CN113930654A - Casting alloy with high hardness and high specific yield strength under high temperature condition and preparation method thereof - Google Patents
Casting alloy with high hardness and high specific yield strength under high temperature condition and preparation method thereof Download PDFInfo
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Abstract
The invention provides a casting alloy with high hardness and high specific yield strength under high temperature and a preparation method thereof, wherein the casting alloy with high hardness and high specific yield strength under high temperature comprises the following components in molar ratio: ni34-40 parts; cr15-28 parts; v22-36 parts; al16-20 parts; and (3) 16-20 parts of Ti. The invention also discloses a preparation method of the casting alloy with high hardness and high specific yield strength under the high-temperature condition, which comprises the following steps: after the raw materials of all the components are mixed, vacuum magnetic suspension smelting is carried out by adopting a vacuum magnetic suspension smelting furnace, and the cast alloy with high hardness and high specific yield strength under the high-temperature condition is obtained. The cast alloy has the characteristics of low density (about 22 percent lower than that of Ni-based high-temperature alloy), high-temperature hardness, high-temperature specific yield strength and good high-temperature softening resistance.
Description
Technical Field
The invention relates to an alloy technology, in particular to a casting alloy with high hardness and specific yield strength under a high-temperature condition and a preparation method thereof.
Background
The high-temperature alloy material is an important strategic material and a typical military and civil fusion material, and the quality and the performance of the high-temperature alloy material directly influence and even determine the performance of advanced equipment such as aerospace, ships, electric power and the like. The high-temperature alloy material in China is subjected to the development process from inexhaustible to ever and from small to large, and also is subjected to different development stages from tracking simulation, improvement and modification to independent innovation and development. But at present, the performance level of the high-temperature alloy in China is still low, the quality stability is poor, the cost is high, the autonomous guarantee capability is poor, more than 40 percent of the high-temperature alloy depends on import, and the high-temperature alloy for the aeroengine is more than 50 percent more expensive than that of developed countries. The high-temperature alloy material is a key core material for supporting and guaranteeing major national strategies such as 'manufacturing strong country', 'military and civil integration', and the like, but the high-grade high-temperature alloy material is forbidden to be exported in the current developed countries, so that the high-temperature alloy material becomes the bottleneck problem of 'two-machine engineering' in China, and the national safety is seriously influenced.
The service temperature of the current Ni-based high-temperature alloy in aeroengines and industrial gas turbines reaches 80 percent of the melting point of the alloy and reaches the limit of the service temperature. Generally, Ni-based superalloys begin to have a sharp decrease in hardness and yield strength at temperatures above about 650 ℃, because the γ "strengthening phase in the alloy gradually transforms into the detrimental δ phase at these temperatures, which results in poor high temperature thermal stability, and lower hardness and yield strength values above 800 ℃. In addition, Ni-based superalloys have a relatively high density, typically 8.2g/cm3The above results in a lower specific yield strength of the Ni-based superalloy.
In order to save energy and reduce emission and meet the service requirements of new-generation gas turbines and high thrust-weight ratio aircraft engines at higher temperature, a casting alloy with high hardness and high specific yield strength under a high-temperature condition is urgently needed.
Disclosure of Invention
The invention aims to provide a casting alloy with high hardness and high specific yield strength under high temperature conditions, which has the characteristics of low density (about 22 percent lower than that of Ni-based high-temperature alloy), high-temperature hardness, high-temperature specific yield strength and good high-temperature softening resistance, aiming at the problems that the existing Ni-based high-temperature alloy has low high-temperature hardness above 650 ℃, low high-temperature specific yield strength and poor high-temperature softening resistance and cannot meet the high-temperature service requirements.
In order to achieve the purpose, the invention adopts the technical scheme that: a casting alloy with high hardness and high specific yield strength under high temperature conditions comprises the following components in molar ratio:
further, the cast alloy with high hardness and high specific yield strength under the high-temperature condition comprises the following components in molar ratio:
furthermore, the Ni, the Cr, the Al and the Ti are all selected from industrial grade pure raw materials with the purity of more than 99.5 wt%.
Further, the cast alloy with high hardness and high specific yield strength under the high-temperature condition also comprises the following components in molar ratio: v22-36 parts, preferably V22-24 parts, and more preferably V32 parts. The V is an industrial grade pure raw material with the purity of more than 99.5 wt%.
Further, the high-temperature condition is 600-1100 ℃.
The invention also discloses a preparation method of the casting alloy with high hardness and high specific yield strength under the high-temperature condition, which comprises the following steps: after the raw materials of all the components are mixed, vacuum magnetic suspension smelting is carried out by adopting a vacuum magnetic suspension smelting furnace, and the cast alloy with high hardness and high specific yield strength under the high-temperature condition is obtained.
