CN110835703A - Single-phase tungsten alloy and preparation method thereof - Google Patents
Single-phase tungsten alloy and preparation method thereof Download PDFInfo
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- CN110835703A CN110835703A CN201911181260.2A CN201911181260A CN110835703A CN 110835703 A CN110835703 A CN 110835703A CN 201911181260 A CN201911181260 A CN 201911181260A CN 110835703 A CN110835703 A CN 110835703A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
Abstract
The tungsten alloy comprises the following components in percentage by mass: 8-17% of Ni, 6-15% of Co, 17-35% of Ta, 10-22% of Nb, 0.5-3% of Zr, 0.1-1% of Gd, 0.5-2% of Ce and the balance of tungsten. The invention enlarges the application range of the tungsten alloy, and further improves the density and the shock resistance of the tungsten alloy on the basis of ensuring the high density and the strong ductility and toughness of the tungsten alloy.
Description
Technical Field
The invention belongs to the technical field of nonferrous metals, and particularly relates to a single-phase tungsten alloy and a preparation method thereof.
Background
The existing manufacturing method of the tungsten alloy material comprises the following steps: the method comprises the steps of firstly, adopting a powder metallurgy method, wherein in the aspect of manufacturing, for a variable cross-section component with a geometric shape, the density distribution is that the end surface and the outer surface have high densities, the middle part has low densities, the density distribution of different parts is uneven, and the density is about 97%; in the aspect of materials, the powder mixed by a plurality of metal materials is adopted, and the powder has different physical properties such as specific gravity, granularity, hardness and the like, so that the layering phenomenon is easy to generate in the conventional die pressing process, the density distribution is also uneven, and the defects cause the comprehensive use performance of the material to be reduced. The other is a vapor deposition method, in which a tungsten alloy material layer is deposited on the surface of a core mold by a physical or chemical method, which has the technical problems of low density (about 98%), high impurity content (about 0.8%) and the like, and the material has high brittleness and poor ductility and toughness, and cannot fully exert the performance advantages of the material.
In order to expand the application field and range of the tungsten alloy material, the uniformity of the material structure and the consistency of the performance must be further improved, and the tungsten alloy material is required to have isotropy, fine and uniform crystal grains and good ductility. The prior art mainly adopts the traditional powder metallurgy, vapor deposition and rolling, and the process has the following defects: firstly, the compactness is not high, the impurity content is high, and the ductility of the material is not enough; secondly, tungsten alloy elements are not uniformly distributed, and the tissue symmetry is poor; and thirdly, brittle compounds are easily formed at the interfaces of the tungsten particles, the plasticity and toughness of the material are poor, and especially under the action of high strain rate, weak bonding layers among the tungsten particles become crack sources.
Disclosure of Invention
The invention aims to provide a single-phase tungsten alloy and a preparation method thereof, which expand the application range of the tungsten alloy and further improve the density and the shock resistance of the tungsten alloy on the basis of ensuring the high density and the strong ductility and toughness of the tungsten alloy.
The purpose of the invention is realized by the following measures:
the tungsten alloy comprises the following components in percentage by mass: 8-17% of Ni, 6-15% of Co, 17-35% of Ta, 10-22% of Nb, 0.5-3% of Zr, 0.1-1% of Gd, 0.5-2% of Ce and the balance of tungsten.
The main components of the alloy and the contents of the components are selected mainly as follows:
ni: the content is 8-17%, Ni, Co, Ta, Nb and W form an alloy matrix structure, the Ni content is lower than 8%, and the effect is not obvious; the Ni content is higher than 20%, Ni and Co form NiCo intermediate compound, and Ni and W form NiW brittle phase, so that the plasticity and toughness of the tungsten alloy are reduced.
The content of Co is 6-15%, Ni, Co, Ta, Nb and W form a matrix structure of the alloy, if the content of Co is less than 5%, the effect is not obvious, and if the content of Co is too high, such as 20%, excessive β phases are formed, and the plasticity is reduced.
Ta: the content of the Ta element is 17-35%, wherein the Ta element is less than 17%, the density of the tungsten alloy can be reduced, and if the Ta element is more than 35%, the cost of the tungsten alloy is high; the corrosion resistance of the tungsten alloy to corrosive media such as strong oxidizing acids and the like can be improved by properly increasing the content of Ta.
