CN101070570A - Method for mixed addition of rare earth and boron element in titanium alloy - Google Patents
Method for mixed addition of rare earth and boron element in titanium alloy Download PDFInfo
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- CN101070570A CN101070570A CN 200710041968 CN200710041968A CN101070570A CN 101070570 A CN101070570 A CN 101070570A CN 200710041968 CN200710041968 CN 200710041968 CN 200710041968 A CN200710041968 A CN 200710041968A CN 101070570 A CN101070570 A CN 101070570A
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Abstract
A method of mixing and adding rare earth and boron element in one kind of titanium alloy, it belongs to the titanium alloy processing technology area. The method of this invention is below: add the rare earth and boron element by the form of boronising rare earth compound or by the form of boronising rare earth mixture to titanium alloy, when adding, make rare-earth element occupy 56% -91% of the mix supplement, and mix it with titanium sponge or titanium powder evenly by using the stirring and mixing method then make it as electrode by using press or extruder, the density of electrode should be controlled between 75% and 90%, at last, processed it using the liquid state or solid state method, finally, it realize to prepare TiB and the new titanium alloy which was strengthened by rare earth oxide compound. The invented rare earth boride is powdery, and it extremely stable, so its ingredient is simple, storage is convenient. It May simplify and reduce the production process of titanium alloy, reduce the preparation cost, suit the volume production.
Description
Technical field
What the present invention relates to is a kind of method of titanium alloy processing technique field, specifically is the method for mixed addition of a kind of titanium alloy middle-weight rare earths and boron.
Background technology
The research that rare earth element is used for titanium or titanium alloy starts from the fifties.The U.S., the Soviet Union, Japan, Britain, China etc. carry out this type of research in succession.In recent years, along with the development of titanium alloy especially high-temperature titanium alloy, the application of rare earth in titanium alloy is noticeable day by day.Yet how rare earth element effectively being added in the titanium alloy is the key issue that the preparation high quality contains the rare earth titanium alloy.When melting contains the titanium alloy of rare earth element, be mostly to adopt pure rare earth or aluminium rare earth intermediate alloy both at home and abroad.But rare earth element has very high chemically reactive, and oxidation takes place in air under the room temperature easily, and transportation and storage in the time of can giving suitability for industrialized production on the one hand bring difficulty, brings difficulty also on the other hand the actual composition of accurate control material.And the pure rare earth fusing point is well below the fusing point of titanium, and therefore in fusion process, rare earth is fusing and preferential the combination with Sauerstoffatom and generate thick nascent rare earth oxide particles before titanium sponge very easily.Prepare titanium alloy with the aluminium rare earth intermediate alloy, for making the aluminium rare earth intermediate alloy severe oxidation does not take place at room temperature, often the content with rare earth is controlled at below 20% (weight percent), and aluminium at the content of master alloy more than 80%.The master alloy of high alumina like this, can not be selected as the master alloy of the not high titanium alloy of general aluminium content, especially the titanium alloy that preparation is contained molybdenum, vanadium, niobium etc., often also be to adopt the aluminium alloy that contains these elements to make master alloy, add in the titanium alloy in this master alloy mode, can cause the alloying ingredient difficulty like this.In addition, the toughness of aluminium rare earth intermediate alloy is better, is difficult for being broken into bulk, can only use with car plane or car bits mode, makes troubles for like this preparation of titanium alloy material and electrode compacting.Meanwhile, to add the titanium alloy to contain rare earth with solid-state approach (as powder metallurgy or mechanical alloying) preparation be impossible at all for such master alloy mode.
Find that by prior art documents people such as Geng Ke are at " Shanghai Communications University's journal ", in February, 2004, the 38th rolls up, and the 2nd phase, 300-303 writes articles " synthetic TiB of original position and Nd
2O
3Strengthen titanium matrix composite ", the document is that one of raw material has prepared TiB and Nd with pure Nd
2O
3The enhanced titanium alloy, its Nd
2O
3Particle is thick, and when content of rare earth is higher, easy nodularization and branch crystallization, thick rare earth oxide becomes the formation of crack of material fragility fracture, causes the deterioration of material property.In addition, recently the titanium alloy of strengthening with TiB has obtained increasing application, but is to add in the titanium alloy in boron powder mode traditionally, however the high purity boron powder cost an arm and a leg, especially on Chinese market, be difficult to obtain the high purity boron powder.For heat-resistant titanium alloy, add the resistance toheat that rare earth and boron realize improving titanium alloy, become a main direction of studying that further improves the resistance toheat of titanium alloy at present both at home and abroad.As previously mentioned, effective key issue that presses for solution into the research of heat resistance titanium alloy, production of having added of rare earth and boron.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, the method for mixed addition of a kind of titanium alloy middle-weight rare earths and boron is provided.Adopt the addition manner of rare-earth boride master alloy to add in the titanium alloy, control contains the microstructure of rare earth titanium alloy, improves performance, and realizes containing the rare earth titanium alloy with the solid-state approach preparation.
