CN101139675A - Titanium nickel aluminium niobium hafnium high-temperature alloy material - Google Patents

Titanium nickel aluminium niobium hafnium high-temperature alloy material Download PDF

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CN101139675A
CN101139675A CNA2007101755117A CN200710175511A CN101139675A CN 101139675 A CN101139675 A CN 101139675A CN A2007101755117 A CNA2007101755117 A CN A2007101755117A CN 200710175511 A CN200710175511 A CN 200710175511A CN 101139675 A CN101139675 A CN 101139675A
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titanium
purity
alloy material
temperature alloy
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CN100577838C (en
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李岩
宋晓云
徐惠彬
于开元
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Beihang University
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Beihang University
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Abstract

The invention discloses a Ti-Ni-Al-Nb-Hf high-temperature alloy material, which is composed of 37at per cent to 52at per cent Ti, 45at per cent to 50at per cent Ni, 1at per cent to 6at per cent Al, 1at per cent to 3at per cent Nb, and 1at per cent to 4at per cent Zr. The alloy is of good durability and excellent anti-oxidation performance. Under 20 DEG C, the yield strength of the alloy is 1200 to 2400 MPa, the deformation rate is more than 10 per cent while under 600-800 DEG C, the yield strength of the alloy is 1450 to 400 MPa.

Description

A kind of titanium nickel aluminium niobium hafnium high-temperature alloy material
Technical field
The present invention relates to a kind of Ti 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4High temperature alloy usually improves a kind of novel high-temperature alloy material of room temperature yield strength, mechanical behavior under high temperature and the enduring quality of Ti-Ni alloy by add Al, Nb, Hf unit in Ti-Ni alloy.
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 low density, high-intensity novel high-temperature alloy to adapt to the needs of related industries field future development.
The binary TiNi alloy is a kind of have good mechanical property, good solidity to corrosion and intermetallic compound of biocompatibility, is widely used in fields such as medical science, industry and lives as the shape memory alloy functional materials.The density of this alloy is 6.3g/cm 3About, than Ni-based, iron-based and cobalt base superalloy low about 20%.
On TiNi alloy basis, can significantly improve alloy at room temperature and hot strength by adding the Al element, have the potentiality of using at aerospace field.The interpolation of Nb element can improve alloy room temperature, mechanical behavior under high temperature and high-temperature oxidation resistance.
On the basis of TiNiAlNb alloy, add certain amount of H f, not only can further improve alloy at room temperature and hot strength, and can obviously improve the enduring quality of alloy, develop novel low density, the alternative conventional high-temperature alloy of high strength superalloy, can alleviate structural weight, raise the efficiency, reduce energy consumption.
Summary of the invention
The objective of the invention is to propose a kind of low density, high specific strength TiNiAlNbHf high temperature alloy, this TiNiAlNbHf superalloy uses at high temperature as structured material, can substitute that traditional high-density is Ni-based, iron-based and cobalt base superalloy material, can alleviate structural weight, raise the efficiency, reduce energy consumption.
A kind of titanium nickel aluminium niobium hafnium high-temperature alloy material of the present invention is made up of the titanium (Ti) of 37at%～52at%, the nickel (Ni) of 45at%～50at%, the aluminium (Al) of 1at%～6at%, the niobium (Nb) of 1at%～3at% and the hafnium (Hf) of 1at%～4at%.
Described high-temperature titanium aluminium niobium alloy materials component is Ti 41Ni 49Al 5Nb 2Hf 3, Ti 37Ni 50Al 6Nb 3Hf 4Perhaps Ti 46Ni 46Al 4Nb 2Hf 2
Described Ti 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4High temperature alloy has good enduring quality and excellent antioxidant property; Yield strength in the time of 20 ℃ is 1200MPa～2400MPa, and deformation rate is greater than 10%; Yield strength in the time of 600 ℃～800 ℃ is 1450MPa～400MPa.
