CN110629071B - Preparation method of titanium alloy with superelasticity and shape memory effect - Google Patents
Preparation method of titanium alloy with superelasticity and shape memory effect Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 20
- 230000003446 memory effect Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 52
- 239000000956 alloy Substances 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002844 melting Methods 0.000 claims abstract description 20
- 230000008018 melting Effects 0.000 claims abstract description 20
- 229910001362 Ta alloys Inorganic materials 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000004663 powder metallurgy Methods 0.000 claims abstract description 18
- 238000003825 pressing Methods 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000462 isostatic pressing Methods 0.000 claims abstract description 4
- 238000003466 welding Methods 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 230000007704 transition Effects 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 4
- 238000010309 melting process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
Classifications
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- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- 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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- 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
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
Abstract
The invention discloses a Ti-Ta intermediate alloy which is prepared by using Ti powder and Ta powder as raw materials and sequentially carrying out powder mixing, isostatic pressing and sintering by a powder metallurgy method; when the powder is mixed by the powder metallurgy method, manual powder mixing and mechanical powder mixing are sequentially carried out, wherein the manual powder mixing is carried out for 3-6 times, and the mechanical powder mixing is carried out for 2-4 hours; during vacuum sintering, the sintering temperature is 1100-1300 ℃, and the temperature is kept for 2-4 h; pressing the Ti-Ta intermediate alloy and the mixture to obtain an electrode block; wherein the mixture consists of 0-grade or 1-grade titanium sponge particles and industrial-grade HZr-1 zirconium sponge particles; assembling and welding a plurality of electrode blocks into a consumable electrode, and performing vacuum consumable melting on the consumable electrode for at least four times to obtain a Ti-Zr-Ta alloy ingot; the invention can adjust the super-elasticity and the shape memory effect of the titanium alloy by controlling the phase transition temperature range and the stability of the titanium alloy.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of titanium material processing, and particularly relates to a preparation method of a titanium alloy with superelasticity and shape memory effect.
[ background of the invention ]
Titanium has good biocompatibility and is the first choice metal material for high-end medical instruments or surgical implants. The Ti-Zr-Ta series titanium alloy has lower elastic modulus, unique superelasticity and shape memory effect, and belongs to novel medical titanium alloy.
The melting of titanium alloy usually adopts methods such as vacuum induction melting, vacuum consumable remelting and the like. If vacuum induction melting is adopted, the melting temperature of the metal can reach about 2000 ℃, the metal tantalum belongs to refractory metal, the melting point is as high as 2996 ℃, and the melting point is more than 1000 ℃ higher than that of titanium and zirconium, and the tantalum is not easy to melt in the vacuum induction melting and becomes an inclusion in the alloy instead. If the consumable electrode needs to be pressed in vacuum consumable remelting, the raw materials of the metal titanium and the metal zirconium are sponge titanium and sponge zirconium, and the metal tantalum with less content is added in the form of tantalum powder. However, in the Ti-Zr-Ta alloy with super elasticity and shape memory effect, the content of tantalum element is over 10 percent, the high content Ta powder and spongy Ti and Zr are mixed unevenly, the material loss and the environmental pollution to a certain degree are caused, and the composition of the cast ingot is also uneven.
The uniformity of components in the titanium alloy is a key factor influencing the alloy characteristics, and the alloy characteristics of the titanium alloy influence the range of phase transition temperature and the stability of phase transition, so that the superelasticity and the shape memory effect of the titanium alloy are difficult to ensure within a specified range.
[ summary of the invention ]
The invention aims to provide a preparation method of a titanium alloy with superelasticity and shape memory effect, which is used for adjusting the superelasticity and shape memory effect of the titanium alloy by controlling the phase transition temperature range and stability of the titanium alloy.
