CN100457933C - Preparation method of intensified tantalum and tantalum alloy material - Google Patents
Preparation method of intensified tantalum and tantalum alloy material Download PDFInfo
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- CN100457933C CN100457933C CNB2006101563324A CN200610156332A CN100457933C CN 100457933 C CN100457933 C CN 100457933C CN B2006101563324 A CNB2006101563324 A CN B2006101563324A CN 200610156332 A CN200610156332 A CN 200610156332A CN 100457933 C CN100457933 C CN 100457933C
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Abstract
The invention discloses a making method of high strong tantalum and tantalum alloy as reinforced microscopic tissue structure, which is characterized by the following: increasing oxygen on the surface; forming hard closed thin case structure on the surface with oxygen solid or low-valent tantalum oxide; proceeding heat isostatic pressing solidifying; obtaining dense block material; disposing in the vacuum; adjusting dynamic property of material without growing under 2200 deg. c.
Description
Technical field
A kind of method of strengthening tantalum and tantalum alloy material for preparing relates to the microstructure enhancement method of high-strength tantalum and tantalum alloy preparation methods, particularly tantalum and tantalum alloy material.
Background technology
The reinforcement of metal has many modes, as solution strengthening, precipitation strength, dispersion-strengthened, work hardening, refined crystalline strengthening and particle strengthening, fiber strengthening, whisker reinforcement and stratiform reinforcement etc.Except refined crystalline strengthening, the mechanism of other several schedule of reinforcements mainly be utilize solute atoms with isolated be present in second among the matrix mutually (precipitated phase, disperse phase, add particle, fiber, whisker etc.) stop the motion of dislocation, to improve the metal deformation drag.Refined crystalline strengthening then is to utilize grain-boundary strength in the polycrystal at room temperature to be higher than the characteristic of intracrystalline intensity, strengthens by the quantity that increases crystal boundary.Work hardening is to utilize the increase of dislocation desity in the metal to cause the mutual entanglement of the distortion of crystal lattice and dislocation to stop the motion of dislocation, makes metal strengthening.
For tantalum and tantalum alloy, main enhancement method is solution strengthening and precipitation strength, and other utilizes platelet and fiber strengthened in addition.But present purposes maximum, the widest tantalum tungsten series alloy that is still the tungsten solution strengthening of consumption.Ultra-fine brilliant the reinforcement is a focus of current metal highly malleablized research.But tantalum and tantalum alloy resistance to deformation are big, in most cases all adopt hot-work, and crystal grain is difficult to refinement, and tangible grain ultrafining effect is not also seen in present research.And tantalum usually is used for thermal structure, and ultra-fine brilliant the reinforcement is not suitable for the pyritous Working environment.
Oxygen has the effect of solution strengthening in tantalum, can make the hardness of tantalum increase by 1～3 times, but reduce the plasticity of tantalum greatly.Generally speaking, the oxygen of solid solution will reduce removal as the harmful element of infringement plasticity and toughness as far as possible in the tantalum.From tantalum, remove high temperature and the high vacuum of solid solution oxygen demand more than 2000 ℃ and spread for a long time, and below 2000 ℃, oxygen has lower rate of diffusion in tantalum, is difficult to remove.Therefore, in the processing and preparing process of tantalum and tantalum alloy, avoid the pollution of oxygen element at present as possible.
Tantalum and tantalum alloy structured material adopt the vacuum melting method preparation more, and solid solution type tantalum alloy mainly depends on the solution strengthening of solute element, as the TaW alloy, intensity improves along with the increase of W content, and W content is 12% o'clock, about intensity 650MPa, during W content 15%, reach as high as 750MPa.But the increase of W content strengthens the difficulty of processing of alloy, so the content of tungsten is limited in below 12% in the present alloy.Added element multiple tantalum alloys such as hafnium, carbon on the basis of tantalum-tungsten alloy, though the high temperature creep-resisting ability increases, its intensity also only can reach about 800MPa, and difficulty of processing further strengthens.
