CN101168812A - Metal element alloyed sheet layer niobium-molybdenum-silicon-base in situ composite material and preparation method thereof - Google Patents
Metal element alloyed sheet layer niobium-molybdenum-silicon-base in situ composite material and preparation method thereof Download PDFInfo
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- CN101168812A CN101168812A CNA2007101787423A CN200710178742A CN101168812A CN 101168812 A CN101168812 A CN 101168812A CN A2007101787423 A CNA2007101787423 A CN A2007101787423A CN 200710178742 A CN200710178742 A CN 200710178742A CN 101168812 A CN101168812 A CN 101168812A
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Abstract
The invention discloses a metal element alloyed sheet layer niobium molybdenum silicon based insitu compound material and a preparation method through a light suspension area melting positioning coagulation method. The Nb-Mo-Si insitu compound material is composed of 30 to 87at percent Nb, 3 to 40at percent Mo and 10 to 30at percent Si. In order to enhance the intensity of the Nb-Mo-Si insitu compound material at the high temperature of 1200 to 1500 DEG C, and 0.1 to 10at percent fourth metal element A can be added to form an Nb-Mo-Si-A insitu compound material. The Nb-Mo-Si insitu compound material of the invention after the fourth metal element A alloying has two phases - (Nb, Mo, A)ss and (Nb, Mo, A)5Si3, and also has a sheet layer structure. The compression yield intensity of the Nb-Mo-Si-A insitu compound material is 300 to 1000 1000MPa at 1200 to 1500 DEG C.
Description
Technical field
The present invention relates to a kind of niobium-molybdenum-silicon high-temperature alloy material, more particularly say, be meant a kind of laminated structure, metal element alloyed, niobium-molybdenum-silicon-base in situ composite material that has, and adopt the molten directional solidification process in light suspension zone to prepare niobium-molybdenum-silicon-base in situ composite material with laminated structure.
Background technology
The a large amount of use held the high high temperature alloy of warm ability in fields such as the energy, petrochemical complex, aerospace, for example the blade material of aero-turbine generally adopts nickel base superalloy, the use temperature of present state-of-the-art third generation nickel-base high-temperature single crystal alloy reaches 1150 ℃, yet this is near 1350 ℃ of the fusing points of nickel base superalloy, and it is little that nickel-base high-temperature single crystal alloy continues the space of development.For the further performance that improves turbine engine, and improve efficiency of combustion, reduce energy consumption and exhaust gas emission, must develop and hold the higher blade material of warm ability.
The binary niobium-silicon alloy that employing casting-heat treating method makes is by niobium sosoloid (Nb
Ss) and intermetallic compound Nb
5Si
3Two phase composites.Eutectic reaction: L → Nb at first takes place at 1920 ℃ in the binary niobium-silicon alloy
Ss+ Nb
3Eutectoid reaction: Nb takes place at 1770 ℃ in Si then
3Si → Nb
Ss+ Nb
5Si
3, the Nb that obtains by two-step reaction
SsAnd Nb
5Si
3Two-phase is because the difficult control of complicated its form of reaction.
Use the method for physical vapor deposition can obtain metal niobium and Nb
5Si
3The laminated structure of two phase composites, but there is following problem in the niobium silicon composite that this method obtains: and crystal grain is tiny, a little less than the creep resistance; The two-phase non-equilibrium thermodynamics, tissue is unstable; Preparation technology is complicated, and cost is higher.
Summary of the invention
The purpose of this invention is to provide a kind of (the lamella percent by volume is greater than 50%) with laminated structure, metal element alloyed, Nb-Mo-Si in-situ composite, this in-situ composite adopts the preparation of light floating zone melting directional solidification method, Nb-Mo-Si in-situ composite after the 4th metal element A alloying has (Nb, Mo, A)
Ss(Nb, Mo, A)
5Si
3Two-phase; Has laminated structure through its microtexture of electron microscope observation; And at 1200～1500 ℃ of compression yield strengths is 300～1000MPa.
Nb-Mo-Si in-situ composite of the present invention, the molybdenum (Mo) of its niobium by 30～87at% (Nb), 3～40at% and the silicon (Si) of 10～30at% are formed.
In order to improve the Nb-Mo-Si in-situ composite at 1200～1500 ℃ compression yield strength, the present invention is by adding the 4th metal element A of 0.1～10at% in the Nb-Mo-Si in-situ composite, described the 4th metal element A is a kind of in aluminium (Al), chromium (Cr), hafnium (Hf), titanium (Ti), tungsten (W) or the tantalum (Ta).The Nb-Mo-Si-A in-situ composite is 300～1000MPa at 1200～1500 ℃ compression yield strength.
Description of drawings
Figure 1A is Nb
72Mo
10Si
18Alloy longitudinal profile back scattering photo.
Figure 1B is Nb
72Mo
10Si
18Alloy horizontal section back scattering photo.
Fig. 2 is Nb
70Mo
10Si
17Al
3Alloy longitudinal profile back scattering photo.
Fig. 3 is Nb
50Mo
30Si
15Cr
5Alloy longitudinal profile back scattering photo.
