CN100510138C - NiAl-Cr(Mo) biphase eutectic crystal intermetallic compound modified by Co - Google Patents
NiAl-Cr(Mo) biphase eutectic crystal intermetallic compound modified by Co Download PDFInfo
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- CN100510138C CN100510138C CNB2007101761141A CN200710176114A CN100510138C CN 100510138 C CN100510138 C CN 100510138C CN B2007101761141 A CNB2007101761141 A CN B2007101761141A CN 200710176114 A CN200710176114 A CN 200710176114A CN 100510138 C CN100510138 C CN 100510138C
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Abstract
The present invention discloses one kind of Co modified two-phase eutectic intermetallic NiAl-Cr(Mo) compound comprising Ni in 33 at.%, Cr in 30 at.%, Mo in 4 at.%, Co 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 Co element with solid solution reinforcing effect to modify and introduce one third plastic phase, the Co modified two-phase eutectic intermetallic NiAl-Cr(Mo) compound has further raised high temperature strength and room temperature toughness and plasticity. The Co modified two-phase eutectic intermetallic NiAl-Cr(Mo) compound has yield strength at 1150 deg.c of 110-130 MPa and density of 6.02-7.06 g/cu cm.
Description
Technical field
The present invention relates to a kind of NiAl-Cr (Mo) biphase eutectic crystal intermetallic compound of Co 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 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, 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) eutectic 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, carrying out further composition design and tissue design, is 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 Co modification, carry out modification by near the reduction Al constituent content eutectic point of NiAl-Cr (Mo) biphase eutectic crystal alloy, interpolation Co element, and the solution strengthening effect of Co element, introduce on the basis of NiAl-Cr (Mo) two-phase structure that suitable plasticity third phase γ comes further to improve the hot strength of NiAl-Cr (Mo) biphase eutectic crystal alloy mutually with γ ' mutually and room temperature is tough, plasticity.Develop 1150 ℃ of structural intermetallic compoundses of high temperature of 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 Co 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 cobalt (Co) of purity 99.999%, composition range is the Ni of 33at%, the Cr of 30at%, the Mo of 4at%, the Co of 1～16at% and the Al of surplus.
In the present invention, the NiAl-Cr of Co modification (Mo) biphase eutectic crystal intermetallic compound can be 33Ni-30Al-30Cr-4Mo-3Co or 33Ni-28Al-30Cr-4Mo-5Co or 33Ni-25Al-30Cr-4Mo-8Co or 33Ni-22Al-30Cr-4Mo-11Co.
In the present invention, the density of the NiAl-Cr of Co modification (Mo) biphase eutectic crystal intermetallic compound is 6.02～7.06g/cm
325 ℃ of yield strengths are that 1500～2600MPa, compression plasticity are greater than 27%; Yield strength in the time of 1150 ℃ is 110～130MPa.
The advantage of the NiAl-Cr of Co modification of the present invention (Mo) biphase eutectic crystal intermetallic compound is:
(1) by reducing the Al constituent content and adding the Co element NiAl-Cr (Mo) biphase eutectic crystal alloy is carried out the solution strengthening effect of modification and Co element, introduce on the basis of NiAl-Cr (Mo) two-phase structure that suitable plasticity third phase γ comes further to improve the hot strength of eutectic alloy mutually with γ ' mutually and room temperature is tough, plasticity, be formed on the structural intermetallic compounds 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 Co modification is 6.02～7.06g/cm
3
(3) yield strength of NiAl-Cr (Mo) biphase eutectic crystal alloy in the time of 25 ℃ after the Co modification is 1500～2600MPa, improved 50%～150% than unmodified NiAl-Cr (Mo) biphase eutectic crystal alloy, than waiting atomic ratio NiAl intermetallic compound to improve 120%～240%; Its compression plasticity has improved 30% greater than 20% than unmodified NiAl-Cr (Mo) biphase eutectic crystal alloy, than waiting atomic ratio NiAl intermetallic compound to improve 170%;
(4) compression yield strength of 33Ni-25Al-30Cr-4Mo-8Co intermetallic compound under 600 ℃, 800 ℃ is respectively 1600MPa, 650MPa, exceeds 160%, 30% than unmodified NiAl-Cr (Mo) biphase eutectic crystal alloy respectively;
(5) yield strength of NiAl-Cr (Mo) biphase eutectic crystal alloy in the time of 1150 ℃ after the Co modification reaches 110～130MPa.
Description of drawings
Fig. 1 is the compression experiment result under 25 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 1150 ℃ of 33Ni-25Al-30Cr-4Mo-8Co intermetallic compound.
