019-10-15 | 日立金属株式会社 | Ni base superalloy and its manufacturing method |
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