Prepare Ti of the present invention 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4The step of high temperature alloy has:
(1) presses Ti 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4It is that 99.9% titanium (Ti), purity are that 99.9% nickel (Ni), purity are that 99.9% aluminium (Al), purity are that 99.9% niobium (Nb) and purity are 99.9% hafnium (Hf) that proportioning takes by weighing purity;
(2) the above-mentioned raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 2 * 10 -3Pa～5 * 10 -3Pa charges into high-purity argon gas to 1.01 * 10 5Pa is smelted into TiNiAlNbHf superalloy ingot at 2700 ℃～3000 ℃ then;
(3) the above-mentioned TiNiAlNbHf superalloy ingot that makes is put into vacuum heat treatment furnace and heat-treat, in vacuum tightness 2 * 10 -3Pa～5 * 10 -3Pa, 850 ℃～1000 ℃ insulation is after 12～24 hours down for thermal treatment temp, and furnace cooling promptly obtains Ti 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4High temperature alloy.
Ti of the present invention 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4The advantage of high temperature alloy: (1) usually improves alloy at room temperature, mechanical behavior under high temperature and high temperature endurance performance by adding high purity Hf unit on TiNiAlNb alloy basis, this class alloy has excellent enduring quality; Yield strength in the time of 20 ℃ is 1200～2400MPa, and deformation rate is greater than 10%; Yield strength in the time of 600 ℃～800 ℃ is 1450MPa～400MPa.100 hours oxidation weight gains are 0.005mg/cm in 600 ℃～800 ℃, still air 2～4.50mg/cm 2600 ℃/400MPa following creep rupture life 〉=110h, 700 ℃/350MPa following creep rupture life 〉=80h; (2) this TiNiAlNbHf high temperature alloy is compared with the TiNiAlNb superalloy with identical Al, Nb atomic percent, has better room temperature, mechanical behavior under high temperature, has more excellent enduring quality at 600 ℃～700 ℃.
Description of drawings
Fig. 1 is Ti 41Ni 49Al 5Nb 2Hf 3The compression testing result curve figure of cylinder sample under 20 ℃, 600 ℃, 650 ℃, 700 ℃ and 800 ℃ of temperature.
Fig. 2 is Ti 37Ni 50Al 6Nb 3Hf 4The compression testing result curve figure of cylinder sample under 650 ℃, 800 ℃ of temperature.
Fig. 3 is Ti 46Ni 46Al 4Nb 2Hf 2The compression testing result curve figure of cylinder sample under 600 ℃, 800 ℃ of temperature.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
The present invention is a kind of Ti 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4High temperature alloy is made up of the titanium (Ti) of 37at%～52at%, the nickel (Ni) of 45at%～50at%, the aluminium (Al) of 1at%～6at%, the niobium (Nb) of 1at%～3at% and the hafnium (Hf) of 1at%～4at%.
Ti of the present invention 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4The preparation method and the step of high temperature alloy are as follows:
(1) presses Ti 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4It is that 99.9% titanium, purity are that 99.9% nickel, purity are that 99.9% aluminium, purity are that 99.9% niobium and purity are 99.9% hafnium that proportioning takes by weighing purity;
(2) the above-mentioned raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 2 * 10 -3Pa～5 * 10 -3Pa charges into high-purity argon gas to 1.01 * 10 5Pa is smelted into TiNiAlNbHf superalloy ingot at 2700 ℃～3000 ℃ then;
(3) the above-mentioned TiNiAlNbHf superalloy ingot that makes is put into vacuum heat treatment furnace and heat-treat, in vacuum tightness 2 * 10 -3Pa～5 * 10 -3Pa, the insulation after 12～24 hours down of 850 ℃～1000 ℃ of thermal treatment temps, furnace cooling promptly obtains the Ti of requirement of the present invention 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4High temperature alloy.