When adopting powder metallurgy sintered legal system to be equipped with tantalum and tantalum alloy, powder surface can adsorb more oxygen, and oxygen solid solution diffusion during high temperature sintering causes the material monolithic oxygen level to increase, though intensity improves, plasticity sharply descends.As the Ta-7.5W alloy with powder metallurgy sintered method preparation, behind press working Cheng Sicai and sheet material, though intensity can reach the higher level of 1170MPa, its unit elongation is impaired greatly, only reaches about the sixth of molten alloy.And use the pre-alloyed Ta-10W powdered alloy of low oxygen content, through the dense material of hot isostatic pressing preparation, its intensity then with molten alloy quite.Therefore, also there is not at present method more suitably further to improve the intensity of tantalum and tantalum alloy.And the people that lowly make of intensity have to increase the consumption of material, and this has just caused the tantalum alloy range of application to be very limited.
Summary of the invention
The objective of the invention is deficiency, a kind of method for preparing good percentage elongation, the high tantalum of intensity and tantalum alloy material is provided at last art prior art existence.
The objective of the invention is to be achieved through the following technical solutions.
A kind of method of strengthening tantalum and tantalum alloy material for preparing is characterized in that tantalum and tantalum alloy powder carrying out surperficial oxygenation and handling under the low oxygen partial pressure condition, powder surface is formed have the sosoloid or the tantalum oxygen compound at a low price of the oxygen of hard sealing shell structure; Tantalum powder after will handling again carries out hot isostatic pressing and solidifies, and obtains fine and close block materials; Carry out vacuum heat treatment at last, adjust the mechanical property of material.
The enhancement method of a kind of tantalum of the present invention and tantalum alloy material, it is characterized in that preparing tantalum and the tantalum alloy powder of strengthening tantalum and tantalum alloy material is tantalum or the tantalum alloy ingot casting that adopts pureization of low impurity content of electronic beam vacuum smelting method preparation, the powder made from the hydrogenation dehydriding.
The enhancement method of a kind of tantalum of the present invention and tantalum alloy material is characterized in that in the preparation process that being is 10 with tantalum and tantalum alloy powder in oxygen partial pressure
-1Pa～10
3Pa, temperature are to carry out surperficial oxygenation under 300 ℃～800 ℃ conditions to handle, and the treatment time is 2～12h.
The enhancement method of a kind of tantalum of the present invention and tantalum alloy material, it is characterized in that preparation process is that pretreated tantalum powder is encapsulated in the jacket, under 1300 ℃～1500 ℃ of temperature, pressure 150MPa～200MPa, carry out hot isostatic pressing and solidify, the block materials that acquisition is fine and close.
The enhancement method of a kind of tantalum of the present invention and tantalum alloy material, it is characterized in that preparation process is after the block materials of the densification that will obtain is removed jacket, under 1800 ℃～2400 ℃ high-temperature, carry out 1～4 hour vacuum heat treatment, the adjustment material mechanical performance.
Method of the present invention is on the basis of traditional material, by changing the intensity that strengthening phase structure in the material structure further improves tantalum and tantalum alloy, the potentiality of abundant excavated material.With traditional to separate hard phase (separating out or disperse second phase, particle, fiber etc.) schedule of reinforcement different, strengthening phase is isotropy and space successive; Also brilliant strengthening differently with ultra-fine, is not to rely on increasing of number of grain boundaries, but is basic point of departure to improve grain-boundary strength.Improve grain-boundary strength and be based on, the solid solution or generate compound and can make tantalum produce hardening effect in tantalum of interstitial element oxygen, thereby raising intensity.Fixed by the surface preparation of powder and hot isostatic pressing subsequently, make and produce the isotropic strengthening phase that constitutes by continuous born of the same parents' shape hard shell spatial network of a kind of macroscopic view in the block materials, the unit cell of strengthening phase is the fruit stone structure, seals continuously, and unit cell inside is the matrix metal of high tenacity.Hard shell structure by the microcell sealing is strengthened material, and the high tenacity matrix metal of shell inner sealing carries out the malleableize of material.The hard shell in the particle surface layer, or forms tantalum oxygen compound layer at a low price by the pre-treatment solid solution of interstitial element oxygen by tantalum or tantalum alloy powder.Pretreated powder is the hot isostatic pressing densification under the temperature more much lower than conventional high-temperature sintering temperature, powder particle with hardened layer is connected by metallurgical binding, in block materials, form born of the same parents' shape hard shell spatial network of isotropy and continuous distribution.Because the temperature of hot isostatic pressing is lower, oxygen is difficult to the diffusion homogenizing at intragranular, and oxygen level and material hardness are still the border floor height and central part is low, so material is strengthened.This block materials is carried out the annealing thermal treatment of higher temperature again, and oxygen can be spread to central part by the frictional belt gradually, and material property changes thereupon.So,, make the mechanical property range expansion of material by the high-temperature heat treatment mechanical property of controlled material greatly.