Fig. 4 is Nb
64Mo
12Si
16Ti
8Alloy longitudinal profile back scattering photo.
Fig. 5 is Nb
64Mo
20Si
12Hf
4Alloy longitudinal profile back scattering photo.
Fig. 6 is Nb
61Mo
25Si
12W
2Alloy longitudinal profile back scattering photo.
Fig. 7 is Nb
65Mo
18Si
14Ta
3Alloy longitudinal profile back scattering photo.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
Nb-Mo-Si in-situ composite of the present invention is made up of the niobium (Nb) of 30～87at%, the molybdenum (Mo) of 3～40at% and the silicon (Si) of 10～30at%.
Nb-Mo-Si-A in-situ composite of the present invention, be on Nb-Mo-Si in-situ composite basis, in order to improve it, in the Nb-Mo-Si in-situ composite, add the 4th metal element A of 0.1～10at% at 1200～1500 ℃ of pyritous compression yield strengths.Described the 4th metal element A is a kind of in aluminium (Al), chromium (Cr), hafnium (Hf), titanium (Ti), tungsten (W) or the tantalum (Ta).
One, the Nb-Mo-Si in-situ composite (alloy) of film-making layer structure
The first step: taking by weighing purity by Nb-Mo-Si target component proportioning is that 99.99% niobium (Nb), purity are that 99.99% molybdenum (Mo), purity are that 99.99% silicon (Si) is stand-by;
Second step: the above-mentioned target component raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 5 * 10
-4Pa～1 * 10
-3Pa charges into high-purity argon gas to 0.5 * 10
5Pa 2700～3000 ℃ of following meltings of smelting temperature 2～5 times, makes alloy pig;
The 3rd step: (A) alloy pig that second step was made adopts the line cutting processing to obtain alloy charge bar and base rod, it is inserted in the light floating zone melting stove then, and charge bar is suspended on upper boom, and the base rod is fixed on lower beam;
(B) be evacuated to 5 * 10
-4Pa～1 * 10
-3Pa, charging into flow velocity is 1～2L/min argon gas, the mobile argon gas plays the refrigerative effect, forms suitable temperature gradient.Charge bar and base rod keep rotation, and sense of rotation is opposite, and speed of rotation is 0～50r/min.
(C) charge bar is begun heating, Heating temperature raises gradually, and heat-up rate is 60～100 ℃/min, until the charge bar fusing, then charge bar is docked with the base rod.The beginning pull, drawing velocity is 0.5～10mm/h, thermograde 100～200K/cm, pull 5～20h, directional freeze finishes, and makes the Nb-Mo-Si in-situ composite (alloy) with laminated structure.
Adopt JSM-5600HV/LV type scanning electronic microscope to do the microtexture analysis the above-mentioned Nb-Mo-Si alloy that makes, its have (Nb, Mo)
Ss(Nb, Mo)
5Si
3Two-phase.Adopt wire cutting method that the Nb-Mo-Si alloy bar material is longitudinally cut open at the center, have laminated structure.Adopting day island proper Tianjin high temperature experimental machine to carry out stress under compression-strain testing to the Nb-Mo-Si alloy, is 1200～2000MPa at the compression yield strength of room temperature (18～25 ℃), is 300～900MPa at 1200～1500 ℃ compression yield strengths.
Two, the Nb-Mo-Si-A in-situ composite (alloy) of film-making layer structure
The first step: taking by weighing purity by Nb-Mo-Si-A target component proportioning is that 99.99% niobium (Nb), purity are that 99.99% molybdenum (Mo), purity are 99.99% silicon (Si), and purity is that 99.99% the 4th metal element A is stand-by;
Second step: the above-mentioned target component raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 5 * 10
-4Pa～1 * 10
-3Pa charges into high-purity argon gas to 0.5 * 10
5Pa 2700～3700 ℃ of following meltings of smelting temperature 2～5 times, makes alloy pig;
The 3rd step: (A) alloy pig that second step was made adopts the line cutting processing to obtain alloy charge bar and base rod, it is inserted in the light floating zone melting stove then, and charge bar is suspended on upper boom, and the base rod is fixed on lower beam;
(B) be evacuated to 5 * 10
-4Pa～1 * 10
-3Pa, charging into flow velocity is 1～2L/min argon gas, the mobile argon gas plays the refrigerative effect, forms suitable temperature gradient.Charge bar and base rod keep rotation, and sense of rotation is opposite, and speed of rotation is 0～50r/min.
(C) charge bar is begun heating, Heating temperature raises gradually, and heat-up rate is 60～100 ℃/min, until the charge bar fusing, then charge bar is docked with the base rod.The beginning pull, drawing velocity is 0.5～10mm/h, thermograde 100～200K/cm,, pull 5～20h, directional freeze finishes, and makes the Nb-Mo-Si-A in-situ composite (alloy) with laminated structure.