Fig. 2 is the compression experiment result under 25 ℃, 800 ℃, 1150 ℃ of 33Ni-22Al-30Cr-4Mo-11Co intermetallic compound.
Fig. 3 is the compression experiment result under 25 ℃, 700 ℃, 800 ℃, 1150 ℃ of 33Ni-30Al-30Cr-4Mo-3Co intermetallic compound.
Fig. 4 is the compression experiment result under 25 ℃, 700 ℃, 800 ℃, 1150 ℃ of 33Ni-28Al-30Cr-4Mo-5Co 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 1400MPa, and compression plasticity is greater than 15%; 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 Co 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 the strong biphase eutectic crystal base alloy of the element modified high temperature height ratio of a kind of Co, this alloy can substitute 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 Co 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 cobalt (Co) of purity 99.999%, composition range is: the Ni of 33at%, the Cr of 30at%, the Mo of 4at%, the Co of 1～16at% and the Al of surplus.
Intermetallic compound of the present invention adopts the preparation of vacuum arc melting method, and this method is to put into non-consumable arc furnace melting ingot casting by the raw material that 33Ni-17～32Al-30Cr-4Mo-1～the 16Co component proportions takes by weighing, and vacuum tightness is greater than 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 cobalt (Co) 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 6.02～7.06g/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 1500～2600MPa, has improved 50%～150% than unmodified NiAl-Cr (Mo) biphase eutectic crystal alloy, than waiting atomic ratio NiAl alloy to improve 120%～240%; Compression plasticity has improved 30% greater than 20% than unmodified NiAl-Cr (Mo) biphase eutectic crystal alloy, than waiting atomic ratio NiAl intermetallic compound to improve 170%.
Intermetallic compound of the present invention is respectively 1600MPa, 650MPa at 600 ℃～800 ℃ high-temperature yield strength, has improved 160%, 30% than the NiAl-Cr that does not add the Co element (Mo) biphase eutectic crystal 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 110～130MPa.
(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 12～18MPam
1/2
Intermetallic compound of the present invention is by suitably reducing the Al constituent content and adding the Co element NiAl-Cr (Mo) two-phase alloys has been carried out modification near the composition range its eutectic point, solution strengthening effect by the Co element, and introduce on the basis of NiAl-Cr (Mo) two-phase structure that suitable plasticity third phase γ comes further to improve the hot strength of eutectic alloy mutually with γ ' mutually and room temperature is tough, plasticity, 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-25Al-30Cr-4Mo-8Co intermetallic compound
According to composition is that 33Ni-25Al-30Cr-4Mo-8Co (atomic percent) prepares burden, and its purity of raw materials is 99.999%.
Adopt non-consumable arc furnace melting 33Ni-25Al-30Cr-4Mo-8Co alloy cast ingot, vacuum tightness is greater than 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-25Al-30Cr-4Mo-8Co 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-25Al-30Cr-4Mo-8Co intermetallic compound density p (π is a pi in the formula), its density is 6.49g/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 yield strength is 2600MPa, and compression plasticity is greater than 27%; Its 500 ℃ of yield strengths are 2300MPa, and compression plasticity is greater than 32%; Its 600 ℃ of yield strengths are 1700MPa, and compression plasticity is greater than 43%; Its 700 ℃ of yield strengths are 950MPa, and compression plasticity is greater than 50%; Its 800 ℃ of yield strengths are 630MPa, and compression plasticity is greater than 50%; Its 1150 ℃ of yield strengths are 126MPa.
Embodiment 2:System 33Ni-22Al-30Cr-4Mo-11Co intermetallic compound
According to composition is that 33Ni-22Al-30Cr-4Mo-11Co (atomic percent) prepares burden, and its purity of raw materials is 99.999%.
Adopt non-consumable arc furnace melting 33Ni-22Al-30Cr-4Mo-11Co 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-22Al-30Cr-4Mo-11Co intermetallic compound is identical with embodiment 1, and its density is 6.70g/cm
3Referring to shown in Figure 2, the room temperature yield strength is 2200MPa, and compression plasticity is greater than 20%; 800 ℃ of yield strengths are 620MPa, and compression plasticity is greater than 60%; 1150 ℃ of yield strengths are 123MPa.
Embodiment 3:System 33Ni-30Al-30Cr-4Mo-3Co intermetallic compound
According to composition is that 33Ni-30Al-30Cr-4Mo-3Co (atomic percent) prepares burden, and its purity of raw materials is 99.999%.
