CN113355618A - Research method and application of trace element phosphorus in deformation high-temperature alloy - Google Patents
Research method and application of trace element phosphorus in deformation high-temperature alloy Download PDFInfo
- Publication number
- CN113355618A CN113355618A CN202110324887.XA CN202110324887A CN113355618A CN 113355618 A CN113355618 A CN 113355618A CN 202110324887 A CN202110324887 A CN 202110324887A CN 113355618 A CN113355618 A CN 113355618A
- Authority
- CN
- China
- Prior art keywords
- alloy
- phosphorus
- equal
- temperature
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 199
- 239000000956 alloy Substances 0.000 title claims abstract description 199
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 86
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000011574 phosphorus Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000011573 trace mineral Substances 0.000 title claims abstract description 22
- 235000013619 trace mineral Nutrition 0.000 title claims abstract description 22
- 238000011160 research Methods 0.000 title abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 230000009471 action Effects 0.000 claims abstract description 18
- 230000007246 mechanism Effects 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 10
- 230000003993 interaction Effects 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims description 39
- 229910000601 superalloy Inorganic materials 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910019589 Cr—Fe Inorganic materials 0.000 claims description 10
- 229910018487 Ni—Cr Inorganic materials 0.000 claims description 10
- 238000005242 forging Methods 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 230000010534 mechanism of action Effects 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 24
- 229910001096 P alloy Inorganic materials 0.000 description 17
- 230000032683 aging Effects 0.000 description 14
- 239000006104 solid solution Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 230000009286 beneficial effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 101000912561 Bos taurus Fibrinogen gamma-B chain Proteins 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229910001247 waspaloy Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- 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
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
-
- 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
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Abstract
The invention aims to provide a method for researching the action mechanism of trace element phosphorus in a deformed high-temperature alloy, which comprises the following steps: different alloy series are formed from simple to complex by changing the components of the deformed high-temperature alloy, different trace elements of phosphorus are added, the existence position and the existence mode of the phosphorus, the action relation between the main alloy element and the strengthened alloy element and the influence on the alloy structure are analyzed by adjusting the heat treatment process, and the influence on the alloy performance caused by the phosphorus element is evaluated, so that the existence mode of the phosphorus in the deformed high-temperature alloy, the interaction with each alloy element and the action mechanism are disclosed. According to the invention, through designing simplified alloy, raw materials are saved, labor cost is saved, and research efficiency is greatly improved.
Description
Technical Field
The invention belongs to the field of high-temperature alloys, and particularly provides a method for researching the action mechanism of trace element phosphorus in a deformed high-temperature alloy and application thereof.
Background
Phosphorus is one of the common trace elements in superalloys, and was earlier thought to be a detrimental element in the alloy. Until the seventies of the last century, people still have little knowledge of the effect of phosphorus in high-temperature alloys, and Bieber and Decker firstly carried out systematic research on the effect of trace elements in high-temperature alloys, and think that phosphorus is beneficial if less and harmful if more. However, they do not provide strong evidence to support this. Since then, researchers have developed studies on the beneficial effects of phosphorus in superalloys.
The beneficial effect of phosphorus in the wrought high-temperature alloy is acknowledged in the last 90 century, and the phosphorus can greatly improve the lasting creep property of some wrought high-temperature alloys, so that new wrought high-temperature alloys are invented at home and abroad. This beneficial effect of phosphorus has the following characteristics: firstly, the phosphorus has alloy selectivity on the beneficial effect of the lasting creep property of the high-temperature alloy; research shows that the lasting life of the phosphorus to the Ni-Cr-Fe base IN718 alloy with the most extensive application is obviously prolonged, and the phosphorus has similar beneficial effects to the IN706 alloy with similar components to the IN718 alloy and the iron base GH2761 alloy; however, the beneficial effects of the Ni-Cr based GH4133 and Ni-Cr-Co based Waspaloy alloys are extremely weak. Secondly, in the high-temperature alloy with beneficial effects added by phosphorus, an optimal content range is always existed, the endurance performance of the alloy reaches a peak value under the optimal phosphorus content, and the endurance life of the alloy is reduced due to the excessively high or low phosphorus content. It is also the interaction between phosphorus and other elements that directly affects the creep endurance properties of the alloy. Surrounding the presence of phosphorus in superalloysAnd the mechanism of action have not been stopped. A number of studies have demonstrated that phosphorus can segregate to grain boundaries in superalloys, and therefore early studies have suggested that the primary strengthening effect of phosphorus in superalloys comes from its effect on grain boundaries. Mainly expressed in that phosphorus can improve grain boundary precipitated phase such as M23C6Or M3B2The form and distribution of the crystal grains improve the bonding force of the crystal grain boundary and prevent oxygen in the environment from invading along the crystal grains.