Further, the raw materials of the components are placed in the order that Al is placed at the lowest part, Ti and Cr are placed in the middle, and Ni is placed at the highest part.
Further, the working conditions of the vacuum magnetic suspension smelting furnace are that the vacuum pumping is carried out to below 10Pa, and the molecular pump is started to carry out the vacuum pumping to 3 multiplied by 10-3Under Pa, filling argon to (3-5) × 102Pa。
Further, the vacuum magnetic suspension smelting comprisesThe following steps: opening 'control power on-off', checking whether the equipment gives an alarm or not, if not, placing the material in the furnace, placing Al at the lowest part, placing Ti and Cr in the middle, placing Ni at the uppermost part, closing the furnace cover, locking the lock catch, vacuumizing to below 10Pa, and opening a molecular pump to vacuumize to 3 x 10-3Under Pa, filling argon to (3-5) × 102And Pa, turning on a heating power switch, slowly and manually adjusting a power adjusting knob (clockwise rotating, 5kW/10min speed up-regulating), after the raw materials are completely melted (materials are completely melted), slowly and manually adjusting the power adjusting knob (anticlockwise rotating, 5kW/3min speed down-regulating) until the raw materials are completely melted, and repeatedly melting for 2-3 times to ensure the uniformity of the components.
The invention also discloses the application of the cast alloy with high hardness and high specific yield strength under high temperature in the field of aeroengines or industrial gas turbines.
Compared with the prior art, the cast alloy with high hardness and specific yield strength under the high-temperature condition and the preparation method thereof have the following advantages:
1) the casting alloy with high hardness and high specific yield strength under the high-temperature condition has multiple strengthening mechanisms: the near-equilibrium eutectic structure forms an in-situ composite material with ordered and disordered alternative arrangement, and can resist the temperature change up to the eutectic reaction point; the nano-scale interlayer spacing promotes the alloy strength to be greatly improved; the alloy contains nearly 70% of a Heusler phase rich in Ni-Al-Ti, which has a very stable L21The structure has a highly ordered and limited slip system, and has outstanding high-temperature hardness, strength and creep resistance; the eutectic two phases have semi-coherent interfaces, belong to strong interface bonding and have high interface bonding strength; a large number of eutectic phase interfaces and high-density interface dislocation networks can block the movement of dislocations; the high density of coherent nano-precipitates contained in the eutectic phase may increase the strength of the alloy through precipitation strengthening. The room temperature hardness of the alloy is detected to be 530HV0.3The hardness at high temperature of 800 ℃ is still up to 490HV0.3Compared with the room temperature, the hardness is only reduced by 7.5 percent; the yield strength of the alloy at room temperature, 600 ℃ and 800 ℃ is respectively as high as 1.55GPa, 1.05GPa and 500MPa, the specific yield strength is respectively up to 240MPa (g cm)-3)-1、164MPa·(g·cm-3)-1、84MPa·(g·cm-3)-1The specific yield strength is much higher than that of the traditional 6061 aluminum alloy, Inconel 718 and Haynes230 high-temperature alloy at corresponding temperature.
2) The preparation method of the casting alloy with high hardness and high specific yield strength under the high-temperature condition is simple, and the casting alloy can be prepared by magnetic suspension smelting in a vacuum atmosphere and cast molding. The alloy can be directly cast and molded, and has the excellent high-temperature mechanical property without heat treatment and subsequent complex processing technology.
Drawings
FIG. 1 is a scanning electron micrograph of a cast alloy having high hardness and high specific yield strength at high temperature in example 1;
FIG. 2 shows the results of Transmission Electron Microscopy (TEM) characterization of the alloy of example 1: wherein (a) a TEM bright field image; (b) high density nano-precipitates in the eutectic Heusler phase; (c) selective electron diffraction results of eutectic Heusler phases; (d) selective electron diffraction results of eutectic BCC phases;
FIG. 3 is the high temperature hardness of the cast alloy of example 1 having high hardness and high specific yield strength at elevated temperature compared to the Inconel 718 superalloy;
FIG. 4 is a compressive engineering stress-strain curve at room temperature, 600 ℃ and 800 ℃ for a cast alloy having high hardness and high specific yield strength at elevated temperature in example 1;
FIG. 5 is the specific yield strength at different temperatures for the cast alloys of example 1 with high hardness and high specific yield strength at elevated temperatures compared to Inconel 718 superalloy, 6061 aluminum alloy, Haynes230 superalloy.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The embodiment discloses a casting alloy with high hardness and high specific yield strength under high temperature conditions, which comprises the following components in molar ratio: al: 19 parts of a mixture; ti: 18 parts of a mixture; ni: 37 parts of; cr: 26 parts of (A). The Al, Ti, Ni and Cr are all selected from industrial grade pure raw materials with the purity of more than 99.5 wt.%.