Adopt JSM-5600HV/LV type scanning electronic microscope to do the microtexture analysis the above-mentioned Nb-Mo-Si-A alloy that makes, its have (Nb, Mo, A)
Ss(Nb, Mo, A)
5Si
3Two-phase.Adopt wire cutting method that the Nb-Mo-Si-A alloy bar material is longitudinally cut open at the center, have laminated structure.Adopting day island proper Tianjin high temperature experimental machine to carry out stress under compression-strain testing to the Nb-Mo-Si-A alloy, is 300～1000MPa at 1200～1500 ℃ compression yield strengths.
Embodiment 1:The Nb of film-making layer structure
72Mo
10Si
18Alloy
The first step: press Nb
72Mo
10Si
18It is that 99.99% niobium (Nb), purity are that 99.99% molybdenum (Mo), purity are that 99.99% silicon (Si) is stand-by that proportioning takes by weighing purity;
Second step: the above-mentioned raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 5 * 10
-4Pa charges into high-purity argon gas to 0.5 * 10
5Pa 3000 ℃ of following meltings of smelting temperature 4 times, makes alloy pig;
The 3rd step: (A) adopt wire cutting method, go on foot the base rod that cuts φ 9mm * 90mm alloy charge bar and φ 9mm * 40mm in the alloy pig that makes with second, it is inserted in the light floating zone melting stove then, charge bar is suspended on upper boom, and the base rod is fixed on lower beam;
(B) be evacuated to 5 * 10
-4Pa, charging into flow velocity is 2L/min argon gas (charging into argon gas is 1 normal atmosphere), and charge bar is opposite with base rod sense of rotation, and speed of rotation is 10r/min.
(C) charge bar is begun heating, Heating temperature raises gradually, and heat-up rate is 60 ℃/minute, until the charge bar fusing, then charge bar is docked with the base rod.The beginning pull, drawing velocity is 5mm/h, thermograde 200K/cm makes the Nb with laminated structure behind the pull 8h
72Mo
10Si
18Alloy.
The method that adopts the line cutting is with the above-mentioned Nb with laminated structure that makes
72Mo
10Si
18Alloy bar material longitudinally center is cut open, and polishes with waterproof abrasive paper, with diamond paste and clear water polishing, is microtexture analysis, Nb with JSM-5600HV/LV type scanning electronic microscope then again
72Mo
10Si
18In the alloy by (Nb, Mo)
SsSosoloid and (Nb, Mo)
5Si
3Intermetallic compound two phase composites.Through the above-mentioned Nb that makes
72Mo
10Si
18No matter alloy is vertical (shown in Figure 1A), and still laterally (shown in Figure 1B) all has laminated structure.
Adopt wire cutting method, at the above-mentioned Nb that makes
72Mo
10Si
18Alloy cuts the right cylinder of φ 3mm * 5mm as the Mechanics Performance Testing sample, adopts day island proper Tianjin high temperature experimental machine to carry out stress under compression-strain testing, and compressive strain speed is 3 * 10
-4s
-1, vacuum tightness is 1 * 10
-3Pa.Experimental temperature is 25 ℃, 1200 ℃.The right cylinder sample carries out surface finish with 1000#SiC sand paper before experiment.Rate of heating is 10 ℃/minute during the high temperature experiment, keeps carrying out in 10 minutes compression experiment, the Nb that makes behind the arrival design temperature again
72Mo
10Si
18The compression yield strength of alloy material in the time of 25 ℃ is 1720MPa, and the compression yield strength in the time of 1200 ℃ is 842MPa.
Adopt the preparation method identical with embodiment 1, make the Nb-Mo-Si alloy with laminated structure of heterogeneity, its Specifeca tion speeification is as shown in the table:
| Alloying constituent (at%) | Probe temperature (℃) | Compression yield strength (MPa) |
| Nb 62Mo 20Si 18 | 25 | 1783 |
| 1200 | 864 | |
| Nb 65Mo 10Si 25 | 25 | 1942 |
| 1200 | 890 | |
| Nb 50Mo 30Si 20 | 25 | 1883 |
| 1200 | 882 |
Embodiment 2:The Nb of film-making layer structure
70Mo
10Si
17Al
3Alloy
The first step: press Nb
70Mo
10Si
17Al
3It is that 99.99% niobium (Nb), purity are that 99.99% molybdenum (Mo), purity are that 99.99% silicon (Si), purity are that 99.99% aluminium (Al) is stand-by that proportioning takes by weighing purity;
Second step: the above-mentioned raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 8 * 10
-4Pa charges into high-purity argon gas to 0.5 * 10
5Pa 2700 ℃ of following meltings of smelting temperature 5 times, makes alloy pig;
The 3rd step: (A) adopt wire cutting method, go on foot the base rod that cuts φ 9mm * 90mm alloy charge bar and φ 9mm * 40mm in the alloy pig that makes with second, it is inserted in the light floating zone melting stove then, charge bar is suspended on upper boom, and the base rod is fixed on lower beam;
(B) be evacuated to 8 * 10
-4Pa, charging into flow velocity is 1.8L/min argon gas (charging into argon gas is 1 normal atmosphere), and charge bar is opposite with base rod sense of rotation, and speed of rotation is 20r/min.
