CN100497701C - NiAl-Cr(Mo) biphase eutectic crystal intermetallic compound modified by V - Google Patents
NiAl-Cr(Mo) biphase eutectic crystal intermetallic compound modified by V Download PDFInfo
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- CN100497701C CN100497701C CNB200710176118XA CN200710176118A CN100497701C CN 100497701 C CN100497701 C CN 100497701C CN B200710176118X A CNB200710176118X A CN B200710176118XA CN 200710176118 A CN200710176118 A CN 200710176118A CN 100497701 C CN100497701 C CN 100497701C
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Abstract
The present invention discloses one kind of V modified two-phase eutectic intermetallic NiAl-Cr(Mo) compound comprising Ni in 33 at.%, Cr in 30 at.%, Mo in 4 at.%, V in 1-16 at.% and Al for the rest. By means of lowering Al content in the two-phase eutectic intermetallic NiAl-Cr(Mo) alloy, and adding V element to modify and form one Heusler phase to reinforce the base and raise the high temperature performance, the V modified two-phase eutectic intermetallic NiAl-Cr(Mo) compound has high room temperature toughness and plasticity and further raised high temperature strength. The V modified two-phase eutectic intermetallic NiAl-Cr(Mo) compound has yield strength at 1150 deg.c of 120-150 MPa and density of 6.0-6.6 g/cu cm.
Description
Technical field
The present invention relates to a kind of NiAl-Cr (Mo) biphase eutectic crystal intermetallic compound of V modification, have NiAl phase, Cr (Mo) phase and Ni in the described intermetallic compound
2The AlV phase.
Background technology
At present, at power, petrochemical industry, transportation, particularly industrial circle such as aviation and space flight, be applied in structural metallic materials more than 600 ℃ and be generally Ni-based, iron-based and cobalt base superalloy.These materials have higher density (generally at 8.0g/cm
3More than), made member and weight of equipment are big, in order to alleviate structural weight, raise the efficiency, and reduce energy consumption, must develop the strong superalloy of low density, height ratio to adapt to the needs of related industries field future development.More urgent is is the superalloy of representative owing to be subjected to the restriction of fusing point with Ni base, Co base at present, near the ultimate temperature of its use.Even added three generations's superalloy monocrystalline of a large amount of precious metals, its use temperature also is no more than 1100 ℃.For satisfying the demand of gas turbine engine of new generation, being badly in need of exploitation, to hold warm ability be 1150 ℃ high-temperature structural material.
The fusing point of B2 structure long-range order NiAl is up to 1638 ℃, and is higher 300～350 ℃ than nickel base superalloy, and use temperature is expected to reach 1250 ℃; Its density 5.86g/cm
3Be 2/3 of nickel base superalloy only, the density after the alloying is 6.0g/cm
3About, thereby can improve specific tenacity effectively, reduce workpiece weight; The thermal conductivity of NiAl is big, and for general nickel base superalloy 4～8 times can make the thermograde of hot-end component reduce, thereby reduce thermal stresses, improve cold and hot fatigue property; In addition, NiAl also has excellent antioxidant property.But the normal temperature plasticity of NiAl is less than 1%, and fracture toughness property is 3～5MPam
1/2, 1000 ℃ of yield strengths of high temperature are less than 100MPa, have seriously limited the utilization of its practicability.
The in-situ authigenic composite technology is one of effective way that solves material room temperature fragility and hot strength problem.By adding transition element, as Cr, Mo, V etc., can form pseudo-two component eutectic with NiAl is to utilize its endogenous refractory metal can make that mutually intensity improves, fracture toughness property increases.The synusia shape of eutectic structure is organized very tiny, and interlamellar spacing has only a few tenths of extremely several micron apart, and the mean free path of dislocation is very little, and the pinning between phase and phase causes the Hall-Petch type to be strengthened; In addition, the plasticity in the eutectic alloy and the NiAl fragility crackle in mutually can produce interaction, shows as the crackle bridge joint intuitively, and crack deflection and crack blunting make the toughness of NiAl pseudoeutectic alloy be improved.Fracture toughness property as NiAl-Cr (Mo) biphase eutectic crystal alloy is 17～22MPam
1/2, its shock resistance also is better than AFN-12.But, the hot strength of NiAl-Cr (Mo) biphase eutectic crystal alloy is improved little, still can't satisfy the service requirements of gas turbine engine of new generation under 1150 ℃ of environment, carry out further composition design and tissue design, be the effective way that improves NiAl intermetallic compound over-all properties.