Recently, we have found that P also affects the alloy intracrystalline structure, and P accelerates the precipitation of intracrystalline strengthening phases of IN706 alloy and IN718 alloy. However, since the composition and structure of the superalloy are quite complex, it is difficult to study the distribution and effect of P therein. So to date, there is no unified conclusion about the existence mode and action mechanism of P in wrought superalloy.
Disclosure of Invention
In order to solve the problems in the prior art, the invention designs a simplified nickel-based wrought superalloy series, and adds different contents of P, wherein the content of P is selected by referring to the research result of P in the complex alloy in the past. The existence form of P in the alloy is obtained by selecting the corresponding heat treatment process of the alloy components. And combining the structure analysis and the mechanical property test to obtain the precipitation mode of P in crystal boundaries and crystal interiors and the interaction with other elements, and disclosing the action mechanism of the P for improving the permanent creep property of the alloy in the deformed high-temperature alloy.
The technical scheme of the invention is as follows:
a method for researching the action mechanism of trace element phosphorus in a deformed high-temperature alloy is characterized in that: different alloy series are formed from simple to complex by changing the components of the deformed high-temperature alloy, different trace elements of phosphorus are added, the existence position and the existence mode of the phosphorus, the action relation between the main alloy element and the strengthened alloy element and the influence on the alloy structure are analyzed by adjusting the heat treatment process, and the influence on the alloy performance caused by the phosphorus element is evaluated, so that the existence mode of the phosphorus in the deformed high-temperature alloy, the interaction with each alloy element and the action mechanism are disclosed.
As a preferred technical scheme:
the wrought superalloy is a nickel-based wrought superalloy.
Different alloy series are formed from simple to complex, and the ranges of the alloy elements of the different alloy series are as follows by mass percent: 10.0-23.0% of Cr, 0-60% of Fe, 0-2.75% of Al, 0-3.6% of Ti, 0-5.50% of Nb, (Mo + W) 0-5.0%, 0-0.090% of P, 0-0.1% of C, 0-0.02% of B, less than or equal to 0.01% of Mg, less than or equal to 0.35% of Mn, less than or equal to 0.35% of Si, less than or equal to 0.015% of S, less than or equal to 0.30% of Cu, less than or equal to 0.01% of Ca, less than or equal to 1.0% of Co, less than or equal to 0.01% of N, less than or equal to 0.01% of O, and the balance of Ni.
Further, the method of the invention relates to two simple to complex alloy series, and the alloy series comprises the following elements:
the series is: Ni-Cr alloy, Cr 10.0-23.0%, Fe content less than or equal to 5%, and Ni in balance;
the series of the second step: Ni-Cr-Fe alloy, Cr 10.0-23.0%, Fe 5-60%, and Ni in balance.
The P element is added in the alloy series, and the content range of the P element in the alloy to be researched can be determined according to the early specific complex alloy research result.
The invention divides the alloy to be researched into two alloy series, namely Ni-Cr series and Ni-Cr-Fe series, in different alloy series, the research range of the previous P is referred, and the content range of the P element is properly enlarged and reduced in consideration of the requirement of simplifying the content of the P element of the alloy.
The heat treatment process of the wrought superalloy comprises the following steps:
heating temperature: 800-1190 ℃; heating time: less than or equal to 50 h;
a cooling mode: furnace cooling or cooling faster than furnace cooling.
The smelting process of the deformed high-temperature alloy comprises the following steps:
adding trace element P in the early stage of casting through intermediate alloy FeP and/or NiP;
adding 1% CaO for deoxidation in the melting period of the alloy without C;
the refining temperature of the alloy is 1500-1600 ℃;
the alloy casting temperature is 1400-1500 ℃.
The hot working process of the wrought superalloy comprises the following steps:
heating temperature: 1000 ℃ to 1170 ℃;
and (3) heat preservation time: the time is more than or equal to 4 hours;
open forging temperature: more than or equal to 1000 +/-10 ℃;
finish forging temperature: is higher than 900 ℃.