Nb: the content of Nb is 10-22%, wherein the Nb content is less than 10%, the activity of the tungsten alloy is reduced, and if the Nb content is more than 22%, the brittleness of the tungsten alloy is increased.
By designing the composition, the tungsten alloy has excellent plasticity and impact toughness, higher density and certain damage after-effect.
In some optional embodiments, the tungsten alloy comprises the following components in percentage by mass: 8-15% of Ni, 8-15% of Co, 20-30% of Ta, 12-20% of Nb, 0.5-2% of Zr, 0.1-0.5% of Gd, 0.5-1% of Ce and the balance of tungsten.
In some optional embodiments, the tungsten alloy comprises the following components in percentage by mass: 8-12% of Ni, 8-12% of Co, 25-30% of Ta, 12-18% of Nb, 0.5-1.5% of Zr, 0.1-0.3% of Gd, 0.5-0.8% of Ce and the balance of tungsten.
In some optional embodiments, the tungsten alloy comprises the following components in percentage by mass: ni 12%, Co 10%, Ta30%, Nb 18%, Zr 1%, Gd 0.2%, Ce 0.6%, and the balance of tungsten.
In some optional embodiments, the tungsten alloy further comprises the following components in percentage by mass: 0.03-0.30% of Nd. By adding a proper amount of Nd into the tungsten alloy, the purity and the plasticity of the tungsten alloy can be improved.
In some optional embodiments, the tungsten alloy further comprises the following components in percentage by mass: 0.4 to 1.5 percent of Fe. The formation of brittle compounds by the excess Co and Ni elements can be reduced.
In some optional embodiments, the tungsten alloy further comprises the following components in percentage by weight: 0.1 to 0.5 percent of Ti. The plasticity and impact toughness of the tungsten alloy are improved. The refined grains are effectively utilized.
Another object of the present invention is to provide a method for preparing a tungsten alloy, which is achieved by the following measures:
a preparation method of a tungsten alloy comprises the following steps:
(1) weighing the components according to the mass percentage;
(2) putting the weighed raw materials into a crucible of a vacuum electromagnetic suspension smelting furnace, vacuumizing to a first set value, then filling protective gas, continuing the raw materials at the first set temperature for a first set time, continuing at a second set temperature for a second set time, and smelting into a tungsten alloy ingot; the smelting can be repeated for 2-4 times;
(3) and putting the tungsten alloy ingot into a vacuum heat treatment furnace for heat treatment to obtain the tungsten alloy.
Wherein, the components can be selected from metal powder of each element, so that the structure of the tungsten alloy is more uniform in the smelting process.
In some optional embodiments, the method further comprises the step of uniformly mixing the weighed raw materials by a ball milling and powder mixing device, and putting the mixture into a consumable vacuum arc furnace.
In some optional embodiments, the method further comprises crushing the raw materials before mixing them uniformly, such that the particle size of each raw material is within a specified range, such as 10-30 μm.
In some of the alternative embodiments, the first and second,the first set value is 1 × 10-2Pa～5×10-2Pa, the first set temperature is 1900-2200 ℃, and the first set time is 10-20 minutes. Wherein, the influence of air on melt metal in the smelting process can be prevented by vacuumizing the vacuum electromagnetic suspension smelting furnace and filling protective gas (nitrogen or helium), and the first set value is 1 multiplied by 10-2Pa～5×10-2Pa, the influence of air on the quality of the smelting process is minimized.
In some optional embodiments, the second set temperature is (2400-2650) degrees Celsius and the duration is 5 minutes to 8 minutes. All the metal powder can be completely melted, and the tungsten alloy ingot can be obtained through cooling.
In some optional embodiments, the heat treatment temperature is 1100-1350 ℃ for 1-3 h, and the tungsten alloy is completely annealed.
Wherein, the electromagnetic suspension smelting stirring technology is adopted in the smelting process, so that the phenomenon of uneven tissue is prevented.
Advantageous effects
1. The tungsten alloy in the embodiment of the invention forms single-phase tungsten alloy through the synergistic effect of the components, so that the tungsten alloy not only has excellent corrosion resistance, but also has uniform structure components, good plasticity and high impact toughness, and can obviously improve the comprehensive use performance of the tungsten alloy.
2. The invention enlarges the application range of the tungsten alloy, and further improves the density and the shock resistance of the tungsten alloy on the basis of ensuring the high density and the strong ductility and toughness of the tungsten alloy.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. Reagents and equipment used in the present invention are commercially available products unless otherwise specified in the examples.