Adopt wire cutting method, at the above-mentioned Ti that makes 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4Cut diameter d=6mm in the high temperature alloy, the right cylinder of height h=9mm is as the Mechanics Performance Testing sample, adopt MTS-880 type universal material experimental machine to carry out compression pressure-strain testing, compressive strain speed is 0.2mm/min, and temperature range is a chosen temperature point between 20 ℃～800 ℃.Adopt wire cutting method to cut long L=10mm, wide W=5mm, the rectangular parallelepiped sample of high H=5mm be as the high temperature oxidation resistance specimen, the mass M of measure sample 1, selected temperature point between 600 ℃～800 ℃, place the still air of this temperature to keep 100 hours the sample after, the mass M of measure sample 2, using formula: X=(M 2-M 1) (L * W+H * L+W * H) calculates the per surface area oxidation weight gain X of alloy to ÷ 2, and adopting tolerance range is 10 -4The quality of the electronic balance measure sample of g, using tolerance range is 10 -2The size of the vernier caliper measurement sample of mm.The lasting sample of preparation standard adopts the SANS beta alloy at 600 ℃/400MPa, the creep rupture life during 700 ℃/350MPa.Ti after tested 37～52Ni 45～ 50Al 1～6Nb 1～3Hf 1～4High temperature alloy each performance perameter such as table 1 under condition of different temperatures, shown in the table 2:
The compression mechanical property and the antioxidant property of table 1 alloy of the present invention
Probe temperature (℃) Yield strength (MPa) Deformation rate (%) Oxidation weight gain (mg/cm 2)
20 1200～2400 10～30 -
600 800～1450 - 0.005～0.01
650 600～1350 - 0.005～0.01
700 500～1000 - 0.03～1.00
800 400～800 - 1.00～4.50
The high temperature endurance performance of table 2 alloy of the present invention
Probe temperature (℃) Experiment stress (MPa) Duration (h)
600 400 ≥110
700 350 ≥80
Ti of the present invention 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4High temperature alloy has higher yield strength, oxidation-resistance property and enduring quality than TiNiAl alloy material, has optimized the performance of TiNiAl base alloy.This Ti 37～ 52Ni 45～50Al 1～6Nb 1～3Hf 1～4High temperature alloy is compared with the TiNiAlNb superalloy with identical Al, Nb atomic percent, has excellent enduring quality, better yield strength, has higher antioxidant property at 600 ℃～800 ℃.
Embodiment 1:System Ti 41Ni 49Al 5Nb 2Hf 3High temperature alloy
(1) taking by weighing 41at% purity is that 99.9% titanium, 49at% purity are that 99.9% nickel, 5at% purity are that 99.9% aluminium, 2at% purity are that 99.9% niobium and 3at% purity are 99.9% hafnium;
(2) above-mentioned titanium, nickel, aluminium, niobium and hafnium raw material are put into non-consumable arc furnace, be evacuated to 2 * 10 -3Pa charges into high-purity argon gas to 1.01 * 10 5Pa is smelted into Ti at 2800 ℃ then 41Ni 49Al 5Nb 2Hf 3The superalloy ingot;
(3) with the above-mentioned Ti that makes 41Ni 49Al 5Nb 2Hf 3The superalloy ingot is put into vacuum heat treatment furnace and is heat-treated, in vacuum tightness 2 * 10 -3Pa, the insulation after 24 hours down of 1000 ℃ of thermal treatment temps, furnace cooling promptly obtains the Ti of requirement of the present invention 41Ni 49Al 5Nb 2Hf 3High temperature alloy.
Adopt wire cutting method, at the above-mentioned Ti that makes 41Ni 49Al 5Nb 2Hf 3Cut diameter d=6mm in the high temperature alloy, the right cylinder of height h=9mm is as the Mechanics Performance Testing sample, adopt MTS-880 type universal material experimental machine to carry out compression pressure-strain testing, compressive strain speed is 0.2nm/min, recording yield strength under 600 ℃ is 1250MPa, and recording yield strength under 650 ℃ is 950MPa.Adopt wire cutting method to cut long L=10mm, wide W=5mm, the rectangular parallelepiped sample of high H=5mm be as the high temperature oxidation resistance specimen, place 600 ℃ still air to keep 100 hours in sample after, the oxidation weight gain of measure sample is 0.005mg/cm 2After placing 650 ℃ still air to keep 100 hours the sample, the oxidation weight gain of measure sample is 0.006mg/cm 2The lasting sample of preparation standard adopts SANS to record alloy and is not less than 130h in the creep rupture life of 600 ℃/400MPa, is not less than 90h the creep rupture life during 700 ℃/350MPa.Fig. 1 illustrates Ti 41Ni 49Al 5Nb 2Hf 3The compression testing result of high temperature alloy under 20 ℃, 600 ℃, 650 ℃, 700 ℃ and 800 ℃ of temperature.Ti of the present invention 41Ni 49Al 5Nb 2Hf 3The yield strength of high temperature alloy in the time of 800 ℃ is minimum, and yield strength is a preferable states between 600 ℃～800 ℃.This Ti 41Ni 49Al 5Nb 2Hf 3High temperature alloy and Ti with identical Al, Nb atomic percent 45Ni 47Al 6Nb 2Superalloy is compared, and has excellent enduring quality, and higher yield strength has better antioxidant property at 600 ℃～800 ℃.