The method can be used for researching the action mechanism of improving the alloy creep resistance of phosphorus in the deformed high-temperature alloy.
Drawings
FIG. 1 shows that the microstructure of two IN706 alloys with P content (a) 0.002% P after being cooled at different cooling rates after being subjected to solid solution at 1190 ℃ for 24h is water-cooled; (b) 0.002% of P, air cooling; (c) 0.025% P, water cooling; (d) 0.025% P, air cooling.
FIG. 2 the microhardness of the samples after cooling at different cooling rates after solutionizing at 1190 ℃ for 24h for two P content IN706 alloys.
FIG. 3 tensile properties of samples of two P content IN706 alloys after solutionizing at 1190 ℃ for 24h and cooling at different cooling rates.
FIG. 4 IN706 alloy A system heat treated microstructure (a) 0.002% P; (b) 0.008% P; (c) 0.013% P; (d) 0.017% P.
FIG. 5 IN706 alloy B system heat treated intra-granular precipitated phase morphology (a) 0.002% P; (b) 0.017% P.
FIG. 6P is a graph showing the effect of heat treatment on the alloy durability at 650 ℃/690MPa of IN706 alloy A.
FIG. 7 IN706 alloy B system heat treated microstructure, (a) 0.002% P; (b) 0.008% P; (c) 0.013% P; (d) 0.017% P.
FIG. 8 is the morphology of an intragranular precipitated phase of the IN706 alloy B after system heat treatment, (a) 0.002% P; (b) 0.017% P.
FIG. 9P is a graph of the effect of heat treatment on the alloy durability at 650 deg.C/650 MPa for IN706 alloy B.
FIG. 10 Ni-Cr alloy 1100 deg.C/1 h, with a microstructure morphology after furnace cooling and heat treatment (a) 0.001% P; (b) 0.040% P; (c) 0.090% P.
FIG. 11 shows the endurance of Ni-Cr alloy at 1100 deg.C/1 h solid solution and 650 deg.C/150 MPa after furnace cooling heat treatment.
FIG. 12 shows the Ni-Cr-Fe system alloy at 1100 deg.C/1 h with a water-cooled texture profile (d) of 0.001% P; (e) 0.004% P; (f) 0.09% P.
FIG. 13P is the effect of in-crystal HV microhardness after solution heat treatment.
FIG. 14 shows the grain boundary structure morphology of the alloy after aging treatment (a) 0.001% P; (b) 0.004% P; (c) 0.09% P.
FIG. 15 shows the alloy after aging treatment with an in-crystal structure morphology (a) of 0.001% P; (b) 0.09% P.
FIG. 160.09 XRD pattern of the% P alloy extract.
FIG. 17 TEM/EDS spectrum of intracrystalline carbide.
FIG. 18P effect on intra-grain HV microhardness of alloys after aging treatment.
FIG. 19 shows the endurance of the alloy at 650 ℃/150MPa after aging heat treatment.
FIG. 20 shows that the carbides precipitated in the crystal act as a dislocation inhibitor.
FIG. 21 shows the in-crystal dislocation configuration (a) of the alloy after aging heat treatment at 650 ℃/150MPa for the permanent sample of 0.001% P; (b) 0.040% P; (c) 0.090% P; (d) segregation of C and P at dislocations.
Detailed Description
In the embodiment of the invention, the alloy is smelted by vacuum induction smelting, which specifically comprises the following steps:
adding trace element P in the early stage of casting through intermediate alloy FeP and/or NiP;
adding 1% CaO for deoxidation in the melting period of the alloy without C;
the refining temperature of the alloy is 1500-1600 ℃;
the alloy casting temperature is 1400-1500 ℃.
Example 1
1. Alloy composition
Smelting a furnace IN706 master alloy, which comprises the following components IN percentage by weight: 41.3Ni, 16.21Cr, 1.92Ti, 3.0Nb, 0.37Al, 0.022C, <0.001B, 0.002P, balance Fe. The mother alloy was cut out, and 6 different amounts of P (0.002%, 0.004%, 0.007%, 0.010%, 0.014%, 0.025) were added to each of the mother alloy, followed by remelting to form a child alloy.