Using the tantalum or the tantalum alloy powder of hydrogenation dehydrogenation, is that 300 ℃～800 ℃, oxygen partial pressure are 10 in temperature
-1Pa～10
3Heat-treat under the condition of Pa, make the powder surface layer form the oxygen solid solution in the sosoloid of tantalum or the low price tantalum pentoxide of oxygen and tantalum formation.Control thickness and the oxygen level that contains the oxygen hard layer by the temperature and the oxygen partial pressure that change the oxygenation processing.
The tantalum or the tantalum alloy powder that will have the surface hard shell structure use pure tantalum container sealing encapsulation, and under 1300 ℃～1500 ℃ of temperature, pressing pressure 150MPa～200MPa condition, hot isostatic pressing is consolidated into the compact block material.The weave construction of material internal is made of the sealing hard shell unit cell aggregate that is similar to the fruit stone structure, the hard shell has constituted crystal boundary of material, intracrystalline is the flexible matrix metal, the aggregate of countless hard shell unit cells constitutes successive isotropy hard shell spatial network, by the main strengthening element of this hard shell spatial network as material.
With tantalum or the tantalum alloy block materials of continuous hard shell spatial network as strengthening phase, high-temperature vacuum thermal treatment by 1800～2400 ℃ of differing tempss, can carry out the regulation and control on a large scale of the strength of materials and plasticity, make the strength of materials by the level of molten alloy up to about the twice of molten alloy.And tantalum alloy material crystal grain after high-temperature heat treatment of this structure is not grown up, and still keeps the weave construction behind the hot isostatic pressing.
Method of the present invention has overcome traditional metal strengthening separation key elements that separated by matrix metal that adopt more and has strengthened, and it is little that each strengthens between key element dependency; Ultra-fine brilliant the reinforcement then strengthened by increasing of number of grain boundaries, can not be used for the shortcoming of thermal structure.With continuous born of the same parents' shape duricrust spacial framework serves as to strengthen key element, and the matrix metal that surrounds with duricrust is the malleableize key element, and main reinforced structure is a hard space shell network.Tantalum or tantalum alloy powder are carried out surperficial oxygenation processing, obtain outer hard interior tough metal-powder, again that the powder hot isostatic pressing is fixed, obtain the compact block material that continuous born of the same parents' shape duricrust spatial network is strengthened, by higher temperature thermal treatment, adjust its mechanical property.The tantalum of this structure and tantalum alloy material be no grain growth phenomenon under 2200 ℃ of high temperature, can be used for thermal structure.
Embodiment
At first adopt the electronic beam vacuum smelting legal system to be equipped with the tantalum or the tantalum alloy ingot casting of pureization of low impurity content, make powder with the hydrogenation dehydriding, again with this powder under lower oxygen partial pressure (10
-1Pa～10
3Pa) be heated to and carry out repeatedly surperficial oxygenation between 300 ℃～800 ℃ and handle, make powder surface form the sosoloid of oxygen or tantalum oxygen compound at a low price; Again pretreated tantalum powder is encapsulated in the jacket, under 1300 ℃～1500 ℃ of temperature, pressure 150MPa～200MPa, carries out hot isostatic pressing and solidify, obtain fine and close block materials; After removing jacket, (1800 ℃～2400 ℃) carry out vacuum heat treatment under higher temperature, adjust the mechanical property of material.