Embodiment 2:System Ti 37Ni 50Al 6Nb 3Hf 4High temperature alloy
(1) taking by weighing 37at% purity is that 99.9% titanium, 50at% purity are that 99.9% nickel, 6at% purity are that 99.9% aluminium, 3at% purity are that 99.9% niobium and 4at% purity are 99.9% hafnium;
(2) above-mentioned titanium, nickel, aluminium, niobium and hafnium raw material are put into non-consumable arc furnace, be evacuated to 5 * 10 -3Pa charges into high-purity argon gas to 1.01 * 10 5Pa is smelted into Ti at 3000 ℃ then 37Ni 50Al 6Nb 3Hf 4The superalloy ingot;
(3) with the above-mentioned Ti that makes 37Ni 50Al 6Nb 3Hf 4The superalloy ingot is put into vacuum heat treatment furnace and is heat-treated, in vacuum tightness 5 * 10 -3Pa, the insulation after 20 hours down of 850 ℃ of thermal treatment temps, furnace cooling promptly obtains the Ti of requirement of the present invention 37Ni 50Al 6Nb 3Hf 4High temperature alloy.
Adopt the testing method test performance identical with embodiment 1, referring to shown in Figure 2, among the figure, recording yield strength under 650 ℃ is 1150MPa; Recording yield strength under 800 ℃ is 750MPa.Adopt wire cutting method to cut long L=10mm, wide W=5mm, the rectangular parallelepiped sample of high H=5mm be as the high temperature oxidation resistance specimen, place 800 ℃ still air to keep 100 hours in sample after, the oxidation weight gain of measure sample is 1.03mg/cm 2
Embodiment 3:System Ti 46Ni 46Al 4Nb 2Hf 2High temperature alloy
(1) taking by weighing 46at% purity is that 99.9% titanium, 46at% purity are that 99.9% nickel, 4at% purity are that 99.9% aluminium, 2at% purity are that 99.9% niobium and 2at% purity are 99.9% hafnium;
(2) the above-mentioned titanium that takes by weighing, nickel, aluminium, niobium and hafnium raw material are put into non-consumable arc furnace, be evacuated to 3 * 10 -3Pa charges into high-purity argon gas to 1.01 * 10 5Pa is smelted into Ti at 2700 ℃ then 46Ni 46Al 4Nb 2Hf 2The superalloy ingot;
(3) with the above-mentioned Ti that makes 46Ni 46Al 4Nb 2Hf 2The superalloy ingot is put into vacuum heat treatment furnace and is heat-treated, in vacuum tightness 3 * 10 -3Pa, the insulation after 17 hours down of 1000 ℃ of thermal treatment temps, furnace cooling promptly obtains the Ti of requirement of the present invention 46Ni 46Al 4Nb 2Hf 2High temperature alloy.
Adopt the testing method test performance identical with embodiment 1, referring to shown in Figure 3, among the figure, recording yield strength under 600 ℃ is 1100MPa; Recording yield strength under 800 ℃ is 460MPa.
Ti of the present invention 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4High temperature alloy is on TiNi alloy basis, usually improve alloy at room temperature yield strength and mechanical behavior under high temperature by interpolation high purity Al, Nb, Hf unit, this class alloy has excellent enduring quality, and the room temperature yield strength is 1200～2400MPa, and deformation rate (plasticity) is greater than 10%; Yield strength in the time of 600 ℃～800 ℃ is 1450MPa～400MPa, has good mechanical performance and high temperature oxidation resistance between 600 ℃～800 ℃.

Claims (7)

1. a high-temperature titanium aluminium niobium alloy materials is characterized in that: be made up of the titanium (Ti) of 37at%～52at%, the nickel (Ni) of 45at%～50at%, the aluminium (Al) of 1at%～6at%, the niobium (Nb) of 1at%～3at% and the hafnium (Hf) of 1at%～4at%.