Adopt non-consumable arc furnace melting 33Ni-30Al-30Cr-4Mo-3Co alloy cast ingot, vacuum tightness 4 * 10
-3Pa, 2800 ℃ of smelting temperatures turn refining 3 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-3Co intermetallic compound is identical with embodiment 1, and its density is 6.15g/cm
3Referring to shown in Figure 3, the room temperature yield strength is 1900MPa, and compression plasticity is greater than 21%; 700 ℃ of yield strengths are 1000MPa, and compression plasticity is greater than 60%; 800 ℃ of yield strengths are 630MPa, and compression plasticity is greater than 60%; 1150 ℃ of yield strengths are 116MPa.
Embodiment 4:System 33Ni-28Al-30Cr-4Mo-5Co intermetallic compound
According to composition is that 33Ni-28Al-30Cr-4Mo-5Co (atomic percent) prepares burden, and its purity of raw materials is 99.999%.
Adopt non-consumable arc furnace melting 33Ni-28Al-30Cr-4Mo-5Co alloy cast ingot, vacuum tightness 4 * 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-28Al-30Cr-4Mo-5Co intermetallic compound is identical with embodiment 1, and its density is 6.28g/cm
3Referring to shown in Figure 4, the room temperature yield strength is 2000MPa, and compression plasticity is greater than 25%; 700 ℃ of yield strengths are 1050MPa, and compression plasticity is greater than 60%; 800 ℃ of yield strengths are 620MPa, and compression plasticity is greater than 60%; 1150 ℃ of yield strengths are 120MPa.
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-1Co | 6.02 | 112 | 1600 |
| 33Ni-29Al-30Cr-4Mo-4Co | 6.24 | 119 | 2050 |
| 33Ni-23Al-30Cr-4Mo-10Co | 6.52 | 125 | 2600 |
| 33Ni-17Al-30Cr-4Mo-16Co | 7.06 | 128 | 2200 |
The inventor is by suitably reducing the Al constituent content and adding the Co element NiAl-Cr (Mo) two-phase alloys has been carried out modification near the composition range 33Ni-17～32Al-30Cr-4Mo-1～16Co intermetallic compound eutectic point, by the solution strengthening effect of Co element, and introduce on the basis of NiAl-Cr (Mo) two-phase structure that suitable plasticity third phase γ comes further to improve the hot strength of eutectic alloy mutually with γ ' mutually and room temperature is tough, plasticity.
Claims (8)
1, a kind of NiAl-Cr of Co modification (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: described intermetallic compound is made up of the Ni of purity 99.999%, Al, the Cr of purity 99.999%, the Mo of purity 99.999% and the Co of purity 99.999% of purity 99.999%, composition range is the Ni of 33at%, the Cr of 30at%, the Mo of 4at%, the Co of 1～16at% and the Al of surplus.
2, the NiAl-Cr of Co modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: described intermetallic compound is 33Ni-30Al-30Cr-4Mo-3Co.
3, the NiAl-Cr of Co modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: described intermetallic compound is 33Ni-28Al-30Cr-4Mo-5Co.
4, the NiAl-Cr of Co modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: described intermetallic compound is 33Ni-25Al-30Cr-4Mo-8Co.
5, the NiAl-Cr of Co modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: described intermetallic compound is 33Ni-22Al-30Cr-4Mo-11Co.
6, the NiAl-Cr of Co modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound, it is characterized in that: intermetallic compound density is 6.02～7.06g/cm
325 ℃ of yield strengths are that 1500～2600MPa, compression plasticity are greater than 27%; Yield strength in the time of 1150 ℃ is 110～130MPa.
7, the NiAl-Cr of Co modification according to claim 1 (Mo) biphase eutectic crystal intermetallic compound is characterized in that: intermetallic compound is in air atmosphere, and behind 1150 ℃ of isothermal oxidation 100h, the unit surface weightening finish is 8～10mg/cm
2
8, a kind of method for preparing NiAl-Cr (Mo) biphase eutectic crystal intermetallic compound of Co modification as claimed in claim 1 is characterized in that: will be by Ni
33Al
17～32Cr
30Mo
4Co
1～16The raw material that composition takes by weighing is put into non-consumable arc furnace melting ingot casting, vacuum tightness 1～5 * 10
-3Pa, 2500 ℃～3000 ℃ of smelting temperatures turn refining 3～6 times, and the raw material melting evenly promptly ends.
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| CN112522542B (en) * | 2020-11-17 | 2022-04-15 | 扬州大学 | La-Mg-Ni-Co based biphase superlattice hydrogen storage alloy 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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