The preparation method of the cast alloy with high hardness and high specific yield strength at high temperature in the embodiment is as follows: when the alloy is melted, Al is arranged at the lowest part, Ti and Cr are arranged in the middle, Ni is arranged at the highest part, a furnace cover is closed, a lock catch is locked, the vacuum is pumped to be below 10Pa, a molecular pump is pumped to be vacuum of 3 multiplied by 10-3Under Pa, filling argon to (3-5) × 102And Pa, turning on a heating power switch, slowly and manually adjusting a power adjusting knob (rotating clockwise and adjusting the speed at 5kW/10min upwards), after the raw materials are smelted, slowly and manually adjusting the power adjusting knob (rotating anticlockwise and adjusting the speed at 5kW/3min downwards) until the raw materials are completely turned off, and repeatedly smelting for 2 times to ensure the uniformity of the components.
As shown in FIG. 1, the low-power morphology of the cast alloy of this example, which has high hardness and higher yield strength at high temperatures, consists of uniform and ultra-fine eutectic phases. FIG. 2(a) is a Transmission Electron Microscope (TEM) bright field image of the cast alloy of this example, in which a large amount of misfit dislocations are observed at the interface between two eutectic phases to form a dislocation network; further amplification of the eutectic Heusler phase inside high density nano-precipitates were observed as shown in fig. 2 (b). FIGS. 2(c) and 2(d) show selected zone electron diffraction of two eutectic phases, further demonstrating that each of the two phases has L21And BCC structures.
Fig. 3 shows the high temperature hardness of the example cast alloy compared to the Inconel 718 superalloy, and it is found that the example cast alloy is much harder than the Inconel 718 superalloy at any room temperature to 900 ℃ temperature, and it should be noted that the hardness of the example cast alloy decreases less significantly with increasing temperature, and has excellent high temperature softening resistance and high temperature thermal stability, while the hardness of the Inconel 718 superalloy decreases significantly with increasing temperature, especially over 700 ℃, and this tendency is more pronounced.
FIG. 4 shows that the yield strengths of the cast alloy of the embodiment at room temperature, 600 deg.C and 800 deg.C are as high as 1.55GPa, 1.05GPa and 500MPa, respectively.
FIG. 5 is a graph of specific yield strength at different temperatures for example cast alloys andcomparison of Inconel 718 superalloy, 6061 aluminum alloy, Haynes230 superalloy. The specific yield strength of the alloy of the embodiment is up to 240MPa (g cm)-3)-1、164MPa·(g·cm-3)-1、84MPa·(g·cm-3)-1The specific yield strength is much higher than that of the traditional 6061 aluminum alloy, Inconel 718 and Haynes230 super alloy at corresponding temperature.
Example 2
The embodiment discloses a casting alloy with high hardness and high specific yield strength under high temperature conditions, which comprises the following components in molar ratio: al: 17 parts of (1); ti: 17 parts of (1); ni: 34 parts of (a); cr: 12 parts of (1); v: 22 parts of. The Al, Ti, Ni, Cr and V are all selected from industrial grade pure raw materials with the purity of more than 99.5 wt.%.
The preparation method of the cast alloy with high hardness and high specific yield strength at high temperature in the embodiment is as follows: when the alloy is melted, Al is arranged at the lowest part, Ti, Cr and V are arranged in the middle, Ni is arranged at the highest part, a furnace cover is closed, a lock catch is locked, the vacuum pumping is carried out to be less than 10Pa, and a molecular pump is started to carry out vacuum pumping to be 3 multiplied by 10-3Under Pa, filling argon to (3-5) × 102And Pa, turning on a heating power switch, slowly and manually adjusting a power adjusting knob (rotating clockwise and adjusting the speed at 5kW/10min upwards), after the raw materials are smelted, slowly and manually adjusting the power adjusting knob (rotating anticlockwise and adjusting the speed at 5kW/3min downwards) until the raw materials are completely turned off, and repeatedly smelting for 2 times to ensure the uniformity of the components.