Example 1
This example provides a tungsten alloy having 9.3% of Ni, 11.5% of Co, 25% of Ta, 17.8% of nb, 0.3% of Zr, 0.2% of Gd, 0.7% of ce, 0.1% of Nd, 0.9% of Fe, 0.2% of Ti, and the balance of tungsten and inevitable impurity elements.
Example 2
This example provides a tungsten alloy having the components Ni 11.4%, Co 10.9%, Ta 28.5%, nb14.6%, Zr 1.2%, Gd 0.25%, Ce 0.6%, Nd 0.15%, Fe 1.2%, Ti 0.4%, and the balance of tungsten and unavoidable impurity elements.
Example 3
This example provides a tungsten alloy having the components Ni 8.6%, Co 9.2%, Ta 26.5%, nb13.5%, Zr 0.8%, Gd 0.28%, Ce 0.55%, Nd 0.2%, Fe 0.5%, Ti 0.25%, and the balance of tungsten and unavoidable impurity elements.
Example 4
This example provides a tungsten alloy having the components Ni 12%, Co 10%, Ta30%, Nb 18%, Zr 1%, Gd 0.2%, Ce 0.6%, Nd 0.1%, Fe 1.3%, Ti 0.45%, and the balance of tungsten and unavoidable impurity elements, respectively.
Example 5
This example provides a tungsten alloy having the components Ni 10.7%, Co 8.2%, Ta 29.4%, nb15.5%, Zr 0.6%, Gd 0.14%, Ce 0.75%, Nd 0.2%, Fe 1.4%, Ti 0.32%, and the balance of tungsten and unavoidable impurity elements.
The preparation process comprises the following steps:
(1) weighing the components according to the mass percentage;
(2) crushing the raw materials to ensure that the granularity of each raw material is 10-30 mu m.
(3) Uniformly mixing the materials by a ball-milling powder mixing device, and putting the mixture into a consumable vacuum arc furnace;
(4) putting the weighed raw materials into a crucible of a vacuum electromagnetic suspension smelting furnace, vacuumizing to a first set value by adopting an electromagnetic suspension smelting stirring technology, then filling protective gas (nitrogen or helium), and continuously keeping the raw materials at the first set temperature for the first timeSetting time, and then continuing the second set time at a second set temperature to smelt into a tungsten alloy ingot; repeatedly smelting for 2-4 times; the first set value is 1 × 10-2Pa～5×10-2Pa, wherein the first set temperature is 1900-2200 ℃, and the first set time is 10-20 minutes; the second set temperature is 2400-2650 ℃ and the duration is 5-8 minutes. All the metal powder can be completely melted, and a tungsten alloy ingot can be obtained through cooling;
(5) putting the tungsten alloy ingot into a vacuum heat treatment furnace for heat treatment to obtain the tungsten alloy; and (3) carrying out complete annealing treatment on the tungsten alloy at the heat treatment temperature of 1100-1350 ℃ for 1-3 h.
Comparative example 1
This comparative example provides a result corresponding to the tungsten alloy of the prior art (90 WNiFe).
TABLE 1 comparison of results of examples and comparative examples
From table 1 above, it can be seen that: the single-phase tungsten alloy in the embodiment of the invention has room temperature tensile strength of more than or equal to 1120MPa, elongation after fracture of more than or equal to 34.5%, reduction of area of more than or equal to 43% and impact absorption energy of more than or equal to 44J, and under the condition of equivalent tensile strength, the elongation after fracture, the reduction of area of more than or equal to 1 time and the impact absorption energy of more than or equal to those of the tungsten alloy prepared by the traditional process; has excellent corrosion resistance in nitric acid, sulfuric acid and hydrochloric acid. Further adopts a modern material analysis method, the content of impurity elements of the single-phase tungsten alloy is less than or equal to 0.02 percent, and the density difference is less than or equal to 0.3 percent.
The density of the tungsten alloy reaches 12g/cm3The density of the alloy is improved by about 20% compared with the traditional pure copper, molybdenum and the like, meanwhile, the alloy contains active elements such as Ta, Zr, Ti and the like, and under the impact collision action of high temperature, high pressure and high strain rate, the tungsten alloy has a combustion effect and can ignite substances such as grass, engineering plastics and the like. Further adopting a pulse X-ray experiment, and the strain rate (10) is under the action of explosive detonation energy5～108) Tungsten alloy formThe maximum speed of the head of the penetration body reaches 9000m/s, the length of the continuous penetration body is about 700mm, and the plastic deformation rate reaches more than 1000%.
