CN100523247C - NiAl-Cr(Mo) biphase eutectic crystal intermetallic compound modified by Hf - Google Patents
NiAl-Cr(Mo) biphase eutectic crystal intermetallic compound modified by Hf Download PDFInfo
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- CN100523247C CN100523247C CNB2007101761156A CN200710176115A CN100523247C CN 100523247 C CN100523247 C CN 100523247C CN B2007101761156 A CNB2007101761156 A CN B2007101761156A CN 200710176115 A CN200710176115 A CN 200710176115A CN 100523247 C CN100523247 C CN 100523247C
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Abstract
The present invention discloses one kind of Hf modified two-phase eutectic intermetallic NiAl-Cr(Mo) compound comprising Ni in 33 at.%, Cr in 30 at.%, Mo in 4 at.%, Hf in 0.1-11 at.% and Al for the rest. By means of lowering Al content in the two-phase eutectic intermetallic NiAl-Cr(Mo) alloy, and adding Hf element to modify and form one Heusler (L21-Ni2AlHf) phase with NiAl, the Hf modified two-phase eutectic intermetallic NiAl-Cr(Mo) compound has high room temperature toughness and plasticity and further raised high temperature strength. The Hf modified two-phase eutectic intermetallic NiAl-Cr(Mo) compound has yield strength at 1150 deg.c of 300-420 MPa and density of 6.02-7.66 g/cu cm.
Description
Technical field
The present invention relates to a kind of NiAl-Cr (Mo) biphase eutectic crystal intermetallic compound of Hf modification.
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 novel high-temperature alloy 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 3～5MPa
, 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, W 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 intermetallic compound 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 intermetallic compound is improved little, still can't satisfy the service requirements of gas turbine engine of new generation under 1150 ℃ of environment.
Summary of the invention
NiAl-Cr (Mo) biphase eutectic crystal intermetallic compound that the purpose of this invention is to provide a kind of Hf modification, by on the basis of NiAl-Cr (Mo) biphase eutectic crystal alloy, suitably reduce the Al constituent content near the composition range its eutectic point, add of the modification of Hf element NiAl-Cr (Mo) biphase eutectic crystal alloy.Hf element and NiAl have and form Heusler (L21-Ni consumingly
2AlHf) trend of phase is introduced the hot strength that suitable Heusler comes further to improve eutectic alloy mutually on the basis of the NiAl-Cr of rich Ni (Mo) two-phase structure preferably in temperature-room type plasticity and toughness.Develop 1150 ℃ of structural intermetallic compoundses of high temperature of novel low density, high specific strength with this, 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 Hf 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 hafnium (Hf) of purity 99.999%, composition range is the Ni of 33at%, the Cr of 30at%, the Mo of 4at%, the Hf of 0.1～11at% and the Al of surplus.
In the present invention, the NiAl-Cr of Hf modification (Mo) biphase eutectic crystal intermetallic compound can be 33Ni-32Al-30Cr-4Mo-1Hf or 33Ni-30Al-30Cr-4Mo-3Hf or 33Ni-28Al-30Cr-4Mo-5Hf or 33Ni-25Al-30Cr-4Mo-8Hf.
In the present invention, the density of the NiAl-Cr of Hf modification (Mo) biphase eutectic crystal intermetallic compound is 6.02～7.66g/cm
325 ℃ of yield strengths are that 1500～2300MPa, compression plasticity are greater than 17%; Yield strength in the time of 1150 ℃ is 300～420MPa.
The advantage of the NiAl-Cr of Hf modification of the present invention (Mo) biphase eutectic crystal intermetallic compound is:
(1) by reduction Al constituent content, interpolation Hf element NiAl-Cr (Mo) biphase eutectic crystal alloy is carried out modification, Hf element and NiAl have intensive Heusler (L21-Ni
2AlHf) form trend mutually, introduce the hot strength that suitable Heusler comes further to improve eutectic alloy mutually on the basis of the NiAl-Cr of rich Ni (Mo) two-phase structure preferably in temperature-room type plasticity and toughness, be formed on the novel texture intermetallic compound that room temperature and high temperature all have better over-all properties with this;
(2) NiAl-Cr (Mo) the biphase eutectic crystal alloy density after the Hf modification is 6.02～7.66g/cm
3
(3) NiAl-Cr (Mo) the biphase eutectic crystal alloy at room temperature yield strength after the Hf modification is 1500～2300MPa, improves 50%～100% than unmodified NiAl-Cr (Mo) alloy, than waiting atomic ratio NiAl intermetallic compound to improve 150%～240%.Compression plasticity is greater than 17%, than waiting atomic ratio NiAl intermetallic compound to improve 70%.