2. Smelting of alloys
Vacuum induction melting
3. Hot working of alloys
Homogenizing cast ingot at 1150 deg.C for 30h +1190 deg.C for 30h
Heating temperature: 1110 +/-10 ℃ for 4 hours
Open forging temperature: 1000 +/-10 deg.C
Finish forging temperature: 950 ℃ C
4. Heat treatment of alloys
Solution treatment: keeping the temperature at 920-1190 ℃ for 5min-4h, and then air cooling/water cooling.
Aging treatment: 845 ℃, 3 hours, 730 ℃, 10 hours, 55 ℃/h furnace cooling, 620 ℃, 8 hours, and air cooling.
5. Alloy structure and properties
1) Alloy structure and performance after solution treatment
(1) Alloy structure
The IN706 alloy with different P contents is added to be kept at 1190 ℃, P is mainly dissolved IN a gamma matrix IN an atomic state, the observation results of the scanning structures of water-cooled and air-cooled samples with 0.002 percent of P alloy and 0.025 percent of P alloy dissolved at 1190 ℃ for 24 hours are shown IN figure 1, and no obvious difference exists between the water-cooled structures and the air-cooled structures of the two P content alloys.
(1) Alloy properties
Microhardness test results are shown in fig. 2, the microhardness values of the 0.002% P alloy water-cooled sample and the air-cooled sample are not much different, and are similar to the value of the 0.025% P alloy water-cooled sample, but the microhardness of the 0.025% P air-cooled alloy sample is twice that of the other three samples. The results of the room temperature tensile properties test are shown in fig. 3, which shows that the yield strength and tensile strength of the 0.025% P air-cooled alloy sample are significantly higher than the other three alloys, while the elongation is much lower than the other three alloys, which is consistent with the results of microhardness. This is because the addition of higher P content promoted the precipitation of the gamma prime phase IN the IN706 alloy, resulting IN the precipitation of the gamma prime phase IN the air-cooled samples, while the remaining three alloy samples did not precipitate this phase.
2) Alloy + post-aging texture and properties
(1) The heat treatment system organization of the alloy at A
The method is characterized IN that the IN706 alloy rolled bar with the four P contents of 0.002%, 0.008%, 0.013% and 0.017% is selected, and after heat treatment of two heat treatment systems, observation and test are carried out on the structure and the durability. A system A is solid solution for 3h at 980 ℃, heat preservation for 3h at 845 ℃, and double aging treatment at 730 ℃ and 620 ℃. Most of the grain boundaries of the 0.002 percent P and 0.008 percent P alloy have no precipitated phase, and only a small amount of grain boundaries precipitate a rod-shaped or strip-shaped eta phase; the alloys of 0.013% P and 0.017% P densely precipitate a large amount of long acicular eta phases under the system, and grow into the crystal in parallel with each other, as shown in FIG. 4. The results show that P has obvious influence on the eta phase of the alloy grain boundary, and the P promotes the precipitation and growth of the eta phase; meanwhile, after the heat treatment of the A system, P atoms in the alloy of 0.002% P and 0.008% P exist in a solid solution state, and most of P atoms in the alloy of 0.013% P and 0.017% P exist in a P compound form. The morphology of the precipitated strengthening phase in the alloy crystal is observed by TEM, as shown in FIG. 5, and P has little influence on the precipitation of the gamma 'and gamma' phases in the crystal.
(2) Heat treatment performance of alloy in A system
The result of the endurance performance test under the A system is shown in FIG. 6, the endurance life of the 0.002% P alloy is 76h, the endurance life of the 0.008% P alloy is 117h, and the endurance lives of the 0.013% P alloy and the 0.017% P alloy are 64 h. The permanent elongation of each alloy does not change much. The P content of the IN706 alloy with the best endurance quality after the A-system heat treatment is near 0.008% P.
(3) Heat treatment organization of alloy in B
After solid solution is carried out for 2h at 1060 ℃, double aging treatment is carried out. The scanning structure morphology is shown in fig. 7, a small amount of white granular carbide is precipitated in the grain boundary or the crystal interior of each alloy, but no eta phase and phosphide are precipitated. The morphology of the precipitated phase in the crystal is observed by TEM, as shown in FIG. 8, and P has little influence on the strengthening phase in the crystal.
(4) Performance of alloy in B heat treatment system
With the continuous increase of the P content, the endurance life of the alloy is continuously prolonged, the endurance life of the 0.002% P alloy is 23 hours, the endurance life of the 0.008% P alloy is 44 hours, the endurance life of the 0.013% P alloy is 56 hours, the endurance life of the 0.017% P alloy is 80 hours, and the endurance life of the 0.002% P alloy is 3-4 times that of the 0.002% P alloy. Meanwhile, the addition of P has no obvious influence on the permanent plasticity of the alloy, as shown in FIG. 9.