Embodiment 1
Use the tantalum alloy sintered bar of composition as Ta-9.2W-0.5Hf, become alloy cast ingot through electronic beam vacuum smelting, carrying out hydrogenation-fragmentation-dehydrogenation handles, obtain 100 orders～300 purpose powder after the screening, carrying out repeatedly low oxygen partial pressure oxygenation at 300 ℃～800 ℃ handles, obtain case-hardened tantalum alloy powder particle, the powder total oxygen content is increased to 0.15% by 0.02% of ingot casting.With this powder elder generation cold isostatic compaction, pressed compact relative density 65%.Again the isostatic cool pressing pressed compact is packed in the tantalum jacket, carry out hip treatment after the soldering and sealing, hot isostatic pressing pressure 200MPa, 1300 ℃ of temperature kept 4 hours, obtained the block materials of relative density 98.8%.The room-temperature mechanical property of material is: tensile strength 1303MPa, yield strength 1269MPa, unit elongation 4.6%, relative reduction in area 15%, improve 125% and 164% respectively than annealed state melting rolled stock intensity, improve 69% and 76% respectively than processing attitude melting rolled stock intensity with composition.
Embodiment 2
The tantalum alloy sintered bar of the Ta-9.2W-0.5Hf of use and embodiment 1 identical component, become alloy cast ingot through electronic beam vacuum smelting, carrying out hydrogenation-fragmentation-dehydrogenation handles, obtain 100 orders～300 purpose powder after the screening, carrying out repeatedly low oxygen partial pressure oxygenation at 300 ℃～800 ℃ handles, obtain case-hardened tantalum alloy powder particle, the powder total oxygen content is increased to 0.15% by 0.02% of ingot casting.With this powder elder generation cold isostatic compaction, pressed compact relative density 65%.Again the isostatic cool pressing pressed compact is packed in the tantalum jacket, carry out hip treatment after the soldering and sealing, hot isostatic pressing pressure 200MPa, 1300 ℃ of temperature kept 4 hours, obtained the block materials of relative density 98.8%.2200 ℃ of vacuum annealing thermal treatments 4 hours, the relative density of material was 98.2% with the hot isostatic pressing material.The material room-temperature mechanical property is: tensile strength 865MPa, yield strength 751MPa, unit elongation 25%, relative reduction in area 34%.Compare strength degradation with embodiment 1, plasticity improves, and intensity and unit elongation still are higher than the melting rolled stock of work hardening.
Embodiment 3
The tantalum alloy sintered bar of the Ta-9.2W-0.5Hf of use and embodiment 1 identical component, become alloy cast ingot through electronic beam vacuum smelting, carrying out hydrogenation-fragmentation-dehydrogenation handles, obtain 100 orders～300 purpose powder after the screening, carrying out repeatedly low oxygen partial pressure oxygenation at 300 ℃～800 ℃ handles, obtain case-hardened tantalum alloy powder particle, the powder total oxygen content is increased to 0.15% by 0.02% of ingot casting.With this powder elder generation cold isostatic compaction, pressed compact relative density 65%.Again the isostatic cool pressing pressed compact is packed in the tantalum jacket, carry out hip treatment after the soldering and sealing, hot isostatic pressing pressure 200MPa, 1500 ℃ of temperature kept 4 hours, obtained the block materials of relative density 99.5%.The room-temperature mechanical property of material is: tensile strength 1220MPa, yield strength 1195MPa, unit elongation 18%, relative reduction in area 33%, improve 110% and 149% respectively than annealed state melting rolled stock intensity, improve 58% and 66% respectively than the intensity of processing attitude melting rolled stock with composition.