(4) compression yield strength of 33Ni-28Al-30Cr-4Mo-5Hf alloy under 800 ℃ is 1600MPa, exceeds 220% than the pseudo-binary eutectic alloy of unmodified NiAl-Cr (Mo).
(5) yield strength of NiAl-Cr (Mo) biphase eutectic crystal alloy in the time of 1150 ℃ after the Hf modification is 300～420MPa
Description of drawings
Fig. 1 is the 33Ni-28Al-30Cr-4Mo-5Hf intermetallic compound 25 ℃, 800 ℃, 850 ℃, 1150 ℃ compression experiment result.
Fig. 2 is the 33Ni-30Al-30Cr-4Mo-3Hf intermetallic compound 25 ℃, 800 ℃, 850 ℃, 1150 ℃ compression experiment result.
Fig. 3 is the 33Ni-32Al-30Cr-4Mo-1Hf intermetallic compound 25 ℃, 800 ℃, 850 ℃, 1150 ℃ compression experiment result.
Fig. 4 is the 33Ni-25Al-30Cr-4Mo-8Hf intermetallic compound 25 ℃, 800 ℃, 850 ℃, 1150 ℃ compression experiment result.
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 Hf modification, be room temperature fragility and hot strength problem at the NiAl intermetallic compound, on the basis of NiAl-Cr (Mo) biphase eutectic crystal alloy, develop the element modified strong intermetallic compound of new type high temperature height ratio of a kind of Hf, this intermetallic compound has substituted the conventional high-temperature alloy, alleviate structural 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 Hf 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 hafnium (Hf) of purity 99.999%, composition range is: the Ni of 33at%, the Cr of 30at%, the Mo of 4at%, the Hf of 0.1～11at% and the Al of surplus.
In the present invention, the preferable span of Hf atomic percent is 3～8.
Intermetallic compound of the present invention 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 hafnium (Hf) unit that adds corresponding content simultaneously.
The intermetallic compound ingot 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 6.02～7.66g/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 1500～2300MPa, improves 50%～100% than unmodified NiAl-Cr (Mo) biphase eutectic crystal alloy, than waiting atomic ratio NiAl intermetallic compound to improve 150%～240%.Compression plasticity is greater than 17%, than waiting atomic ratio NiAl intermetallic compound to improve 70%.
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 300～420MPa.
(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 5～10MPam
1/2
Intermetallic compound of the present invention is by suitably reducing the Al constituent content near the composition range its eutectic point and adding the Hf element NiAl-Cr (Mo) biphase eutectic crystal alloy has been carried out modification, by Hf element and NiAl intensive Heusler (L21-Ni
2AlHf) form trend mutually, introduce the hot strength that suitable Heusler comes further to improve eutectic alloy mutually on the basis of the NiAl-Cr of rich Ni (Mo) two-phase structure preferably in temperature-room type plasticity and toughness, be formed on the novel texture intermetallic compound that room temperature and high temperature all have better over-all properties with this.
The present invention develops a kind of novel low density, the intermetallic compound of 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-28Al-30Cr-4Mo-5Hf intermetallic compound
According to composition is that 33Ni-28Al-30Cr-4Mo-5Hf (atomic percent) prepares burden, and its purity of raw materials is 99.999%.
Adopt non-consumable arc furnace melting 33Ni-28Al-30Cr-4Mo-5Hf alloy cast ingot, vacuum tightness 3 * 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-28Al-30Cr-4Mo-5Hf 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 Ni-28Al-30Cr-4Mo-5Hf intermetallic compound density p (π is a pi in the formula), its density is 6.76g/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 2200MPa, and compression plasticity is greater than 21%; Its 800 ℃ of yield strengths are 1400MPa, and compression plasticity is greater than 40%; Its 850 ℃ of yield strengths are 1250MPa, and compression plasticity is greater than 50%; Its 1150 ℃ of yield strengths are 420MPa.
Embodiment 2:System 33Ni-30Al-30Cr-4Mo-3Hf intermetallic compound
According to composition is that 33Ni-30Al-30Cr-4Mo-3Hf (atomic percent) prepares burden, and its purity of raw materials is 99.999%.