Example 2
1. The composition of the Ni-Cr alloy is shown in Table 1
Table 1 composition (wt.%) of Ni-Cr-based alloy with different P contents
2. Smelting of alloys
Vacuum induction melting
3. Hot working of alloys
Heating temperature: 1110 +/-10 ℃ for 4 hours
Open forging temperature: 1000 +/-10 deg.C
Finish forging temperature: 950 ℃ C
4. Heat treatment of alloys
Solution treatment: 1100 deg.C, 1 hr, water cooling and furnace cooling
Aging treatment: cooling at 720 deg.C for 10 hr, furnace cooling at 55 deg.C/h, furnace cooling at 620 deg.C for 8 hr, and air cooling
5. Alloy structure and properties
The Ni-Cr alloys are subjected to solid solution for 1 hour at 1100 ℃, the difference of the structure and the appearance of the alloys is obvious in different cooling modes, the alloys are rapidly cooled by water, and no precipitated phase exists in a crystal boundary and a crystal interior. Slow furnace cooling, with precipitated phases at the grain boundaries and no precipitated phases within the grains, as shown in fig. 10. And with the increase of the P content, the number of crystal boundary precipitated phases is increased, and the appearance is changed from a rod shape to a particle shape. The alloy after furnace cooling is tested with 650 ℃ tensile property and 650 ℃ 150MPa endurance property, the tensile strength and endurance life are obviously reduced along with the increase of P content, and the endurance elongation rate is also in a descending trend, as shown in Table 2 and figure 11.
TABLE 2 tensile properties of Ni-Cr alloy 1100 deg.C/1 h, 650 deg.C after furnace cooling and heat treatment
Example 3
1. The composition of the Ni-Cr-Fe alloy is shown in Table 3
TABLE 3 composition (wt.%) of Ni-Cr-Fe system alloys of different P contents
2. Alloy smelting and hot working
Alloy melting and hot working were the same as in example 2.
3. Heat treatment of alloys
Solution treatment: 1100 deg.C, 1 hour, water cooling
Aging treatment: water cooling at 800 deg.C for 8 hr
4. Alloy structure and properties
1) Alloy structure and performance after solution treatment
(1) Alloy structure
The structure and the morphology of the Ni-Cr-Fe alloy under the solid solution condition are shown in figure 12, after the alloy is subjected to solid solution for 1 hour at 1100 ℃, the alloy is cooled in a furnace, a large amount of carbide is precipitated on a grain boundary, and no precipitated phase exists in the grain.
(2) Tensile Properties
When the alloy is tested to have the tensile property of 650 ℃ after furnace cooling, the yield strength of the alloy is not obviously changed when the content of P is increased, the tensile strength is obviously increased, and the elongation and the reduction of area are also slightly increased, as shown in Table 4.
TABLE 4 tensile properties of Ni-Cr-Fe alloy 1100 deg.C/1 h at 650 deg.C after furnace cooling and heat treatment
(3) Microhardness
The alloy is subjected to water cooling after being subjected to solution treatment at 1100 ℃ for 1 hour, the intracrystalline HV microhardness is shown in figure 13, and P has no significant influence on the intracrystalline HV microhardness.
2) Structure and performance after solid solution and aging
(1) Alloy structure
When the alloy is subjected to solid solution for 1 hour at 1100 ℃ and water cooling, and then is subjected to aging for 8 hours and water cooling treatment at 800 ℃, the grain boundaries of the alloy with different P contents are precipitated, the number of precipitated phases is increased along with the increase of the P content, and the shape is gradually changed from a short rod shape to a particle shape, as shown in FIG. 14. Meanwhile, each alloy has a precipitated phase in the crystal, the number of the precipitated phases is obviously increased along with the increase of the P content, and the precipitated phases are granular, short flat plates and long flat plates, and fig. 15 shows the morphology of the precipitated phases in the crystal with low P content and high P content. As shown in FIG. 16, when 0.09% P alloy precipitated phase was extracted by electrochemically etching the matrix, XRD analysis showed that both grain boundary and intragranular precipitated phase were M23C6The volume fraction of the alloy intragranular precipitated phase is about 20.8%, while the volume fraction of the grain boundary precipitated phase is only 0.4%, thus extracting M23C6Mainly from intragranular, chemical analysis shows that M23C6The P content in the crystal was 0.15% (0.09% in the matrix), indicating that P is in the intragranular M23C6Has enrichment in it. Meanwhile, high-resolution transmission electron microscopy and energy spectrum analysis show that a certain amount of P atoms are dissolved in solid solution in the intracrystalline carbide, and the figure is shown in figure 17. By finding that P is in-crystal M23C6Solid solution confirmed the presence of P in the alloy matrix.