(C) charge bar is begun heating, Heating temperature raises gradually, and heat-up rate is 80 ℃/minute, until the charge bar fusing, then charge bar is docked with the base rod.The beginning pull, drawing velocity is 8mm/h, thermograde 180K/cm, pull 6h makes the Nb with laminated structure
70Mo
10Si
17Al
3Alloy.
The method that adopts the line cutting is with the above-mentioned Nb with laminated structure that makes
70Mo
10Si
17Al
3Alloy bar material longitudinally center is cut open, and polishes with waterproof abrasive paper, with diamond paste and clear water polishing, is microtexture analysis, Nb with JSM-5600HV/LV type scanning electronic microscope then again
70Mo
10Si
17Al
3Have in the alloy (Nb, Mo, Al)
SsPhase (in the Nb sosoloid Mo, Al partly substitute Nb) and (Nb, Mo, Al)
5Si
3Phase (Nb
5Si
3Mutually middle Mo, Al partly substitute Nb), and have laminated structure, referring to shown in Figure 2.
Adopt wire cutting method, at the above-mentioned Nb that makes
70Mo
10Si
17Al
3Alloy cuts the right cylinder of φ 3mm * 5mm as the Mechanics Performance Testing sample, adopts day island proper Tianjin high temperature experimental machine to carry out stress under compression-strain testing.Compressive strain speed is 3 * 10
-4s
-1, vacuum tightness is 1 * 10
-3Pa is when experimental temperature is 1200 ℃.The right cylinder sample carries out surface finish with 1000#SiC sand paper before experiment.Rate of heating is 10 ℃/minute during the high temperature experiment, keeps carrying out in 10 minutes compression experiment behind the arrival design temperature again.The above-mentioned Nb that makes
70Mo
10Si
17Al
3The compression yield strength of alloy in the time of 1200 ℃ is 825MPa.
Adopt the preparation method identical with embodiment 2, make the Nb-Mo-Si-Al alloy with laminated structure of heterogeneity, its Specifeca tion speeification is as shown in the table:
| Alloying constituent | Probe temperature (℃) | Compression yield strength (MPa) |
| Nb 58Mo 20Si 18Al 4 | 1500 | 426 |
| 1200 | 852 | |
| Nb 43Mo 35Si 14Als | 1200 | 806 |
| Nb 4sMo 30Si 12Al 10 | 1200 | 902 |
Embodiment 3:The Nb of film-making layer structure
50Mo
30Si
15Cr
5Alloy
The first step: press Nb
50Mo
30Si
15Cr
5It is that 99.99% niobium (Nb), purity are that 99.99% molybdenum (Mo), purity are that 99.99% silicon (Si), purity are that 99.99% chromium (Cr) is stand-by that proportioning takes by weighing purity;
Second step: the above-mentioned raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 8 * 10
-4Pa charges into high-purity argon gas to 0.5 * 10
5Pa 2800 ℃ of following meltings of smelting temperature 3 times, makes alloy pig;
The 3rd step: (A) adopt wire cutting method, go on foot the base rod that cuts φ 9mm * 90mm alloy charge bar and φ 9mm * 40mm in the alloy pig that makes with second, it is inserted in the light floating zone melting stove then, charge bar is suspended on upper boom, and the base rod is fixed on lower beam;
(B) be evacuated to 5 * 10
-4Pa, charging into flow velocity is 1.6L/min (charging into argon gas is 1 normal atmosphere), and charge bar is opposite with base rod sense of rotation, and speed of rotation is 40r/min.
(C) charge bar is begun heating, Heating temperature raises gradually, and heat-up rate is 80 ℃/minute, until the charge bar fusing, then charge bar is docked with the base rod.The beginning pull, drawing velocity is 3mm/h, thermograde 160K/cm, the alloy bar material speed of rotation is 40r/min, directional freeze 15h makes the Nb with laminated structure
50Mo
30Si
15Cr
5Alloy.
The method that adopts the line cutting is with the above-mentioned Nb with laminated structure that makes
50Mo
30Si
15Cr
5Alloy bar material longitudinally center is cut open, and polishes with waterproof abrasive paper, with diamond paste and clear water polishing, is microtexture analysis, Nb with JSM-5600HV/LV type scanning electronic microscope then again
50Mo
30Si
15Cr
5Have in the alloy (Nb, Mo, Cr)
SsPhase (in the Nb sosoloid Mo, Cr partly substitute Nb) and (Nb, Mo, Cr)
5Si
3Phase (Nb
5Si
3Mutually middle Mo, Cr partly substitute Nb), and have laminated structure, referring to shown in Figure 3.
Adopt wire cutting method, at the above-mentioned Nb that makes
50Mo
30Si
15Cr
5Alloy cuts the right cylinder of φ 3mm * 5mm as the Mechanics Performance Testing sample, the above-mentioned Nb that makes
50Mo
30Si
15Cr
5The compression yield strength of alloy material in the time of 1200 ℃ is 856MPa, and gain in weight is 70mg/cm behind 1250 ℃ of oxidation 100h
2(use the high-temperature tubular electric furnace, model is SK
2-25-13S tests oxidation-resistance).
