CN101358302A - Method capable of accurately controlling oxygen content and manufacturing alloy by smelting process - Google Patents
Method capable of accurately controlling oxygen content and manufacturing alloy by smelting process Download PDFInfo
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- CN101358302A CN101358302A CNA2007100123393A CN200710012339A CN101358302A CN 101358302 A CN101358302 A CN 101358302A CN A2007100123393 A CNA2007100123393 A CN A2007100123393A CN 200710012339 A CN200710012339 A CN 200710012339A CN 101358302 A CN101358302 A CN 101358302A
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Abstract
The invention relates to a method for manufacturing alloy by using oxides to accurately control the oxygen content (herinafter referred to as oxygen smelting method) and the smelting method, particularly provides a method for manufacturing multifunctional titanium alloy with the oxygen smelting method. The method solves the problems of high cost of metal powders of production raw materials, complex process and equipment, long production period, low production efficiency, high manufacturing cost, etc. existing in the multifunctional titanium alloy manufacture with a powder metallurgic method. The detailed steps of the method are as follows: (1) the necessary oxygen content in the alloy is controlled by the alloy element oxide with a lower melting point; (2) the alloy is manufactured by the smelting method. The invention can accurately and conveniently control the oxygen content in the alloy; moreover, as for the multifunctional titanium alloy, the invention can shorten the production period and reduce the raw material cost and the manufacture cost.
Description
Technical field
The present invention relates to a kind of oxide compound that uses element in the alloy and accurately control the method for the necessary oxygen level of alloy, manufacturing alloy by smelting process, a kind of low-cost method of making multifunctional titanium of the molten method of oxygen of using is provided especially.
Background technology
Oxygen is generally considered to be the impurity element in the alloy and is controlled its content by strictness, yet but it is considered as requisite element in some alloys, for example multifunctional titanium " Gum Metal ".Multifunctional titanium is a kind of new titanium alloy that people such as Japanese scientist Takashi Saito succeeded in developing in recent years, and this alloy has numerous super performances, for example (1) room temperature superplasticity; (2) low elastic modulus (the minimum 40GPa that reaches of E); (3) high strength (room temperature breaking tenacity σ
bAbout 1200MPa); (4) super-elasticity (surpassing 4% at about 2.5% ,-196 o'clock during room temperature); (5) performance of Invar alloy (invar is also referred to as invar) and constant modulus alloy (Elinvar, Ai Linwa alloy) etc.
So many super performance makes this alloy have wide Application Areas, as artificial bone, medicine equipment, medical science shaping, and sports goods, auto parts machinery, manufacturing ultralight spring, and aviation of in severe environment, working and space accurate device etc.This alloy puts goods on the market in Japan at present.
In fact, its representative is a class alloy.Obtain such alloy, must possess following condition simultaneously.(1) the flat fare electronic number (e/a) of composition is about 4.24; (2) about 2.87 Bo value (based on DV-X α bundle method); (3) the Md value of about 2.45eV; (4) have zr element and oxygen element to exist, and Control for Oxygen Content is at 0.7～3.0mol.%; (5) follow-up cold deformation to a certain degree.The composition of this class alloy is so that Ti-24 (Nb+Ta+V)-(Zr, Hf)-O (mol.%) is the basis, typical composition has Ti-9Nb-12Ta-3V-6Zr-1.2O, Ti-23Nb-0.7Ta-2Zr-1.2O and Ti-20Nb-3.5Ta-3.4Zr-1.2O (mol.%) etc.
Because wherein contain a large amount of high-melting-point element nbs, Ta (about 2470 ℃ of Nb fusing point, about 3000 ℃ of Ta fusing point), and in order accurately to control alloying element content, such alloy uses the powder metallurgy method manufacturing at present, technology is as follows always:
(1) the pure metal powder with Ti, Nb, Ta, V, Zr mixes back high-energy ball milling 0.5～2h;
(2) mixed uniformly metal powder isostatic cool pressing under 392MPa;
(3) with raw material 10
-3The following 1300 ℃ of sintering 4h of the vacuum of Pa, stove is chilled to room temperature;
(4) blank is 1150 ℃ of forge hots;
(5) forge rod and roll rod at 800 ℃;
(6) salt shrend behind 1000 ℃ of solid solution 1h in argon gas;
(7) certain deflection is cold rolling.Oxygen level in the alloy is the titanium valve control of 4mol.% by oxygen level.