Claims (10)
1. A tungsten alloy comprises the following components in percentage by mass: 8-17% of Ni, 6-15% of Co, 17-35% of Ta, 10-22% of Nb, 0.5-3% of Zr, 0.1-1% of Gd, 0.5-2% of Ce and the balance of tungsten.
2. The tungsten alloy of claim 1 comprising the following components in mass percent: 8-15% of Ni, 8-15% of Co, 20-30% of Ta, 12-20% of Nb, 0.5-2% of Zr, 0.1-0.5% of Gd, 0.5-1% of Ce and the balance of tungsten.
3. The tungsten alloy according to claim 1 or 2, comprising the following components in mass percent: 8-12% of Ni, 8-12% of Co, 25-30% of Ta, 12-18% of Nb, 0.5-1.5% of Zr, 0.1-0.3% of Gd, 0.5-0.8% of Ce and the balance of tungsten.
4. The tungsten alloy according to claim 1, 2 or 3, comprising the following components in mass percent: ni 12%, Co 10%, Ta30%, Nb 18%, Zr 1%, Gd 0.2%, Ce 0.6%, and the balance of tungsten.
5. The tungsten alloy according to any one of claims 1 to 4, comprising the following components in percentage by mass: 0.03-0.30% of Nd.
6. The tungsten alloy according to any one of claims 1 to 5, comprising the following components in mass percent: 0.4 to 1.5 percent of Fe.
7. The tungsten alloy according to any of claims 1 to 6, comprising the following components in weight percent: 0.1 to 0.5 percent of Ti.
8. A method of making the tungsten alloy of claims 1-7 comprising the steps of:
(1) weighing the components according to the mass percentage;
(2) putting the weighed raw materials into a crucible of a vacuum electromagnetic suspension smelting furnace, vacuumizing to a first set value, then filling protective gas, continuing the raw materials at the first set temperature for a first set time, continuing at a second set temperature for a second set time, and smelting into a tungsten alloy ingot; the smelting can be repeated for 2 to 4 times;
(3) and putting the tungsten alloy ingot into a vacuum heat treatment furnace for heat treatment to obtain the tungsten alloy.
9. The method for preparing tungsten alloy according to claims 1-8, further comprising the steps of mixing the weighed raw materials uniformly by a ball milling and powder mixing device, and placing the mixture into a consumable vacuum arc furnace; before uniformly mixing, crushing the raw materials to ensure that the granularity of each raw material is within a specified range, such as 10-30 mu m.
10. The method for preparing the tungsten alloy according to claims 1-9, wherein the first set value is 1 x 10-2Pa～5×10-2Pa, wherein the first set temperature is 1900-2200 ℃, and the first set time is 10-20 minutes; the second set temperature is 2400-2650 ℃ and the duration is 5-8 minutes; the heat treatment temperature is 1100-1350 ℃ and the time is 1-3 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113122756A (en) * | 2021-04-20 | 2021-07-16 | 西北工业大学 | Titanium-aluminum alloy with multistage twin crystal staggered structure and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3947269A (en) * | 1970-01-07 | 1976-03-30 | Trw Inc. | Boron-hardened tungsten facing alloy |
| CN109338160A (en) * | 2018-11-08 | 2019-02-15 | 钢铁研究总院 | The castable forging solid solution tungsten alloy of one kind and preparation method |
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2019
- 2019-11-27 CN CN201911181260.2A patent/CN110835703A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3947269A (en) * | 1970-01-07 | 1976-03-30 | Trw Inc. | Boron-hardened tungsten facing alloy |
| CN109338160A (en) * | 2018-11-08 | 2019-02-15 | 钢铁研究总院 | The castable forging solid solution tungsten alloy of one kind and preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113122756A (en) * | 2021-04-20 | 2021-07-16 | 西北工业大学 | Titanium-aluminum alloy with multistage twin crystal staggered structure and preparation method thereof |
| CN113122756B (en) * | 2021-04-20 | 2022-03-22 | 西北工业大学 | Titanium-aluminum alloy with multistage twin crystal staggered structure and preparation method thereof |
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