Block L2 of the cast alloy of this example having high hardness and high specific yield strength under high temperature conditions1Primary phase and eutectic phase, the eutectic phase has L21And BCC structures. The yield strengths of the cast alloy of the embodiment at room temperature, 600 ℃ and 800 ℃ are respectively as high as 1.45GPa, 1.15GPa and 700 MPa. The specific yield strength is respectively up to 220MPa (g cm)-3)-1、～175MPa·(g·cm-3)-1、～110MPa·(g·cm-3)-1。
Example 3
The embodiment discloses a casting alloy with high hardness and high specific yield strength under high temperature conditions, which comprises the following components in molar ratio: al: 17 parts of (1); ti: 17 parts of (1); ni: 34 parts of (a); v: 32 parts of. The Al, Ti, Ni and V are all selected from industrial grade pure raw materials with the purity of more than 99.5 wt.%.
The preparation method of the cast alloy with high hardness and high specific yield strength at high temperature in the embodiment is as follows: when the alloy is melted, Al is arranged at the lowest part, Ti and V are arranged in the middle, Ni is arranged at the highest part, a furnace cover is closed, a lock catch is locked, the vacuum is pumped to be below 10Pa, a molecular pump is pumped to be vacuum of 3 multiplied by 10-3Under Pa, filling argon to (3-5) × 102And Pa, turning on a heating power switch, slowly and manually adjusting a power adjusting knob (rotating clockwise and adjusting the speed at 5kW/10min upwards), after the raw materials are smelted, slowly and manually adjusting the power adjusting knob (rotating anticlockwise and adjusting the speed at 5kW/3min downwards) until the raw materials are completely turned off, and repeatedly smelting for 2 times to ensure the uniformity of the components.
The cast alloy of this example, which has high hardness and high specific yield strength at high temperature, is composed of uniform and ultra-fine eutectic phases having L21And BCC structures. The yield strengths of the cast alloy of the embodiment at room temperature, 600 ℃ and 800 ℃ are respectively as high as 1.42GPa, 1.18GPa and 770 MPa. The specific yield strength is up to 230MPa (g cm)-3)-1、～190MPa·(g·cm-3)-1、～125MPa·(g·cm-3)-1。
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A cast alloy having high hardness and high specific yield strength at elevated temperatures, comprising the following components in molar proportions:
2. the cast alloy of claim 1, having a high hardness at elevated temperatures and a high specific yield strength, comprising the following components in molar proportions:
3. the cast alloy of claim 1, which has a high hardness at high temperatures and a high specific yield strength, wherein Ni, Cr, Al and Ti are all technical grade pure materials having a purity of 99.5 wt% or more.
4. The cast alloy of claim 1, having a high hardness at elevated temperatures and a high specific yield strength, further comprising the following components in molar proportions: and V22-36 parts.
5. A method for producing a cast alloy having high hardness and high specific yield strength at high temperatures according to any one of claims 1 to 4, comprising the steps of: after the raw materials of all the components are mixed, vacuum magnetic suspension smelting is carried out by adopting a vacuum magnetic suspension smelting furnace, and the cast alloy with high hardness and high specific yield strength under the high-temperature condition is obtained.
6. The method of producing a cast alloy having high hardness and high specific yield strength under high temperature conditions according to claim 5, wherein the raw materials of the respective components are placed in the order of Al being placed at the lowermost, Ti and Cr being placed in the middle, and Ni being placed at the uppermost.
7. The alloy according to claim 5, which has high hardness and high specific yield strength under high temperature conditionsThe preparation method of the casting alloy is characterized in that the working condition of the vacuum magnetic suspension smelting furnace is that the vacuum pumping is carried out to below 10Pa, and the molecular pump is started to carry out the vacuum pumping to 3 multiplied by 10-3Under Pa, filling argon to (3-5) × 102Pa。
8. The method for preparing the casting alloy with high hardness and high specific yield strength under the high-temperature condition as claimed in claim 5, wherein the vacuum magnetic suspension smelting comprises the following steps: opening 'control power on-off', checking whether the equipment gives an alarm or not, if not, placing the material in the furnace, placing Al at the lowest part, placing Ti and Cr in the middle, placing Ni at the uppermost part, closing the furnace cover, locking the lock catch, vacuumizing to below 10Pa, and opening a molecular pump to vacuumize to 3 x 10-3Under Pa, filling argon to (3-5) × 102And Pa, turning on a heating power switch, slowly and manually adjusting a power adjusting knob, and after the raw materials are completely smelted, slowly and manually adjusting the power adjusting knob until the raw materials are completely turned off, and repeatedly smelting for 2-3 times to ensure the uniformity of the components.
9. Use of a cast alloy having a high hardness and a high specific yield strength at high temperatures according to any one of claims 1 to 4 in the field of aeroengines or industrial gas turbines.
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