2. titanium nickel aluminium niobium hafnium high-temperature alloy material according to claim 1 is characterized in that: titanium nickel aluminium niobium hafnium high-temperature alloy material is Ti 41Ni 49Al 5Nb 2Hf 3
3. titanium nickel aluminium niobium hafnium high-temperature alloy material according to claim 1 is characterized in that: titanium nickel aluminium niobium hafnium high-temperature alloy material is Ti 37Ni 50A L6Nb 3Hf 4
4. titanium nickel aluminium niobium hafnium high-temperature alloy material according to claim 1 is characterized in that: titanium nickel aluminium niobium hafnium high-temperature alloy material is Ti 46Ni 46Al 4Nb 2Hf 2
5. high-temperature titanium aluminium niobium alloy materials according to claim 1 is characterized in that: the yield strength of this alloy material in the time of 20 ℃ is 1200～2400MPa, and deformation rate is greater than 10%; Yield strength in the time of 600～800 ℃ is 1450～400MPa.
6. high-temperature titanium aluminium niobium alloy materials according to claim 1 is characterized in that: this alloy material 100 hours oxidation weight gains in 600～800 ℃, still air are 0.005～4.50mg/cm 2
7. the method for preparing titanium nickel aluminium niobium hafnium high-temperature alloy material as claimed in claim 1 is characterized in that comprising the following steps:
(1) presses Ti 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4It is that 99.9% titanium (Ti), purity are that 99.9% nickel (Ni), purity are that 99.9% aluminium (Al), purity are that 99.9% niobium (Nb) and purity are 99.9% hafnium (Hf) that proportioning takes by weighing purity;
(2) the above-mentioned raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 2 * 10 -3～5 * 10 -3Pa charges into high-purity argon gas to 1.01 * 10 5Pa is smelted into the TiNiAlNbHf ingot at 2700～3000 ℃ then;
(3) the above-mentioned TiNiAlNbHf ingot that makes is put into vacuum heat treatment furnace and heat-treat, in vacuum tightness 2 * 10 -3～5 * 10 -3Pa, 850～1000 ℃ insulation is after 12～24 hours down for thermal treatment temp, and furnace cooling promptly obtains Ti 37～52Ni 45～50Al 1～6Nb 1～3Hf 1～4High temperature alloy.
CN200710175511A 2007-09-30 2007-09-30 Titanium nickel aluminium niobium hafnium high-temperature alloy material Expired - Fee Related CN100577838C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102251146A (en) * 2011-07-14 2011-11-23 北京航空航天大学 Nickel-titanium-aluminum-based high-temperature alloy material and isothermal forging preparation method thereof
CN105599382A (en) * 2015-12-23 2016-05-25 常熟市东方特种金属材料厂 Compound anti-oxidative special metal material
CN107142478A (en) * 2017-05-08 2017-09-08 北京师范大学 A kind of novel wear resistant corrosion-resistant finishes
CN113652592A (en) * 2021-07-22 2021-11-16 中国科学院金属研究所 TiNbHfFeNi eutectic high-entropy alloy with high strength and high elastic strain and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102251146A (en) * 2011-07-14 2011-11-23 北京航空航天大学 Nickel-titanium-aluminum-based high-temperature alloy material and isothermal forging preparation method thereof
CN102251146B (en) * 2011-07-14 2013-04-24 北京航空航天大学 Nickel-titanium-aluminum-based high-temperature alloy material and isothermal forging preparation method thereof
CN105599382A (en) * 2015-12-23 2016-05-25 常熟市东方特种金属材料厂 Compound anti-oxidative special metal material
CN107142478A (en) * 2017-05-08 2017-09-08 北京师范大学 A kind of novel wear resistant corrosion-resistant finishes
CN107142478B (en) * 2017-05-08 2019-06-04 北京师范大学 A kind of novel wear resistant corrosion-resistant finishes
CN113652592A (en) * 2021-07-22 2021-11-16 中国科学院金属研究所 TiNbHfFeNi eutectic high-entropy alloy with high strength and high elastic strain and preparation method thereof
CN113652592B (en) * 2021-07-22 2022-03-18 中国科学院金属研究所 TiNbHfFeNi eutectic high-entropy alloy with high strength and high elastic strain and preparation method thereof

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