Embodiment 4
The tantalum alloy sintered bar of the Ta-9.2W-0.5Hf of use and embodiment 1 identical component, become alloy cast ingot through electronic beam vacuum smelting, carrying out hydrogenation-fragmentation-dehydrogenation handles, obtain 100 orders～300 purpose powder after the screening, carrying out repeatedly low oxygen partial pressure oxygenation at 300 ℃～800 ℃ handles, obtain case-hardened tantalum alloy powder particle, the powder total oxygen content is increased to 0.15% by 0.02% of ingot casting.With this powder elder generation cold isostatic compaction, pressed compact relative density 65%.Again the isostatic cool pressing pressed compact is packed in the tantalum jacket, carry out hip treatment after the soldering and sealing, hot isostatic pressing pressure 200MPa, 1500 ℃ of temperature kept 4 hours, obtained the block materials of relative density 99.5%.2200 ℃ of vacuum heat treatment 4 hours, density of material was 99.1% with the hot isostatic pressing material.The room-temperature mechanical property of material is: tensile strength 879MPa, yield strength 764MPa, unit elongation 28%, relative reduction in area 45%, intensity and plasticity all are higher than melting processing material and 1300 ℃ the hot isostatic pressing and the congruent material of 2200 ℃ of vacuum heat treatment of work hardening.
Claims (1)
1. one kind prepares the method for strengthening tantalum and tantalum alloy material, it is characterized in that adopting the tantalum or the tantalum alloy ingot casting of pureization of low impurity content of electronic beam vacuum smelting method preparation, and tantalum and the tantalum alloy powder made with the hydrogenation dehydriding are 10 in oxygen partial pressure
- 1Pa～10
3Pa, temperature are 300 ℃～800 ℃, and the treatment time is under the low oxygen partial pressure condition of 2～12h, carry out surperficial oxygenation and handle, and powder surface is formed have sosoloid or the low price tantalum oxygen compound that hard seals the oxygen of shell structure; Tantalum powder after will handling again is encapsulated in the jacket, carries out hot isostatic pressing and solidify under 1300 ℃～1500 ℃ of temperature, pressure 150MPa～200MPa, obtains fine and close block materials; After removing jacket at last, under 1800 ℃～2400 ℃ high-temperature, carry out 1～4 hour vacuum heat treatment, adjust the mechanical property of material.
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| CNB2006101563324A CN100457933C (en) | 2006-12-29 | 2006-12-29 | Preparation method of intensified tantalum and tantalum alloy material |
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| CN100457933C true CN100457933C (en) | 2009-02-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9994929B2 (en) | 2013-03-15 | 2018-06-12 | Ati Properties Llc | Processes for producing tantalum alloys and niobium alloys |
| US9260765B2 (en) * | 2013-03-15 | 2016-02-16 | Ati Properties, Inc. | Process for producing tantalum alloys |
| CN103894442B (en) * | 2014-03-26 | 2016-04-06 | 宁夏东方钽业股份有限公司 | Tantalum pipe and preparation method thereof |
| CN104046822B (en) * | 2014-07-08 | 2016-01-13 | 西北有色金属研究院 | A kind of solution strengthening preparation has the method for the tantalum-base alloy of gradient-structure |
| CN107029306B (en) * | 2016-02-04 | 2020-05-15 | 中国科学院金属研究所 | Marker capable of developing degradation stent under X-ray and preparation method thereof |
| CN114888291B (en) * | 2022-05-20 | 2023-05-26 | 西北有色金属研究院 | Method for improving plasticity of powder metallurgy high tungsten tantalum alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1393571A (en) * | 2001-06-23 | 2003-01-29 | 西北稀有金属材料研究院 | SGS Ta material or Ta product and its preparing process |
| CN1560300A (en) * | 2004-03-09 | 2005-01-05 | 株洲硬质合金集团有限公司 | Preparation method of Taw Yalloy bar |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1393571A (en) * | 2001-06-23 | 2003-01-29 | 西北稀有金属材料研究院 | SGS Ta material or Ta product and its preparing process |
| CN1560300A (en) * | 2004-03-09 | 2005-01-05 | 株洲硬质合金集团有限公司 | Preparation method of Taw Yalloy bar |
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