Powder metallurgic method is made this alloy and had following shortcoming: the cost of (1) raw materials for production metal powder is higher; (2) technology, equipment complexity, the production cycle is long, and productivity is lower, and manufacturing cost is higher.These shortcomings have limited the use of this alloy to a certain extent, and the method that therefore designs a kind of low-cost this alloy of manufacturing is very necessary and has practical significance.
Summary of the invention
The object of the present invention is to provide a kind of method of using oxide compound accurately to control oxygen level, manufacturing alloy by smelting process, a kind of low-cost method of making multifunctional titanium of the molten method of oxygen of using is provided especially, exist when solving powder metallurgic method manufacturing multifunctional titanium: the cost of raw materials for production metal powder is higher, and technology, equipment complexity, production cycle is long, productivity is lower, and manufacturing cost is than problems such as height.
Technical scheme of the present invention is:
A kind of method of using oxide compound accurately to control oxygen level, manufacturing alloy by smelting process, concrete steps are as follows:
(1) use the oxide compound of element in the alloy to control the necessary oxygen level of alloy;
(2) use manufacturing alloy by smelting process.
In making multifunctional titanium, uses oxide compound, titanium sponge, zirconium sponge or/and hafnium, niobium bits or/and vanadium is considered to be worth doing or/and the tantalum powder is raw material, use traditional smelting process to make this alloy.The oxide compound that uses can be TiO
2, Ta
2O
5, Nb
2O
5, V
2O
5A kind of or two or three or four kind, adopt described oxide compound control alloy oxygen level during batching, adopt non-consumable stove vacuum melting or self-consuming furnace vacuum melting.
Advantage of the present invention and beneficial effect are as follows:
1, the invention provides a kind of method of using oxide compound control oxygen level, manufacturing alloy by smelting process, accurately control the necessary oxygen level of alloy, use manufacturing alloy by smelting process by using cheap oxide compound.
2, the invention provides a kind of use oxide compound, titanium sponge, zirconium sponge or/and hafnium, niobium bits or/and the vanadium bits, use the technology of traditional smelting process manufacturing multifunctional titanium or/and the tantalum powder is raw material.Thereby, can accurately control oxygen level easily, shorten the production cycle, reduce starting material and manufacturing cost.
3, the present invention adopts the oxide compound of element in the alloy to control the necessary oxygen level of alloy as raw material, especially can use the oxide compound of refractory metal; Because the oxide compound fusing point is lower with respect to alloying element, can partly or entirely replace the add-on of refractory metal.Owing to have dystectic alloy element Nb, Ta in the multifunctional titanium, be not easy melting, adopt powder metallurgy process to prepare multifunctional titanium traditionally.Be different from tradition and adopt powder metallurgy process to prepare multifunctional titanium, adopt the inventive method, further go out satisfactory multifunctional titanium by smelting method for preparing.
Description of drawings
Fig. 1 (a)-(d) is the binary phase diagram of Ti-O, Ta-O and Nb-O.Wherein, Fig. 1 (a) is Ti-O; Fig. 1 (b) is Ta-O; Fig. 1 (c) is Nb-O; Fig. 1 (d) is V-O.
The XRD spectrum of the multifunctional titanium of the molten manufactured of Fig. 2 oxygen.
First vegetarian noodles in the multifunctional titanium of the molten manufactured of Fig. 3 oxygen distributes.Wherein, (a) be secondary electron image; (b) be the mapping of Ti element; (c) be the mapping of Nb element; (d) be the mapping of Ta element; (e) be the mapping of Zr element; (f) be the mapping of O element.