The invention adopts the following technical scheme: the preparation method of the titanium alloy with superelasticity and shape memory effect comprises the following steps:
mixing powder, isostatic pressing and sintering sequentially by using Ti powder and Ta powder as raw materials by adopting a powder metallurgy method to prepare a Ti-Ta intermediate alloy; when the powder is mixed by the powder metallurgy method, manual powder mixing and mechanical powder mixing are sequentially carried out, wherein the manual powder mixing is carried out for 3-6 times, and the mechanical powder mixing is carried out for 2-4 hours; during vacuum sintering, the sintering temperature is 1100-1300 ℃, and the temperature is kept for 2-4 h;
pressing the Ti-Ta intermediate alloy and the mixture to obtain an electrode block; wherein the mixture consists of 0-grade or 1-grade titanium sponge particles and industrial-grade HZr-1 zirconium sponge particles;
and assembling and welding a plurality of electrode blocks into a consumable electrode, and performing vacuum consumable melting on the consumable electrode for at least four times to obtain a Ti-Zr-Ta alloy ingot.
Furthermore, the particle sizes of the 0-grade or 1-grade titanium sponge particles and the industrial-grade HZr-1 zirconium sponge particles are both 3-12.7 mm.
Furthermore, the mesh number of the Ti powder and the Ta powder is more than 200 meshes.
Further, the Ti-Ta master alloy was (Φ 40mm) × (250-280 mm).
And further, when the electrode block is pressed, the 1/2 mixture is added before and after the Ti-Ta intermediate alloy is added into the pressing die, and the Ti-Ta intermediate alloy rod is placed in the center of the pressing die cavity.
The invention has the beneficial effects that: the invention prepares the intermediate alloy in advance by a powder metallurgy method, then presses the intermediate alloy, the mixture of sponge titanium and sponge zirconium into the electrode block, in the consumable melting process, the metal Ta after the metal Ti is melted is converted into the Ta bracket with a porous structure, compared with the metal Ta or Ti-Ta alloy of crystal, the Ta bracket with the porous structure enhances the activity of the Ta bracket per se, accelerates the melting speed, and is synchronously melted with the mixture of the sponge titanium and the sponge zirconium around, finally the Ti-Zr-Ta alloy cast ingot with uniform components is obtained, and the Ti-Zr-Ta alloy cast ingot has the phase transition temperature range and stability, and good superelasticity and shape memory effect.
[ detailed description ] embodiments
The present invention will be described in detail with reference to the following embodiments.
The invention discloses a preparation method of a titanium alloy with superelasticity and shape memory effect, which comprises the following steps:
firstly, Ti powder and Ta powder are used as raw materials, the mesh number of the Ti powder and the mesh number of the Ta powder are both larger than 200 meshes, powder mixing, isostatic pressing and sintering are sequentially carried out by adopting a powder metallurgy method, and a Ti-Ta intermediate alloy is prepared, wherein the Ti-Ta intermediate alloy is a bar material, and the external dimension is (phi 40mm) × (250-280mm), manual powder mixing and mechanical powder mixing are sequentially carried out when the powder mixing is carried out by adopting the powder metallurgy method, the powder mixing is carried out for 3-6 times manually so as to eliminate hardening, hard blocks and the like in the powder material, the mechanical powder mixing is carried out for 2-4 h, a V-shaped powder mixing machine is adopted, the uniform mixing of the powder material with increased density difference is favorably realized, and the sintering temperature is 1100-1300 ℃ and the heat is preserved for 2-4 h;
and pressing the Ti-Ta intermediate alloy and the mixture to obtain the electrode block. When the electrode block is pressed, 1/2 mixed materials are respectively added before and after the Ti-Ta intermediate alloy is added into a pressing die, namely the mixed materials are divided into two parts in advance, and after all the raw materials are added, the Ti-Ta intermediate alloy rod needs to be ensured to be placed in the center of a pressing die cavity. Wherein the mixture consists of 0-grade or 1-grade titanium sponge particles and industrial-grade HZr-1 zirconium sponge particles, and the mixture is formed by adopting a mechanical mixing method. The particle sizes of the 0-grade or 1-grade titanium sponge particles and the industrial-grade HZr-1 zirconium sponge particles are both 3-12.7 mm.