Summary of the invention
NiAl-Cr (Mo) biphase eutectic crystal intermetallic compound that the purpose of this invention is to provide a kind of V modification carries out modification by reduction Al constituent content, interpolation V element near the composition range the eutectic point of NiAl-Cr (Mo) biphase eutectic crystal alloy.V uniquely can form pseudo-two component eutectic system and Heusler element mutually simultaneously, and the effect of V and Cr is similar, will be dissolved among α-Cr in a large number, and separate out with α-Cr precipitated phase, and then play the effect of precipitation strength.Simultaneously, V can form the Heusler phase, and then strengthens matrix, helps improving high-temperature behavior.V has low-density characteristics, can develop 1150 ℃ of structural intermetallic compoundses of high temperature of low density, high specific strength, alleviate structural weight, raise the efficiency, reduce energy consumption, need reach the requirement of holding 1150 ℃ of warm abilities with alloy thereby bring huge social and economic benefit and satisfy gas turbine engine of new generation.
The present invention is a kind of NiAl-Cr (Mo) biphase eutectic crystal intermetallic compound of V modification, form by the nickel (Ni) of purity 99.999%, the aluminium (Al) of purity 99.999%, the chromium (Cr) of purity 99.999%, the molybdenum (Mo) of purity 99.999% and the vanadium (V) of purity 99.999%, composition range is the Ni of 33at%, the Cr of 30at%, the Mo of 4at%, the V of 1～16at% and the Al of surplus.
In the present invention, the NiAl-Cr of V modification (Mo) biphase eutectic crystal intermetallic compound can be 33Ni-30Al-30Cr-4Mo-3V or 33Ni-28Al-30Cr-4Mo-5V or 33Ni-25Al-30Cr-4Mo-8V or 33Ni-22Al-30Cr-4Mo-11V.
The advantage of the NiAl-Cr of V modification of the present invention (Mo) biphase eutectic crystal intermetallic compound is:
(1) by reduction Al constituent content, interpolation V element NiAl-Cr (Mo) biphase eutectic crystal alloy has been carried out modification.V uniquely can form pseudo-two component eutectic system and Heusler element mutually simultaneously, and the effect of V and Cr is similar, will be dissolved among α-Cr in a large number, and separate out with α-Cr precipitated phase, and then play the effect of precipitation strength.Simultaneously, V can form the Heusler phase, and then strengthens matrix, helps improving high-temperature behavior.Temperature-room type plasticity and toughness introduce on the basis of the NiAl-Cr of rich Ni (Mo) two-phase structure preferably suitable Heusler mutually and α-Cr precipitated phase further improve the hot strength of eutectic alloy, be formed on the structural intermetallic compounds that room temperature and high temperature all have better over-all properties with this.
(2) density of the NiAl-Cr of V modification (Mo) biphase eutectic crystal intermetallic compound is 6.0～6.6g/cm
3, yield strength is 1500～2500MPa in the time of 25 ℃, improves 50%～150% than unmodified NiAl-Cr (Mo) biphase eutectic crystal alloy, than waiting atomic ratio NiAl intermetallic compound to improve 120%～240%.Yield strength in the time of 1150 ℃ reaches 120～150MPa.
(3) compression plasticity of the NiAl-Cr of V modification (Mo) biphase eutectic crystal intermetallic compound improves 40% greater than 24% than unmodified NiAl-Cr (Mo) biphase eutectic crystal alloy, waits atomic ratio NiAl intermetallic compound to improve 140%.The toughness value of the fracture toughness property of alloy and NiAl-Cr (Mo) biphase eutectic crystal alloy is suitable after the modification, can reach 12～16MPam
1/2
(4) compression yield strength of 33Ni-22Al-30Cr-4Mo-11V alloy under 600 ℃, 800 ℃ is respectively 1800MPa, 700MPa, exceeds 157% and 40% than unmodified NiAl-Cr (Mo) alloy respectively.