Adopt the preparation method identical with embodiment 3, make the Nb-Mo-Si-Cr alloy with laminated structure of heterogeneity, its Specifeca tion speeification is as shown in the table:
| Alloying constituent | Probe temperature (℃) | Compression yield strength (MPa) |
| Nb 50Mo 30Si 18Cr 2 | 1500 | 428 |
| 1200 | 857 | |
| Nb 62Mo 12Si 22Cr 4 | 1500 | 432 |
| 1200 | 875 | |
| Nb 42Mo 28Si 24Cr 6 | 1500 | 452 |
| 1200 | 902 | |
| Nb 46Mo 35Si 12Cr 7 | 1200 | 762 |
| Nb 71Mo 5Si 16Cr 8 | 1200 | 789 |
Embodiment 4:The Nb of film-making layer structure
64Mo
12Si
16Ti
8Alloy
The first step: press Nb
64Mo
12Si
16Ti
8It is that 99.99% niobium (Nb), purity are that 99.99% molybdenum (Mo), purity are that 99.99% silicon (Si), purity are that 99.99% titanium (Ti) is stand-by that proportioning takes by weighing purity;
Second step: the above-mentioned raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 8 * 10
-4Pa charges into high-purity argon gas to 0.5 * 10
5Pa 2700 ℃ of following meltings of smelting temperature 5 times, makes alloy pig;
The 3rd step: (A) adopt wire cutting method, go on foot the base rod that cuts φ 9mm * 90mm alloy charge bar and φ 9mm * 40mm in the alloy pig that makes with second, it is inserted in the light floating zone melting stove then, charge bar is suspended on upper boom, and the base rod is fixed on lower beam;
(B) be evacuated to 8 * 10
-4Pa, charging into flow velocity is 1.6L/min (charging into argon gas is 1 normal atmosphere), and charge bar is opposite with base rod sense of rotation, and speed of rotation is 40r/min.
(C) charge bar is begun heating, Heating temperature raises gradually, and heat-up rate is 80 ℃/minute, until the charge bar fusing, then charge bar is docked with the base rod.The beginning pull, drawing velocity is 3mm/h, thermograde 160K/cm, the alloy bar material speed of rotation is 40r/min, directional freeze 15h makes the Nb with laminated structure
64Mo
12Si
16Ti
8Alloy.
The method that adopts the line cutting is with the above-mentioned Nb with laminated structure that makes
64Mo
12Si
16Ti
8Alloy bar material longitudinally center is cut open, and polishes with waterproof abrasive paper, with diamond paste and clear water polishing, is microtexture analysis, Nb with JSM-5600HV/LV type scanning electronic microscope then again
64Mo
12Si
16Ti
8Have in the alloy (Nb, Mo, Ti)
SsPhase (in the Nb sosoloid Mo, Ti partly substitute Nb) and (Nb, Mo, Ti)
5Si
3Phase (Nb
5Si
3Mutually middle Mo, Ti partly substitute Nb), and have laminated structure, referring to shown in Figure 4.
Adopt wire cutting method, at the above-mentioned Nb that makes
64Mo
12Si
16Ti
8Alloy cuts the right cylinder of φ 3mm * 5mm as the Mechanics Performance Testing sample, the above-mentioned Nb that makes
64Mo
12Si
16Ti
8The compression yield strength of alloy material in the time of 1200 ℃ is 806MPa.
Adopt wire cutting method, at the above-mentioned Nb that makes
64Mo
12Si
16Ti
8Alloy cuts the sample of 3mm * 6mm * 30mm, and polishes with waterproof abrasive paper, cuts a finedraw that 3mm is dark at the sample center, on SANS microcomputer control electronics universal testing machine, carry out, span is 24mm, and the translational speed of pressure head is 0.01mm/min, and the fracture toughness property that records in the time of 25 ℃ is 12MPam
1/2
Adopt the preparation method identical with embodiment 4, make the Nb-Mo-Si-Ti alloy with laminated structure of heterogeneity, its Specifeca tion speeification is as shown in the table:
| Alloying constituent | Probe temperature (℃) | Compression yield strength (MPa) |
| Nb 55Mo 25Si 18Ti 2 | 1200 | 858 |
| Nb 54Mo 18Si 24Ti 4 | 1200 | 917 |
Embodiment 5:The Nb of film-making layer structure
64Mo
20Si
12Hf
4Alloy
The first step: press Nb
64Mo
20Si
12Hf
4It is that 99.99% niobium (Nb), purity are that 99.99% molybdenum (Mo), purity are that 99.99% silicon (Si), purity are that 99.99% hafnium (Hf) is stand-by that proportioning takes by weighing purity;
Second step: the above-mentioned raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 8 * 10
-4Pa charges into high-purity argon gas to 0.5 * 10
5Pa 3400 ℃ of following meltings of smelting temperature 5 times, makes alloy pig;
The 3rd step: (A) adopt wire cutting method, go on foot the base rod that cuts φ 9mm * 90mm alloy charge bar and φ 9mm * 40mm in the alloy pig that makes with second, it is inserted in the light floating zone melting stove then, charge bar is suspended on upper boom, and the base rod is fixed on lower beam;
(B) be evacuated to 7 * 10
-4Pa, charging into flow velocity is 1.7L/min (charging into argon gas is 1 normal atmosphere), and charge bar is opposite with base rod sense of rotation, and speed of rotation is 30r/min.