Pattern before and after Fig. 4 sample is colded pressing, high deformation 45mm → 10.5mm.Wherein, (a) for before colding pressing; (b) for after colding pressing.
Microstructure before and after the multifunctional titanium cold deformation of the molten manufactured of Fig. 5 oxygen.Wherein, (a) 1010 ℃/0.5h, WQ; (b) cold pressing the back perpendicular to the plane of pressure; (c) be parallel to the plane of pressure after colding pressing.
Tensile stress-strain curve after the multifunctional titanium of the molten manufactured of Fig. 6 oxygen is colded pressing.
Thermal expansion curve after the multifunctional titanium of the molten manufactured of Fig. 7 oxygen is colded pressing.
Embodiment
The invention provides a kind of method of using oxide compound control oxygen level, manufacturing alloy by smelting process, provide especially a kind of use oxide compound, titanium sponge, zirconium sponge or/and hafnium, niobium bits or/and the vanadium bits, use the technology of traditional smelting process manufacturing multifunctional titanium or/and the tantalum powder is raw material.Its characteristics are to use the cheap necessary oxygen level of oxide compound control alloy, make multifunctional titanium with traditional smelting process.Fig. 1 (a)-Fig. 1 (d) is the binary phase diagram of Ti-O, Ta-O, Nb-O and V-O, can see, compares oxide compound TiO with Nb, Ta
2, Ta
2O
5, Nb
2O
5And V
2O
5The all lower (TiO of fusing point
2About 1870 ℃ of fusing point, Ta
2O
5About 1880 ℃ of fusing point, Nb
2O
5About 1510 ℃ liquid phase appears, V
2O
5About 680 ℃ of fusing point).When Nb, Ta melted, all raw materials were liquid phase, and this moment, oxygen element will no longer exist with oxide form, but was solidly soluted in the alloy with the form of interstitial atom.As seen, using the molten manufactured multifunctional alloy of oxygen is practicable in theory.Obviously, the present invention is equally applicable to the Control for Oxygen Content in the alloy of other type, and fundamental principle is that to select more low-melting oxide compound of element in the alloy be raw material.
To the present invention be described in detail in detail by embodiment below.
Embodiment
Ti-23Nb-0.7Ta-2Zr-1.2O (mol%) is a typical multifunctional titanium, compare with other above-mentioned multifunctional titanium, because its cost of material density minimum, alloy is less, and do not contain bio-toxicity elements such as V, become present research at most and the multifunctional titanium of application prospect is arranged most, therefore only select this alloy as an example here.
The technological process of molten this alloy of manufactured of oxygen is as follows:
(1) raw material is selected titanium sponge, zirconium sponge, Nb bits, Ta powder and TiO for use
2Powder calculates preparation according to the composition requirement of Ti-23Nb-0.7Ta-2Zr-1.2O (mol%), has used 757.9g titanium sponge, 39.0g zirconium sponge, 465.4g Nb bits, 27.3g Ta powder and 10.4g TiO
2Powder; Then, adopt three vacuum melting of non-consumable stove;
(2) 1200 ℃ of coggings;
(3) 750 ℃ of forge hots;
Cold water is quenched behind (4) 1010 ℃ of solid solution 0.5h;
(5) cold deformation (adopting unidirectional colding pressing) of certain deflection.
The chemical analysis composition is Ti-22.4Nb-0.73Ta-2.0Zr-1.34O (mol%), and the alloy electronic parameter is e/a～4.231, Bo～2.867, Md～2.452.As seen, the alloying constituent of this method manufacturing and electronic parameter and existing multifunctional titanium are very approaching.XRD analysis shows Nb and the Ta that nothing is not molten, does not also have TiO
2(see figure 2), element mapping show that alloying constituent is even, and element-free is poly-partially, see Fig. 3 (a)-(f).