Description of drawings
Fig. 1 is the compression experiment result under 25 ℃, 500 ℃, 600 ℃, 800 ℃, 1150 ℃ of 33Ni-22Al-30Cr-4Mo-11V intermetallic compound.
Fig. 2 is the compression experiment result under 25 ℃, 600 ℃, 800 ℃, 1150 ℃ of 33Ni-30Al-30Cr-4Mo-3V intermetallic compound.
Fig. 3 is the compression experiment result under 25 ℃, 600 ℃, 800 ℃, 1150 ℃ of 33Ni-28Al-30Cr-4Mo-5V intermetallic compound.
Fig. 4 is the compression experiment result under 25 ℃, 600 ℃, 800 ℃, 1150 ℃ of 33Ni-25Al-30Cr-4Mo-8V intermetallic compound.
Fig. 5 is the compression experiment result of 33Ni-33Al-30Cr-4Mo biphase eutectic crystal alloy under 25 ℃, 600 ℃, 800 ℃, 1150 ℃ of non-modified.Among the figure, 25 ℃ of yield strengths are 1100MPa, and compression plasticity is greater than 12%; 600 ℃ of yield strengths are 700MPa, and compression plasticity is greater than 43%; 800 ℃ of yield strengths are 500MPa, and compression plasticity is greater than 55%; Its 1150 ℃ of yield strengths are 100MPa.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
The present invention is a kind of NiAl-Cr (Mo) biphase eutectic crystal intermetallic compound of V modification, be room temperature fragility and hot strength problem at the NiAl intermetallic compound, on the basis of the two-way eutectic alloy of NiAl, develop a kind of strong biphase eutectic crystal base alloy of high temperature height ratio of V element modification, this alloy can substitute the conventional high-temperature alloy, alleviate structural remodeling weight, cut down the consumption of energy and bring huge social and economic benefit, and further satisfy gas turbine engine of new generation and need reach the requirement of holding 1150 ℃ of warm abilities with alloy.
The NiAl-Cr of V modification of the present invention (Mo) biphase eutectic crystal intermetallic compound, desired raw material is made up of the nickel (Ni) of purity 99.999%, the aluminium (Al) of purity 99.999%, the chromium (Cr) of purity 99.999%, the molybdenum (Mo) of purity 99.999% and the vanadium (V) of purity 99.999%, composition range is: the Ni of 33at%, the Cr of 30at%, the Mo of 4at%, the V of 1～16at% and the Al of surplus.
The NiAl-Cr of V modification of the present invention (Mo) biphase eutectic crystal intermetallic compound adopts the preparation of vacuum arc melting method, and this method is that the raw material that takes by weighing is in proportion put into non-consumable arc furnace melting ingot casting, vacuum tightness 1 * 10
-3～5 * 10
-3Pa, 2500 ℃～3000 ℃ of smelting temperatures turn refining 3～6 times, and the raw material melting evenly gets final product.In its preparation process, usually control alloy at room temperature and mechanical behavior under high temperature by content that changes Aluminum in Alloy (Al) element and vanadium (V) unit that adds corresponding content simultaneously.
NiAl-Cr (Mo) the biphase eutectic crystal intermetallic compound intermetallic compound ingot of the V modification that makes is carried out mechanics property analysis:
(1) adopt wire cutting method to cut sample and carry out proximate analysis, by the quality and the volume of accurate measure sample, the density of calculating intermetallic compound is 6.0～6.6g/cm
3, sample is diameter 6mm, the right cylinder of length 9mm.