(C) charge bar is begun heating, Heating temperature raises gradually, and heat-up rate is 70 ℃/min, until the charge bar fusing, then charge bar is docked with the base rod.The beginning pull, drawing velocity is 7mm/h, thermograde 170K/cm, the alloy bar material speed of rotation is 30r/min, directional freeze 10h makes the Nb with laminated structure
64Mo
20Si
12Hf
4Alloy.
The method that adopts the line cutting is with the above-mentioned Nb with laminated structure that makes
64Mo
20Si
12Hf
4Alloy bar material longitudinally center is cut open, and polishes with waterproof abrasive paper, with diamond paste and clear water polishing, is microtexture analysis, Nb with JSM-5600HV/LV type scanning electronic microscope then again
64Mo
20Si
12Hf
4Have in the alloy (Nb, Mo, Hf)
SsPhase (in the Nb sosoloid Mo, Hf partly substitute Nb) and (Nb, Mo, Hf)
5Si
3Phase (Nb
5Si
3Mutually middle Mo, Hf partly substitute Nb), and have laminated structure, referring to shown in Figure 5.
Adopt wire cutting method, at the above-mentioned Nb that makes
64Mo
20Si
12Hf
4Alloy cuts the right cylinder of φ 3mm * 5mm as the Mechanics Performance Testing sample, and its compression yield strength in the time of 1200 ℃ is 765MPa.
Adopt the preparation method identical with embodiment 5, make the Nb-Mo-Si-Hf alloy with laminated structure of heterogeneity, its Specifeca tion speeification is as shown in the table:
| Alloying constituent | Probe temperature (℃) | Compression yield strength (MPa) |
| Nb 53Mo 27Si 18Hf 2 | 1500 | 456 |
| 1350 | 670 | |
| Nb 56Mo 15Si 26Hf 3 | 1500 | 508 |
| 1200 | 912 | |
| Nb 50Mo 25Si 20Hf 5 | 1500 | 473 |
| 1200 | 897 | |
| Nb 46Mo 35Si 13Hf 6 | 1200 | 785 |
| Nb 51Mo 30Si 11Hf 8 | 1400 | 570 |
Embodiment 6:The Nb of film-making layer structure
61Mo
25Si
12W
2Alloy
The first step: press Nb
61Mo
25Si
12W
2It is that 99.99% niobium (Nb), purity are that 99.99% molybdenum (Mo), purity are that 99.99% silicon (Si), purity are that 99.99% tungsten (W) is stand-by that proportioning takes by weighing purity;
Second step: the above-mentioned raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 8 * 10
-4Pa charges into high-purity argon gas to 0.5 * 10
5Pa 3700 ℃ of following meltings of smelting temperature 5 times, makes alloy pig;
The 3rd step: (A) adopt wire cutting method, go on foot the base rod that cuts φ 9mm * 90mm alloy charge bar and φ 9mm * 40mm in the alloy pig that makes with second, it is inserted in the light floating zone melting stove then, charge bar is suspended on upper boom, and the base rod is fixed on lower beam;
(B) be evacuated to 8 * 10
-4Pa, charging into flow velocity is 1.6L/min (charging into argon gas is 1 normal atmosphere), and charge bar is opposite with base rod sense of rotation, and speed of rotation is 40r/min.
(C) charge bar is begun heating, Heating temperature raises gradually, and heat-up rate is 80 ℃/minute, until the charge bar fusing, then charge bar is docked with the base rod.The beginning pull, drawing velocity is 3mm/h, thermograde 160K/cm, the alloy bar material speed of rotation is 40r/min, directional freeze 15h makes the Nb with laminated structure
61Mo
25Si
12W
2Alloy.
The method that adopts the line cutting is with the above-mentioned Nb with laminated structure that makes
61Mo
25Si
12W
2Alloy bar material longitudinally center is cut open, and polishes with waterproof abrasive paper, with diamond paste and clear water polishing, is microtexture analysis, Nb with JSM-5600HV/LV type scanning electronic microscope then again
61Mo
25Si
12W
2Have in the alloy (Nb, Mo, W)
SsPhase (in the Nb sosoloid Mo, W partly substitute Nb) and (Nb, Mo, W)
5Si
3Phase (Nb
5Si
3Mutually middle Mo, W partly substitute Nb), and have laminated structure, referring to shown in Figure 6.
Adopt wire cutting method, at the above-mentioned Nb that makes
61Mo
25Si
12W
2Alloy cuts the right cylinder of φ 3mm * 5mm as the Mechanics Performance Testing sample, and its compression yield strength in the time of 1200 ℃ is 780MPa.