Adopt non-consumable arc furnace melting 33Ni-30Al-30Cr-4Mo-3Hf alloy cast ingot, vacuum tightness 5 * 10
-3Pa, 2700 ℃ 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-30Al-30Cr-4Mo-3Hf intermetallic compound is identical with embodiment 1, and its density is 6.11g/cm
3Referring to shown in Figure 2, among the figure, room temperature (25 ℃) yield strength is 2000MPa, and compression plasticity is greater than 17%; 800 ℃ of yield strengths are 1300MPa, and compression plasticity is greater than 30%; 850 ℃ of yield strengths are 1200MPa, and compression plasticity is greater than 35%; 1150 ℃ of yield strengths are 354MPa.
Embodiment 3:System 33Ni-32Al-30Cr-4Mo-1Hf intermetallic compound
According to composition is that 33Ni-32Al-30Cr-4Mo-1Hf (atomic percent) prepares burden, and its purity of raw materials is 99.999%.
Adopt non-consumable arc furnace melting 33Ni-32Al-30Cr-4Mo-1Hf alloy cast ingot, vacuum tightness 5 * 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-32Al-30Cr-4Mo-1Hf intermetallic compound is identical with embodiment 1, and its density is 6.03g/cm
3Referring to shown in Figure 3, among the figure, room temperature (25 ℃) yield strength is 1900MPa, and compression plasticity is greater than 21%; 800 ℃ of yield strengths are 1150MPa, and compression plasticity is greater than 35%; 850 ℃ of yield strengths are 960MPa, and compression plasticity is greater than 50%; 1150 ℃ of yield strengths are 323MPa.
Embodiment 4:System 33Ni-25Al-30Cr-4Mo-8Hf intermetallic compound
According to composition is that 33Ni-25Al-30Cr-4Mo-8Hf (atomic percent) prepares burden, and its purity of raw materials is 99.999%.
Adopt non-consumable arc furnace melting 33Ni-25Al-30Cr-4Mo-8Hf alloy cast ingot, vacuum tightness 5 * 10
-3Pa, 3000 ℃ 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-25Al-30Cr-4Mo-8Hf intermetallic compound is identical with embodiment 1, and its density is 6.21g/cm
3Referring to shown in Figure 4, among the figure, room temperature (25 ℃) yield strength is 2200MPa, and compression plasticity is greater than 21%; 800 ℃ of yield strengths are 1250MPa, and compression plasticity is greater than 28%; 850 ℃ of yield strengths are 1050MPa, and compression plasticity is greater than 50%; 1150 ℃ of yield strengths are 345MPa.
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-32.5Al-30Cr-4Mo-0.5Hf | 6.03 | 314 | 1500 |
| 33Ni-29Al-30Cr-4Mo-4Hf | 6.56 | 372 | 2100 |
| 33Ni-26Al-30Cr-4Mo-7Hf | 7.08 | 386 | 2250 |
| 33Ni-22Al-30Cr-4Mo-11Hf | 7.66 | 367 | 2150 |
The inventor is by suitably reducing the Al constituent content near the composition range 33Ni-22～32.9Al-30Cr-4Mo-0.1～11Hf intermetallic compound eutectic point and adding the Hf element NiAl-Cr (Mo) biphase eutectic crystal alloy has been carried out modification, by Hf element and NiAl intensive Heusler (L21-Ni
2AlHf) form trend mutually, introduce the hot strength that suitable Heusler comes further to improve eutectic alloy mutually on the basis of the NiAl-Cr of rich Ni (Mo) two-phase structure preferably in temperature-room type plasticity and toughness.
Claims (2)
1, a kind of NiAl-Cr of Hf modification (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: described intermetallic compound is made up of nickel (Ni), aluminium (Al), chromium (Cr), molybdenum (Mo) and hafnium (Hf), composition range is the Ni of 33at%, the Cr of 30at%, the Mo of 4at%, the Hf of 0.1～11at% and the Al of surplus;
Have NiAl phase, Cr (Mo) phase, Ni in the described intermetallic compound
2The Solid solution of AlHf phase (Heusler phase) and Hf;
Described intermetallic compound density is 6.02～7.66g/cm
325 ℃ of yield strengths are that 1500～2300MPa, compression plasticity are greater than 17%; Yield strength in the time of 1150 ℃ is 300～420MPa;
Described intermetallic compound is in air atmosphere, and through 1150 ℃ of isothermal oxidation 100h, the unit surface weightening finish is 3～6mg/cm
2
2, a kind of method for preparing NiAl-Cr (Mo) biphase eutectic crystal intermetallic compound of Hf modification as claimed in claim 1, it is characterized in that: will take by weighing 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 hafnium (Hf) of purity 99.999% in proportion and 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.
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