(2) adopt material mechanics experiment machine (MTS) to carry out the test of room temperature and mechanical behavior under high temperature:
Its room temperature (25 ℃) yield strength is 1500～2500MPa, improves 50%～150% than unmodified NiAl-Cr (Mo) alloy, waits atomic ratio NiAl alloy to improve 120%～240%; Its compression plasticity improves 40% greater than 24% than unmodified NiAl-Cr (Mo) eutectic alloy, than waiting atomic ratio NiAl intermetallic compound to improve 140%.
Intermetallic compound of the present invention is respectively 1800MPa, 700MPa at 600 ℃～800 ℃ high-temperature yield strength, has improved 157% and 40% than the NiAl-Cr that does not add V element (Mo) alloy.
Adopt Instrons equipment to carry out the test of 1150 ℃ of mechanical properties of high temperature, laboratory sample is diameter 6mm, the right cylinder of length 9mm; Its yield strength is 120～150MPa.
(3) adopt material mechanics experiment machine (MTS) to carry out the test of room temperature material fracture toughness, laboratory sample is the square body of 6mm * 6mm * 30mm, and the strain rate during test is 0.02mm/min, and the fracture toughness property value is 12～16MPam
1/2
Intermetallic compound of the present invention is by suitably reducing the Al constituent content and adding V element NiAl-Cr (Mo) two-phase alloys has been carried out modification near the composition range its eutectic point.V uniquely can form pseudo-two component eutectic system and Heusler element mutually simultaneously, and the effect of V and Cr is similar, will be dissolved among α-Cr in a large number, and separate out with α-Cr precipitated phase, and then play the effect of precipitation strength.Simultaneously, V can form the Heusler phase, and then strengthens matrix, helps improving high-temperature behavior.Temperature-room type plasticity and toughness introduce on the basis of the NiAl-Cr of rich Ni (Mo) two-phase structure preferably suitable Heusler mutually and α-Cr precipitated phase further improve the hot strength of eutectic alloy, be formed on the structural intermetallic compounds that room temperature and high temperature all have better over-all properties with this.
The present invention develops the intermetallic compound of a kind of low density, high specific strength, can alleviate structural weight, raise the efficiency, reduce energy consumption, need reach the requirement of holding 1150 ℃ of warm abilities with alloy thereby bring huge social and economic benefit and satisfy gas turbine engine of new generation.
Embodiment 1:System 33Ni-22Al-30Cr-4Mo-11V intermetallic compound
According to composition is that 33Ni-22Al-30Cr-4Mo-11V (atomic percent) prepares burden, and its purity of raw materials is 99.999%.Adopt non-consumable arc furnace melting 33Ni-22Al-30Cr-4Mo-11V alloy cast ingot, vacuum tightness 5 * 10
-3Pa, 3000 ℃ of smelting temperatures turn refining 4 times, and the raw material melting evenly gets final product.
Adopt the high-temperature heat treatment stove to cool to room temperature with the furnace after 12 hours the intermetallic compound bar that makes in insulation under 1200 ℃.
Adopt the 33Ni-22Al-30Cr-4Mo-11V ingot of wire cutting method after the thermal treatment to cut diameter 6mm, the right cylinder sample of height 9mm and the square body of 6mm * 6mm * 30mm carry out Mechanics Performance Testing.
Adopting 1111 type tolerance range is 10
-4The mass M of the electronic balance measure sample of g, using tolerance range is 10
-2The end face diameter D and the length L of the vernier caliper measurement sample of mm adopt formula: ρ=4M * D-2 * (π L)
-1Calculate 33Ni-22Al-30Cr-4Mo-11V intermetallic compound density p (π is a pi in the formula), its density is 6.39g/cm
3
See also shown in Figure 1ly, adopt MTS-880 type universal material experimental machine to carry out Mechanics Performance Testing, its room temperature (25 ℃) yield strength is 2300MPa, and compression plasticity is greater than 24%; 500 ℃ of yield strengths are 2500MPa, and compression plasticity is greater than 36%; 600 ℃ of yield strengths are 1800MPa, and compression plasticity is greater than 40%; 800 ℃ of yield strengths are 700MPa, and compression plasticity is greater than 50%; 1150 ℃ of yield strengths are 142MPa.