Adopt the preparation method identical with embodiment 6, make the Nb-Mo-Si-W alloy with laminated structure of heterogeneity, its Specifeca tion speeification is as shown in the table:
| Alloying constituent | Probe temperature (℃) | Compression yield strength (MPa) |
| Nb 57Mo 18Si 20W 5 | 1500 | 478 |
| Nb 47Mo 35Si 10W 8 | 1200 | 756 |
Embodiment 7:The Nb of film-making layer structure
65Mo
18Si
14Ta
3Alloy
The first step: press Nb
65Mo
18Si
14Ta
3It is that 99.99% niobium (Nb), purity are that 99.99% molybdenum (Mo), purity are that 99.99% silicon (Si), purity are that 99.99% tantalum (Ta) is stand-by that proportioning takes by weighing purity;
Second step: the above-mentioned raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 8 * 10
-4Pa charges into high-purity argon gas to 0.5 * 10
5Pa 3600 ℃ of following meltings of smelting temperature 3 times, makes alloy pig;
The 3rd step: (A) adopt wire cutting method, go on foot the base rod that cuts φ 9mm * 90mm alloy charge bar and φ 9mm * 40mm in the alloy pig that makes with second, it is inserted in the light floating zone melting stove then, charge bar is suspended on upper boom, and the base rod is fixed on lower beam;
(B) be evacuated to 5 * 10
-4Pa, charging into flow velocity is 2L/min (charging into argon gas is 1 normal atmosphere), and charge bar is opposite with base rod sense of rotation, and speed of rotation is 20r/min.
(C) charge bar is begun heating, Heating temperature raises gradually, and heat-up rate is 80 ℃/minute, until the charge bar fusing, then charge bar is docked with the base rod.The beginning pull, drawing velocity is 6mm/h, thermograde 200K/cm, the alloy bar material speed of rotation is 20r/min, directional freeze 8h makes the Nb with laminated structure
65Mo
18Si
14Ta
3Alloy.
The method that adopts the line cutting is with the above-mentioned Nb with laminated structure that makes
65Mo
18Si
14Ta
3Alloy bar material longitudinally center is cut open, and polishes with waterproof abrasive paper, with diamond paste and clear water polishing, is microtexture analysis, Nb with JSM-5600HV/LV type scanning electronic microscope then again
65Mo
18Si
14Ta
3Have in the alloy (Nb, Mo, Ta)
SsPhase (in the Nb sosoloid Mo, Ta partly substitute Nb) and (Nb, Mo, Ta)
5Si
3Phase (Nb
5Si
3Mutually middle Mo, Ta partly substitute Nb), and have laminated structure, referring to shown in Figure 7.
Adopt wire cutting method, at the above-mentioned Nb that makes
65Mo
18Si
14Ta
3Alloy cuts the right cylinder of φ 3mm * 5mm as the Mechanics Performance Testing sample, and its compression yield strength in the time of 1200 ℃ is 769MPa.
Adopt the preparation method identical with embodiment 7, make the Nb-Mo-Si-Ta alloy with laminated structure of heterogeneity, its Specifeca tion speeification is as shown in the table:
| Alloying constituent | Probe temperature (℃) | Compression yield strength (MPa) |
| Nb 58Mo 22Si 18Ta 2 | 1500 | 458 |
| 1200 | 883 | |
| Nb 44Mo 30Si 21Ta 5 | 1500 | 493 |
| 1200 | 914 | |
| Nb 52Mo 30Si 12Ta 6 | 1500 | 396 |
| 1200 | 796 | |
| Nb 57Mo 25Si 10Ta 8 | 1200 | 752 |
Claims (8)
1. metal element alloyed sheet layer niobium-molybdenum-silicon-base in situ composite material, it is characterized in that: the Nb-Mo-Si in-situ composite is made up of the niobium (Nb) of 30～87at%, the molybdenum (Mo) of 3～40at% and the silicon (Si) of 10～30at%.
2. niobium-molybdenum-silicon-base in situ composite material according to claim 1, it is characterized in that: add the 4th metal element A of 0.1～10at% in the Nb-Mo-Si in-situ composite, described the 4th metal element A is a kind of in aluminium (Al), chromium (Cr), hafnium (Hf), titanium (Ti), tungsten (W) or the tantalum (Ta).
3. niobium-molybdenum-silicon-base in situ composite material according to claim 2 is characterized in that: the composition of niobium molybdenum silicon in-situ composite has Nb
70Mo
10Si
17Al
3, Nb
50Mo
30Si
15Cr
5, Nb
64Mo
12Si
16Ti
8, Nb
64Mo
20Si
12Hf
4, Nb
61Mo
25Si
12W
2, Nb
65Mo
18Si
14Ta
3
4. niobium-molybdenum-silicon-base in situ composite material according to claim 2 is characterized in that: the Nb-Mo-Si-A in-situ composite is 300～1000MPa at 1200～1500 ℃ compression yield strength.
5. niobium-molybdenum-silicon-base in situ composite material according to claim 1 is characterized in that: the Nb-Mo-Si in-situ composite have (Nb, Mo)
Ss(Nb, Mo)
5Si
3Two-phase.