Fig. 4 (a)-(b) is the sample pattern before and after colding pressing, and Fig. 5 (a)-(c) is the microstructure before and after colding pressing.The experiment of colding pressing shows, the alloy of the molten manufactured of oxygen has the room temperature superplasticity equally, this alloy high shrinkage rate under the compression speed of 0.1mm/s reaches 77%, and can further compress, and the hardness test before and after colding pressing shows that alloy does not have obvious work hardening (seeing Table 1).The tensile property of table 2 after for the multifunctional titanium cold deformation of the molten manufactured of oxygen; The stress-strain curves (Fig. 6) of alloy shows that this alloy at room temperature has non-linear elasticity and super-elasticity (～2.3%) equally after colding pressing, and low elastic modulus (～45GPa); Fig. 7 is the thermal expansion curve after colding pressing, and has in the scope of room temperature～300 ℃ and approaches zero the coefficient of expansion, sharply increases at about 350 ℃ of after coefficients.
Every performance of the multifunctional titanium of the molten manufactured of oxygen is made much at one with powder metallurgic method, some performance even be better than the alloy of powder metallurgic method manufacturing.
HV value before and after the multifunctional titanium cold deformation of the molten manufactured of table 1 oxygen
Tensile property after the multifunctional titanium cold deformation of the molten manufactured of table 2 oxygen
| Draft temperature (℃) | σ 0.2(Mpa) | σ b(Mpa) | δ(％) | Ψ(％) |
| -196 | 1640 | 1800 | 6.5 | 21.0 |
| 20 | 1050 | 1080 | 13.5 | 56.5 |
Claims (3)
- But 1, the method for a kind of accurately controlling oxygen content, manufacturing alloy by smelting process is characterized in that:(1) use the oxide compound of element in the alloy to control the necessary oxygen level of alloy;(2) use manufacturing alloy by smelting process.
- But 2, according to the method for the described accurately controlling oxygen content of claim 1, manufacturing alloy by smelting process, it is characterized in that: adopt element in the alloy oxide compound, titanium sponge, zirconium sponge or/and hafnium, niobium bits or/and the vanadium bits or/and the tantalum powder is a raw material, use smelting process to make multifunctional titanium.
- But 3,, it is characterized in that: adopt non-consumable stove vacuum melting or self-consuming furnace vacuum melting according to the method for the described accurately controlling oxygen content of claim 1, manufacturing alloy by smelting process.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100123393A CN101358302A (en) | 2007-08-01 | 2007-08-01 | Method capable of accurately controlling oxygen content and manufacturing alloy by smelting process |
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|---|---|---|---|
| CNA2007100123393A CN101358302A (en) | 2007-08-01 | 2007-08-01 | Method capable of accurately controlling oxygen content and manufacturing alloy by smelting process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103914088A (en) * | 2014-03-19 | 2014-07-09 | 中国科学院近代物理研究所 | Device and method for controlling oxygen content in liquid lead bismuth alloy |
| CN111690834A (en) * | 2020-04-22 | 2020-09-22 | 南京国重新金属材料研究院有限公司 | Preparation method of nickel-based high-temperature alloy with gradient oxygen content |
| CN115301950A (en) * | 2022-08-11 | 2022-11-08 | 西北工业大学 | Preparation method of high-oxygen-content industrial pure titanium with accurately controlled oxygen content |
-
2007
- 2007-08-01 CN CNA2007100123393A patent/CN101358302A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103914088A (en) * | 2014-03-19 | 2014-07-09 | 中国科学院近代物理研究所 | Device and method for controlling oxygen content in liquid lead bismuth alloy |
| CN103914088B (en) * | 2014-03-19 | 2016-01-13 | 中国科学院近代物理研究所 | Control device for oxygen content and method in liquid lead bismuth alloy |
| CN111690834A (en) * | 2020-04-22 | 2020-09-22 | 南京国重新金属材料研究院有限公司 | Preparation method of nickel-based high-temperature alloy with gradient oxygen content |
| CN115301950A (en) * | 2022-08-11 | 2022-11-08 | 西北工业大学 | Preparation method of high-oxygen-content industrial pure titanium with accurately controlled oxygen content |
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