Embodiment 2:System 33Ni-30Al-30Cr-4Mo-3V intermetallic compound
According to composition is that 33Ni-30Al-30Cr-4Mo-3V (atomic percent) prepares burden, and its purity of raw materials is 99.999%.Adopt non-consumable arc furnace melting 33Ni-30Al-30Cr-4Mo-3V alloy cast ingot, vacuum tightness 3 * 10
-3Pa, 2700 ℃ of smelting temperatures turn refining 6 times, and the raw material melting evenly gets final product.
Adopt the high-temperature heat treatment stove to cool to room temperature with the furnace after 12 hours the intermetallic compound bar that makes in insulation under 1200 ℃.
The Mechanics Performance Testing condition of 33Ni-30Al-30Cr-4Mo-3V intermetallic compound is identical with embodiment 1, and its density is 6.07g/cm
3Referring to shown in Figure 2, among the figure, yield strength is 2100MPa in the time of 25 ℃, and compression plasticity is greater than 23%; 600 ℃ of yield strengths are 1250MPa, and compression plasticity is greater than 40%; 800 ℃ of yield strengths are 620MPa, and compression plasticity is greater than 50%; 1150 ℃ of yield strengths are 124MPa.
Embodiment 3:System 33Ni-28Al-30Cr-4Mo-5V intermetallic compound
According to composition is that 33Ni-28Al-30Cr-4Mo-5V (atomic percent) prepares burden, and its purity of raw materials is 99.999%.Adopt non-consumable arc furnace melting 33Ni-28Al-30Cr-4Mo-5V alloy cast ingot, vacuum tightness 4 * 10
-3Pa, 2800 ℃ of smelting temperatures turn refining 5 times, and the raw material melting evenly gets final product.
Adopt the high-temperature heat treatment stove to cool to room temperature with the furnace after 12 hours the intermetallic compound bar that makes in insulation under 1200 ℃.
The Mechanics Performance Testing condition of 33Ni-28Al-30Cr-4Mo-5V intermetallic compound is identical with embodiment 1, and its density is 6.15g/cm
3Referring to shown in Figure 3, among the figure, yield strength is 2150MPa in the time of 25 ℃, and compression plasticity is greater than 25%; 600 ℃ of yield strengths are 1200MPa, and compression plasticity is greater than 40%; 800 ℃ of yield strengths are 615MPa, and compression plasticity is greater than 50%; 1150 ℃ of yield strengths are 128MPa.
Embodiment 4:System 33Ni-25Al-30Cr-4Mo-8V intermetallic compound
According to composition is that 33Ni-25Al-30Cr-4Mo-8V (atomic percent) prepares burden, and its purity of raw materials is 99.999%.Adopt non-consumable arc furnace melting 33Ni-25Al-30Cr-4Mo-8V alloy cast ingot, vacuum tightness is greater than 5 * 10
-3Pa, 2500 ℃ of smelting temperatures turn refining 6 times, and the raw material melting evenly gets final product.
Adopt the high-temperature heat treatment stove to cool to room temperature with the furnace after 12 hours the intermetallic compound bar that makes in insulation under 1200 ℃.
The Mechanics Performance Testing condition of 33Ni-25Al-30Cr-4Mo-8V intermetallic compound is identical with embodiment 1, and its density is 6.27g/cm
3Referring to shown in Figure 4, among the figure, yield strength is 2500MPa in the time of 25 ℃, and compression plasticity is greater than 27%; 600 ℃ of yield strengths are 1450MPa, and compression plasticity is greater than 40%; 800 ℃ of yield strengths are 650MPa, and compression plasticity is greater than 50%; 1150 ℃ of yield strengths are 132MPa.