(2) Tensile Properties
The tensile properties of the samples subjected to solid solution treatment (1100 ℃ C.. times.1 h, WC) and then aging heat treatment (800 ℃ C.. times.8 h, WC) are shown in Table 5, and as the content of P is increased, the yield strength of the alloy is obviously increased, the tensile strength is not changed greatly, and the elongation and the reduction of area are also improved greatly.
TABLE 5 tensile Properties after aging Heat treatment
(3) Microhardness
The alloy has HV microhardness as shown in FIG. 18, the intra-grain HV microhardness increases with increasing P content, and the microhardness of the 0.09P alloy is significantly higher than that of the 0.001P alloy and the 0.040 alloy. The results of microhardness are consistent with the change in yield strength of the tensile specimens.
(4) Durability performance
As shown in FIG. 19, the Ni-Cr-Fe system alloy showed a significant increase in the endurance life with an increase in the P content, and showed no significant change in the elongation. The microstructure observation of different alloys shows that as the content of P is increased, a sufficient amount of P element is dissolved in the alloy matrix so as to promote the precipitation of P-rich carbide in the crystal, the dislocation blocking effect of the carbide is increased, and the strengthening effect is enhanced (as shown in figure 20). The P content is increased, the distortion degree of matrix crystal lattice is increased, the effect of preventing dislocation is enhanced, and the line scanning EDS of TEM shows that C and P elements are enriched near dislocation, which shows that P and C can be deviated to the dislocation and prevent dislocation movement, as shown in FIG. 21. Meanwhile, the grain boundary precipitation state of the alloy is beneficial to the improvement of the endurance life of the alloy (see fig. 14).
The invention can confirm the existence mode of P in different alloy systems and the action mode between P and other elements by simplifying the concept of the alloy, and effectively reveals the action mechanism of P in the deformed high-temperature alloy. The method provides a direct reference method for the research of another important trace element B in the deformed high-temperature alloy in the alloy, and has important reference value in the aspect of the performance optimization design of the trace element on the deformed high-temperature alloy. Through the alloy of design simplification, not only practiced thrift raw and other materials, still saved the human cost, improved research efficiency greatly.
The invention is not the best known technology.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A method for researching the action mechanism of trace element phosphorus in a deformed high-temperature alloy is characterized in that: different alloy series are formed from simple to complex by changing the components of the deformed high-temperature alloy, different trace elements of phosphorus are added, the existence position and the existence mode of the phosphorus, the action relation between the main alloy element and the strengthened alloy element and the influence on the alloy structure are analyzed by adjusting the heat treatment process, and the influence on the alloy performance caused by the phosphorus element is evaluated, so that the existence mode of the phosphorus in the deformed high-temperature alloy, the interaction with each alloy element and the action mechanism are disclosed.
2. The method for studying the mechanism of action of trace element phosphorus in wrought superalloy as in claim 1, wherein: the wrought superalloy is a nickel-based wrought superalloy.
3. A method for studying the mechanism of action of trace element phosphorus in wrought superalloy according to claim 1 or 2, comprising: different alloy series are formed from simple to complex, and the ranges of the alloy elements of the different alloy series are as follows by mass percent: 10.0-23.0% of Cr, 0-60% of Fe, 0-2.75% of Al, 0-3.6% of Ti, 0-5.50% of Nb, (Mo + W) 0-5.0%, 0-0.090% of P, 0-0.1% of C, 0-0.02% of B, less than or equal to 0.01% of Mg, less than or equal to 0.35% of Mn, less than or equal to 0.35% of Si, less than or equal to 0.015% of S, less than or equal to 0.30% of Cu, less than or equal to 0.01% of Ca, less than or equal to 1.0% of Co, less than or equal to 0.01% of N, less than or equal to 0.01% of O, and the balance of Ni.