6. niobium-molybdenum-silicon-base in situ composite material according to claim 2 is characterized in that: the Nb-Mo-Si-A in-situ composite have (Nb, Mo, A)
Ss(Nb, Mo, A)
5Si
3Two-phase.
7. method that adopts light floating zone melting directional freeze to prepare niobium-molybdenum-silicon-base in situ composite material as claimed in claim 1 is characterized in that the following step is arranged:
The first step: taking by weighing purity by Nb-Mo-Si target component proportioning is that 99.99% niobium (Nb), purity are that 99.99% molybdenum (Mo), purity are that 99.99% silicon (Si) is stand-by;
Second step: the above-mentioned target component raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 5 * 10
-4Pa～1 * 10
-3Pa charges into high-purity argon gas to 0.5 * 10
5Pa 2700～3000 ℃ of following meltings of smelting temperature 2～5 times, makes alloy pig;
The 3rd step: (A) alloy pig that second step was made adopts the line cutting processing to obtain alloy charge bar and base rod, it is inserted in the light floating zone melting stove then, and charge bar is suspended on upper boom, and the base rod is fixed on lower beam;
(B) be evacuated to 5 * 10
-4Pa～1 * 10
-3Pa, charging into flow velocity is 1～2L/min argon gas, the mobile argon gas plays the refrigerative effect, forms suitable temperature gradient.Charge bar and base rod keep rotation, and sense of rotation is opposite, and speed of rotation is 0～50r/min.
(C) charge bar is begun heating, Heating temperature raises gradually, and heat-up rate is 60～100 ℃/min, until the charge bar fusing, then charge bar is docked with the base rod.The beginning pull, drawing velocity is 0.5～10mm/h, thermograde 100～200K/cm, pull 5～20h, directional freeze finishes, and makes the Nb-Mo-Si in-situ composite with laminated structure.
8. method that adopts light floating zone melting directional freeze to prepare niobium-molybdenum-silicon-base in situ composite material as claimed in claim 2 is characterized in that the following step is arranged:
The first step: taking by weighing purity by Nb-Mo-Si-A target component proportioning is that 99.99% niobium (Nb), purity are that 99.99% molybdenum (Mo), purity are 99.99% silicon (Si), and the 4th metal element A is stand-by;
Second step: the above-mentioned target component raw material that takes by weighing is put into non-consumable arc furnace, be evacuated to 5 * 10
-4Pa～1 * 10
-3Pa charges into high-purity argon gas to 0.5 * 10
5Pa 2700～3700 ℃ of following meltings of smelting temperature 2～5 times, makes alloy pig;
The 3rd step: (A) alloy pig that second step was made adopts the line cutting processing to obtain alloy charge bar and base rod, it is inserted in the light floating zone melting stove then, and charge bar is suspended on upper boom, and the base rod is fixed on lower beam;
(B) be evacuated to 5 * 10
-4Pa～1 * 10
-3Pa, charging into flow velocity is 1～2L/min argon gas, the mobile argon gas plays the refrigerative effect, forms suitable temperature gradient.Charge bar and base rod keep rotation, and sense of rotation is opposite, and speed of rotation is 0～50r/min.
(C) charge bar is begun heating, Heating temperature raises gradually, and heat-up rate is 60～100 ℃/min, until the charge bar fusing, then charge bar is docked with the base rod.The beginning pull, drawing velocity is 0.5～10mm/h, thermograde 100～200K/cm, pull 5～20h, directional freeze finishes, and makes the Nb-Mo-Si-A in-situ composite with laminated structure.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013028834A (en) * | 2011-07-27 | 2013-02-07 | Hokkaido Univ | Nb-Si-BASED HIGH-TEMPERATURE ALLOY |
| CN106119649A (en) * | 2016-06-24 | 2016-11-16 | 西北有色金属研究院 | A kind of Nb Si Ti Mo B sheet alloy and preparation method thereof |
| CN108411136A (en) * | 2018-03-30 | 2018-08-17 | 陕西理工大学 | SiGeC three niobiums enhancing Nb based high-temperature alloys of one kind and preparation method thereof |
| US10227680B2 (en) | 2008-06-18 | 2019-03-12 | The University Of Sheffield | Alloys |
-
2007
- 2007-12-05 CN CNB2007101787423A patent/CN100523245C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10227680B2 (en) | 2008-06-18 | 2019-03-12 | The University Of Sheffield | Alloys |
| JP2013028834A (en) * | 2011-07-27 | 2013-02-07 | Hokkaido Univ | Nb-Si-BASED HIGH-TEMPERATURE ALLOY |
| CN106119649A (en) * | 2016-06-24 | 2016-11-16 | 西北有色金属研究院 | A kind of Nb Si Ti Mo B sheet alloy and preparation method thereof |
| CN108411136A (en) * | 2018-03-30 | 2018-08-17 | 陕西理工大学 | SiGeC three niobiums enhancing Nb based high-temperature alloys of one kind and preparation method thereof |
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