For titanium alloy with more alloy element content, the consumable electrode block is in a specification as small as possible, and is beneficial to realizing uniform diffusion of the alloy element in a smaller volume range.
And assembling and welding a plurality of electrode blocks into a consumable electrode, and performing vacuum consumable melting on the consumable electrode for at least four times to obtain a Ti-Zr-Ta alloy ingot.
The invention prepares the intermediate alloy in advance by a powder metallurgy method, then presses the intermediate alloy, the mixture of sponge titanium and sponge zirconium into the electrode block, in the consumable melting process, the metal Ta after the metal Ti is melted is converted into the Ta bracket with a porous structure, compared with the metal Ta or Ti-Ta alloy of crystal, the Ta bracket with the porous structure enhances the activity of the Ta bracket per se, accelerates the melting speed, and is synchronously melted with the mixture of the sponge titanium and the sponge zirconium around, finally the Ti-Zr-Ta alloy cast ingot with uniform components is obtained, and the Ti-Zr-Ta alloy cast ingot has the phase transition temperature range and stability, and good superelasticity and shape memory effect.
The method of the invention adopts a powder metallurgy method to prefabricate the Ti-Ta intermediate alloy, and the theoretical density of the Ti-Ta intermediate alloy is lower than that of metal Ta. In the consumable melting process, metal Ta is converted into a Ta support with a porous structure, so that the rapid and uniform melting of Ta is promoted, and a Ti-Zr-Ta alloy ingot with uniform components is obtained.
The Ti-Ta intermediate alloy is prefabricated by a powder metallurgy method, and Ti powder and Ta powder are directly used as raw materials. The conventional operations of mixing powder and sintering can be realized. Moreover, the component proportion and the external dimension of the Ti-Ta alloy can be properly adjusted according to the component proportion of the final Ti-Zr-Ta alloy, and the Ti-Ta alloy has strong flexibility and strong operability.
When the electrode block is pressed, the Ti-Ta intermediate alloy prefabricated by a powder metallurgy method is directly placed in the middle of the mixture of the sponge Ti and the sponge Zr, and the electrode block is pressed at one time, so that good compactness is ensured. Compared with the method for prefabricating the Ti-Ta intermediate alloy by directly using Ta powder, the method has the advantages that the problems of powder loss and pollution in the pressing and transferring processes of the electrode block are solved.
The key effect of the invention is reflected in the melting process of the consumable electrode. On one hand, the theoretical density of the Ti-Ta intermediate alloy prefabricated by the powder metallurgy method is lower than that of metal Ta, and the Ti-Ta intermediate alloy is favorable for good clamping of the intermediate alloy and surrounding materials. On the other hand, Ti in the Ti-Ta master alloy prepared by the powder metallurgy method has a low melting point and is melted preferentially. In the Ti-75Ta master alloy, the volume percentage of Ti powder is about 55 percent. In the Ti-55Ta master alloy, the volume percentage of Ti powder is about 75 percent. Furthermore, the sintered Ti-Ta master alloy still has 5-10% porosity. After more than half of the volume of Ti powder is melted, the residual Ta is gradually changed into a Ta bracket with a random porous structure. Compared with the metal Ta of crystal or Ti-Ta alloy, the Ta support with the porous structure enhances the activity of the Ta support and accelerates the melting speed. The synchronous melting with the surrounding titanium sponge and zirconium sponge mixture is basically realized. And the Ta bracket with a porous structure has very low density, is easy to keep the surrounding materials in a stable state, can not fall off, and eliminates the hidden trouble of generating high-melting-point Ta component segregation.
Therefore, in the process of vacuum consumable melting of the Ti-Ta intermediate alloy prefabricated by the powder metallurgy method, metal Ta is converted into a Ta support with a porous structure. The melting speed of Ta is accelerated, the stable state of material melting is maintained, and the Ti-Zr-Ta alloy ingot with uniform components is realized.