4. A method for studying the mechanism of action of trace element phosphorus in wrought superalloy according to claim 1 or 2, comprising: different alloy series are formed from simple to complex, and the element ranges of the alloy series are as follows:
the series is: Ni-Cr alloy, Cr 10.0-23.0%, Fe content less than or equal to 5%, and Ni in balance;
the series of the second step: Ni-Cr-Fe alloy, Cr 10.0-23.0%, Fe 5-60%, and Ni in balance.
5. The method for researching the action mechanism of the trace element phosphorus in the wrought superalloy according to claim 1, wherein the heat treatment process of the wrought superalloy is as follows: heating temperature: 800-1190 ℃; heating time: less than or equal to 50 h;
a cooling mode: furnace cooling or cooling faster than furnace cooling.
6. The method for researching the action mechanism of the trace element phosphorus in the wrought superalloy according to claim 1, wherein the wrought superalloy is prepared by a smelting process comprising the following steps:
adding trace element P in the early stage of casting through intermediate alloy FeP and/or NiP;
adding 1% CaO for deoxidation in the melting period of the alloy without C;
the refining temperature of the alloy is 1500-1600 ℃;
the alloy casting temperature is 1400-1500 ℃.
7. The method for researching the action mechanism of the trace element phosphorus in the wrought superalloy according to claim 1, wherein the hot working process of the wrought superalloy is as follows:
heating temperature: 1000 ℃ to 1170 ℃;
and (3) heat preservation time: the time is more than or equal to 4 hours;
open forging temperature: more than or equal to 1000 +/-10 ℃;
finish forging temperature: is higher than 900 ℃.
8. Use of the method according to claim 1 for studying the mechanism of action of phosphorus in wrought superalloy for improving the creep resistance of the alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110324887.XA CN113355618A (en) | 2021-03-26 | 2021-03-26 | Research method and application of trace element phosphorus in deformation high-temperature alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110324887.XA CN113355618A (en) | 2021-03-26 | 2021-03-26 | Research method and application of trace element phosphorus in deformation high-temperature alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113355618A true CN113355618A (en) | 2021-09-07 |
Family
ID=77525032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110324887.XA Pending CN113355618A (en) | 2021-03-26 | 2021-03-26 | Research method and application of trace element phosphorus in deformation high-temperature alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113355618A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114686662A (en) * | 2022-03-28 | 2022-07-01 | 江西宝顺昌特种合金制造有限公司 | GH2132 high-temperature alloy and heat treatment method for improving hardness of GH2132 high-temperature alloy |
| CN115821146A (en) * | 2022-12-12 | 2023-03-21 | 江苏新核合金科技有限公司 | Reinforced high-temperature alloy plate and manufacturing process thereof |
| CN116024460A (en) * | 2022-12-29 | 2023-04-28 | 承德天大钒业有限责任公司 | Nickel-phosphorus-boron intermediate alloy and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002173722A (en) * | 2000-12-06 | 2002-06-21 | Nippon Yakin Kogyo Co Ltd | Ni BASED ALLOY SLAB FOR HOT ROLLING AND ITS PRODUCTION METHOD |
| US20040007472A1 (en) * | 2000-10-25 | 2004-01-15 | Alfons Hollander | Lead-free chemical nickel alloy |
| CN103981373A (en) * | 2014-05-29 | 2014-08-13 | 大连理工大学 | Method for preparing nickel-based high-temperature alloy |
| CN105483448A (en) * | 2015-12-28 | 2016-04-13 | 钢铁研究总院 | Manufacturing method of nuclear nickel-base high-temperature alloy GH 4145 wire |
| 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 |
| CN106319255A (en) * | 2015-07-06 | 2017-01-11 | 中国科学院金属研究所 | Purified smelting process for nickel-based high-temperature alloy |
-
2021
- 2021-03-26 CN CN202110324887.XA patent/CN113355618A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040007472A1 (en) * | 2000-10-25 | 2004-01-15 | Alfons Hollander | Lead-free chemical nickel alloy |