Following table is that the intermetallic compound of different components is in vacuum tightness 3 * 10
-3Mechanical property under Pa, 3000 ℃ of smelting temperatures, 6 conditions of turning refining:
| Intermetallic compound | Density (g/cm 3) | Yield strength in the time of 1150 ℃ (MPa) | Yield strength in the time of 25 ℃ (MPa) |
| 33Ni-32Al-30Cr-4Mo-1V | 5.99 | 120 | 1500 |
| 33Ni-29Al-30Cr-4Mo-4V | 6.18 | 127 | 1850 |
| 33Ni-30Al-30Cr-4Mo-13V | 6.41 | 136 | 2270 |
| 33Ni-17Al-30Cr-4Mo-16V | 6.59 | 140 | 2200 |
The inventor is by near the composition range 33Ni-17～32Al-30Cr-4Mo-1～16V intermetallic compound eutectic point, suitably reduces the Al constituent content, adds V element NiAl-Cr (Mo) biphase eutectic crystal alloy is carried out modification.V uniquely can form pseudo-two component eutectic system and Heusler element mutually simultaneously, and the effect of V and Cr is similar, will be dissolved among α-Cr in a large number, and separate out with α-Cr precipitated phase, and then play the effect of precipitation strength.Simultaneously, V can form the Heusler phase, and then strengthens matrix, helps improving high-temperature behavior.Temperature-room type plasticity and toughness introduce on the basis of the NiAl-Cr of rich Ni (Mo) two-phase structure preferably suitable Heusler mutually and α-Cr precipitated phase further improve the hot strength of eutectic alloy.
Claims (9)
1, a kind of NiAl-Cr of V modification (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: described intermetallic compound is made up of the nickel (Ni) of purity 99.999%, the aluminium (Al) of purity 99.999%, the chromium (Cr) of purity 99.999%, the molybdenum (Mo) of purity 99.999% and the vanadium (V) of purity 99.999%, composition range is the Ni of 33at%, the Cr of 30at%, the Mo of 4at%, the V of 1～16at% and the Al of surplus.
2, the NiAl-Cr of V modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: described intermetallic compound is 33Ni-30Al-30Cr-4Mo-3V.
3, the NiAl-Cr of V modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: described intermetallic compound is 33Ni-28Al-30Cr-4Mo-5V.
4, the NiAl-Cr of V modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: described intermetallic compound is 33Ni-25Al-30Cr-4Mo-8V.
5, the NiAl-Cr of V modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: described intermetallic compound is 33Ni-22Al-30Cr-4Mo-11V.
6, the NiAl-Cr of V modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound is characterized in that: have NiAl phase, Cr (Mo) phase and Ni in the described intermetallic compound
2The AlV phase.
7, the NiAl-Cr of V modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: intermetallic compound density is 6.0～6.6g/cm
325 ℃ of yield strengths are 1500～2500MPa, and compression plasticity is greater than 24%; Yield strength in the time of 1150 ℃ reaches 120～150MPa.
8, the NiAl-Cr of V modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound is characterized in that: intermetallic compound is in air atmosphere, and through 1150 ℃ of isothermal oxidation 100h, the unit surface weightening finish is 5～8mg/cm
2
9, a kind of method for preparing NiAl-Cr (Mo) biphase eutectic crystal intermetallic compound of V modification as claimed in claim 1, it is characterized in that: the raw material that will take by weighing is in proportion put into non-consumable arc furnace melting ingot casting, vacuum tightness 1 * 10
-3～5 * 10
-3Pa, 2500 ℃～3000 ℃ of smelting temperatures turn refining 3～6 times, and the raw material melting evenly promptly ends.
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| CN113444955B (en) * | 2021-06-01 | 2022-03-22 | 西安理工大学 | High-entropy alloy containing eutectic structure and preparation method thereof |
| CN113930654B (en) * | 2021-10-22 | 2022-07-29 | 大连理工大学 | Casting alloy with high hardness and high specific yield strength under high temperature condition and preparation method thereof |
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Non-Patent Citations (2)
| Title |
|---|
| NiAl(Ti)-Cr(Mo)共晶合金的微观组织和力学性能. 肖旋，郭建亭，于海朋.金属学报，第42卷第10期. 2006 |
| NiAl(Ti)-Cr(Mo)共晶合金的微观组织和力学性能. 肖旋，郭建亭，于海朋.金属学报，第42卷第10期. 2006 * |
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