Example 1:
the preparation method of the Ti-20Zr-10Ta (at%) alloy ingot comprises the steps of selecting 0-level or 1-level titanium sponge, sponge zirconium, titanium powder and tantalum powder as raw materials, enabling the particle sizes of the titanium sponge and the sponge zirconium to be 3-12.7 mm, enabling the titanium powder and the tantalum powder to be larger than 200 meshes, converting the alloy ratio into Ti-26Zr-26Ta (wt%) alloy, prefabricating a Ti-Ta intermediate alloy by a powder metallurgy method, enabling the element ratio to be Ti-75Ta (wt%), enabling the unit weight to be 4.4Kg, enabling the measured size to be phi 40mm × 280mm, conducting fast pressing on a consumable electrode, mixing 5.0Kg of titanium sponge and 3.3Kg of sponge zirconium, pouring the mixture into a pressing die twice, adding the Ti-75Ta intermediate alloy in the middle, enabling the unit weight to be 12.7Kg, enabling the external size to be □ 100 × 300mm, namely, enabling square blanks with the side length to be 100mm, enabling the square blanks to be pressed into 40 electrode blocks, enabling each 5Ta block to be welded into a consumable electrode with a phi 8Kg, enabling the ingot to be manufactured into Ti-26Zr ingot blanks with different structures, and enabling the Ti-26Zr ingot to be manufactured through smelting and enabling the ingot to be obtained through a chemical ingot casting process according to obtain a subsequent ingot with different Ti-26Zr ingot with different metallurgical ingot structure and a uniform segregation table.
TABLE 1 chemical composition (wt%) of Ti-26Zr-26Ta alloy ingot
| Location of a body part | Zr | Ta |
| On the upper part | 26.22 | 26.16 |
| In | 25.94 | 26.24 |
| Lower part | 26.10 | 26.35 |
Example 2:
46.5Ti-46.5Zr-7Ta (at%) alloy ingot preparation method, the raw materials select 0 or 1 grade titanium sponge, sponge zirconium, titanium powder, tantalum powder as raw materials, the granularity of the titanium sponge and the sponge zirconium is 3-12.7 mm, the titanium powder and the tantalum powder are both larger than 200 meshes, the alloy proportion is converted into Ti-55Zr-16Ta (wt%) alloy, a powder metallurgy method is adopted to prefabricate Ti-Ta intermediate alloy, the element proportion is Ti-55Ta (wt%), the unit weight is 3.7Kg, the actual measurement size is phi 40mm × 260mm, when the consumable electrode is pressed quickly, 2.0Kg titanium sponge and 7.0Kg zirconium sponge are mixed, the mixture is poured into a pressing die twice, the middle is added with the Ti-55Ta intermediate alloy, the unit weight of the electrode is 12.7Kg, the external dimension is □ 100 × 300mm, namely 100mm, the blank stock of Ta is pressed into 40 electrode blocks, and each Ta-55 Ta intermediate alloy ingot is manufactured into a square ingot with different length according to the actual situation, each 5 Ti-7 Ta alloy ingot is manufactured by smelting, the ingot is manufactured according to the side length, the chemical composition, the ingot is different from the square ingot, the ingot is manufactured by smelting, the ingot, the side length is 8-ingot is different from the ingot, the ingot is 8-ingot, the ingot is calculated by the average ingot, the average ingot is calculated by the average.