| JP2002173722A (en) * | 2000-12-06 | 2002-06-21 | Nippon Yakin Kogyo Co Ltd | Ni BASED ALLOY SLAB FOR HOT ROLLING AND ITS PRODUCTION METHOD |
| CN103981373A (en) * | 2014-05-29 | 2014-08-13 | 大连理工大学 | Method for preparing nickel-based high-temperature 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 |
| CN106319255A (en) * | 2015-07-06 | 2017-01-11 | 中国科学院金属研究所 | Purified smelting process for nickel-based high-temperature alloy |
| CN105483448A (en) * | 2015-12-28 | 2016-04-13 | 钢铁研究总院 | Manufacturing method of nuclear nickel-base high-temperature alloy GH 4145 wire |
Non-Patent Citations (3)
| Title |
|---|
| NA LI等: "Effect of P and B on the creep behavior of alloy 718", 《MATERIALS LETTERS》 * |
| 廉心桐: "P与高温合金主要基体元素间的交互作用", 《中国博士学位论文全文数据库 （电子期刊）》 * |
| 李振荣等: "微量元素P、B对GH4169合金组织与蠕变性能的影响", 《材料科学与工艺》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114686662A (en) * | 2022-03-28 | 2022-07-01 | 江西宝顺昌特种合金制造有限公司 | GH2132 high-temperature alloy and heat treatment method for improving hardness of GH2132 high-temperature alloy |
| CN114686662B (en) * | 2022-03-28 | 2023-09-19 | 江西宝顺昌特种合金制造有限公司 | GH2132 high-temperature alloy and heat treatment method for improving hardness of GH2132 high-temperature alloy |
| CN115821146A (en) * | 2022-12-12 | 2023-03-21 | 江苏新核合金科技有限公司 | Reinforced high-temperature alloy plate and manufacturing process thereof |
| CN116024460A (en) * | 2022-12-29 | 2023-04-28 | 承德天大钒业有限责任公司 | Nickel-phosphorus-boron intermediate alloy and preparation method thereof |
| CN116024460B (en) * | 2022-12-29 | 2024-04-30 | 承德天大钒业有限责任公司 | Nickel-phosphorus-boron intermediate alloy and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9945019B2 (en) | Nickel-based heat-resistant superalloy | |
| CN110317990B (en) | Ni-Co-Al-Cr-Fe monocrystal high-entropy high-temperature alloy and preparation method thereof | |
| CN113355618A (en) | Research method and application of trace element phosphorus in deformation high-temperature alloy | |
| US10260137B2 (en) | Method for producing Ni-based superalloy material | |
| US10344367B2 (en) | Method for producing Ni-based superalloy material | |
| CN102076877A (en) | Ni-based single crystal superalloy and alloy member using the same as base | |
| CN110952041B (en) | Fe-Mn-Ni-Cr four-component high-entropy alloy | |
| CN107090555B (en) | Ni base superalloy for hot forging | |
| CN113737071B (en) | Heat-resistant magnesium alloy and preparation method and application thereof | |
| CN110983144B (en) | Nitride reinforced high-entropy alloy and preparation method thereof | |
| CN104583431B (en) | The resource-conserving titanium alloy member and its manufacture method of intensity and tenacity excellent | |
| CN113604706B (en) | Low-density low-expansion high-entropy high-temperature alloy and preparation method thereof | |
| CN107090556B (en) | Ni base superalloy for hot forging | |
| CN109967674B (en) | Manufacturing method of high-temperature alloy forging for nuclear power steam generator | |
| CN109763008A (en) | A kind of high strength and high flexibility copper alloy containing niobium and preparation method thereof | |
| WO2004013364A1 (en) | Age-hardenable, zinc-containing magnesium alloys | |
| CN114480984A (en) | Ti alloyed low-density high-strength steel and preparation method thereof | |
| CN113584371A (en) | Precipitation strengthening type high-entropy alloy with truss structure and preparation method thereof | |
| KR101888049B1 (en) | Method for preparing Ti-Al-Nb-Fe alloy improved fracture toughness and creep properties | |
| Li et al. | Effects of Ag on microstructure and mechanical properties of 2519 aluminum alloy | |
| RU2219272C1 (en) | Refractory castable nickel-based alloy | |
| CN118064784A (en) | TiNi-based high-temperature high-entropy shape memory alloy with excellent strong plasticity and high recoverable strain | |
| CN116607060A (en) | Nano lamellar epsilon-phase reinforced nickel-based multi-principal element alloy, design method and preparation method | |
| CN116356181A (en) | Cobalt-based deformation superalloy and preparation method thereof | |
| CN118166187A (en) | Ultra-supercritical steam turbine rotor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210907 |