TABLE 2 chemical composition (wt%) of Ti-55Zr-16Ta alloy ingot
| Location of a body part | Zr | Ta |
| On the upper part | 55.21 | 16.16 |
| In | 55.04 | 16.05 |
| Lower part | 55.16 | 15.85 |
Claims (4)
1. The preparation method of the titanium alloy with superelasticity and shape memory effect is characterized by comprising the following steps:
mixing powder, isostatic pressing and sintering sequentially by using Ti powder and Ta powder as raw materials by adopting a powder metallurgy method to prepare a Ti-Ta intermediate alloy; when the powder is mixed by the powder metallurgy method, manual powder mixing and mechanical powder mixing are sequentially carried out, wherein the manual powder mixing is carried out for 3-6 times, and the mechanical powder mixing is carried out for 2-4 hours; during vacuum sintering, the sintering temperature is 1100-1300 ℃, and the temperature is kept for 2-4 h;
pressing the Ti-Ta intermediate alloy and the mixture to obtain an electrode block, wherein the mixture consists of 0-grade or 1-grade titanium sponge particles and industrial-grade HZr-1 zirconium sponge particles, and the Ti-Ta intermediate alloy is phi 40mm × (250-280 mm);
and assembling and welding a plurality of electrode blocks into a consumable electrode, and performing vacuum consumable melting on the consumable electrode for at least four times to obtain a Ti-Zr-Ta alloy ingot.
2. The method for preparing the titanium alloy with superelasticity and shape memory effect according to claim 1, wherein the titanium sponge particles of grade 0 or grade 1 and the zirconium sponge particles of technical grade HZr-1 both have a particle size of 3-12.7 mm.
3. The method of claim 2 wherein the Ti and Ta powders are both greater than 200 mesh in size.
4. The method of preparing a titanium alloy having superelasticity and shape memory effect according to any one of claims 1-3, wherein 1/2 of said mixture is added before and after the addition of said Ti-Ta master alloy to the pressing mold during pressing of the electrode block, said Ti-Ta master alloy rod being placed in the center of the cavity of the pressing mold.
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| CN114540689B (en) * | 2022-01-22 | 2022-10-18 | 华东交通大学 | Antibacterial medical tantalum alloy with ultralow elastic modulus and preparation method thereof |
| CN115488341A (en) * | 2022-09-26 | 2022-12-20 | 吉林大学 | Integrated preparation method of low-modulus biomedical titanium alloy with bionic structure |
| CN115896507B (en) * | 2022-11-23 | 2024-04-09 | 宁夏中色金航钛业有限公司 | Niobium hafnium titanium zirconium tantalum tungsten alloy and preparation process thereof |
| CN115948670A (en) * | 2023-01-13 | 2023-04-11 | 湘潭大学 | AM decomposition type shape memory alloy and preparation method thereof |
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| JP2002060804A (en) * | 2000-08-11 | 2002-02-28 | Sumitomo Metal Ind Ltd | Hydrogen storage alloy excellent in durability and its production method |
| US9199308B2 (en) * | 2011-09-20 | 2015-12-01 | GM Global Technology Operations LLC | Method of producing composite articles and articles made thereby |
| CN107904442A (en) * | 2017-12-18 | 2018-04-13 | 西安赛特思迈钛业有限公司 | A kind of processing method of fine grain pure titanium rod material |
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| CN101724764B (en) * | 2009-12-10 | 2011-07-20 | 中南大学 | Process for preparing biomedical beta-titanium alloy |
| CN103773969B (en) * | 2013-12-25 | 2016-01-20 | 西安西工大超晶科技发展有限责任公司 | A kind of preparation method of the electrode for titanium alloy vacuum consumable smelting containing tantalum |
| CN104342583B (en) * | 2014-09-25 | 2016-12-07 | 中南大学 | A kind of Ti-Ta alloy and its preparation method and application |
| CN108517441B (en) * | 2018-04-15 | 2019-04-16 | 烟台浩忆生物科技有限公司 | Low transformation temperature titanium zirconium niobium tantalum marmem, preparation method and applications |
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| JP2002060804A (en) * | 2000-08-11 | 2002-02-28 | Sumitomo Metal Ind Ltd | Hydrogen storage alloy excellent in durability and its production method |
| US9199308B2 (en) * | 2011-09-20 | 2015-12-01 | GM Global Technology Operations LLC | Method of producing composite articles and articles made thereby |
| CN107904442A (en) * | 2017-12-18 | 2018-04-13 | 西安赛特思迈钛业有限公司 | A kind of processing method of fine grain pure titanium rod material |
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