The present invention is achieved by the following technical solutions, and the inventive method is specially:
Rare earth and boron are added in the titanium alloy with the boronation rare earth compound or in the mixture mode of boronation rare earth, add fashionable, make the weight percent of rare earth element account for 56%～91% of mixing additive, and utilize the method mix that itself and sponge titanium or ti powder are mixed, utilize press or extrusion machine to make electrode then, the density of electrode is controlled between the 75%-90%, utilize liquid state or solid-state approach to process at last, the final new titanium alloy of realizing that preparation TiB and rare earth oxide are strengthened.
Described boronation rare earth compound is meant: hexaboride, four borides or both mixtures.
Described liquid method is meant: vacuum consumable arc-melting, vacuum non-consumable arc melting, any method of electron-beam cold bed furnace melting that titanium alloy is commonly used.
Described solid-state approach is meant: powder metallurgy process or mechanical alloying method.
It is 56%～83% that described rare earth element, its weight percent account for the preferable range of mixing additive.
Described rare earth element comprises all cerium groups and yttrium group element, or mixed rare-earth elements.
The present invention proposes a kind of new rare earth addition manner and controls the microstructure that contains the rare earth titanium alloy in order to help the microtexture that suitability for industrialized production and acquisition contain the rare earth titanium alloy preferably, improves performance, and realizes containing the rare earth titanium alloy with the solid-state approach preparation.Be that the present invention adopts the addition manner of rare-earth boride master alloy to add titanium alloy.Rare-earth boride is Powdered, and highly stable, and therefore batching is simple, and it is convenient to store.Simultaneously can simplify and shorten the Production Flow Chart of titanium alloy, reduce preparation cost, be fit to produce in batches.
The present invention selects for use the mode of boronation rare earth or its mixture to add in the titanium alloy and has the following advantages:
(1) chemical property is stable at normal temperatures for compound, oxidizing reaction can not take place, thereby bring convenience to the production of its transportation, storage and titanium alloy; (2) fusing point height, helping adding in melting makes the rare earth oxide small and dispersed distribute man-hour, avoided traditional pure rare earth to be directly used in configuration during titanium alloy, owing in air, severe oxidation can take place, thereby made titan alloy casting ingot be easy to generate thick rare earth oxide metallurgical imperfection such as to be mingled with; Studies show that (3) add the B element in the titanium matrix and can produce the TiB ceramic particle, TiB and titanium matrix bond are good, can significantly improve the mechanical property of titanium matrix, are expected to produce the complex intensifying effect, and the titanium alloy of boracic has also obtained increasing application; (4) crumbly mass is Powdered, helps batching, and can realize containing the rare earth titanium alloy with solid-state approach (powder metallurgy, mechanical alloying) preparation.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.Below among each embodiment the mixture of raw material boronation rare earth compound or boronation rare earth be commercially available.
Embodiment 1
Present embodiment is implemented under following implementation condition and technical requirements condition:
Utilize vacuum consumable arc-melting method preparation 2.5% (La
2O
3+ TiB)/the Ti alloy.
Take by weighing one-level titanium sponge (mass percent 98.9%), lanthanum hexaborane (mass percent of lanthanum in compound is 70%) powder (mass percent 1.1%) according to proportioning, after it is mixed, utilize press to be pressed into stick electrode (density of electrode reaches 75%), pack into behind the electrode assembly welding in the vacuum consumable electrode arc furnace (commercially available), vacuum consumable electrode arc furnace is vacuumized, the working vacuum degree is 0.1Pa, utilize vacuum consumable electrode arc furnace to carry out melting then, sample melting secondary, last furnace cooling makes the titanium alloy of TiB and rare earth lanthanum oxide complex intensifying.
Find that through microscopic examination the present embodiment method prepares synthetic TiB and rare earth lanthanum oxide is very tiny, and distributes very evenly.Especially the rare earth lanthanum oxide size reaches nano level.And in the titanium alloy that the TiB of traditional method preparation and rare earth lanthanum oxide are strengthened, the size of rare earth oxide reaches 10 micron orders, and skewness.Both compare, and it is less that the present embodiment method prepares titanium alloy performance dispersity, and intensity, plasticity all improve more than 15% than the titanium alloy with the traditional method preparation.
Embodiment 2
Present embodiment is implemented under following implementation condition and technical requirements condition:
Utilize powder metallurgy process preparation 2.0% (Y
2O
3+ TiB)/the Ti-6Al-4V alloy.
Take by weighing titanium sponge (mass percent 89.5%) according to proportioning, six yttrium borides (mass percent of yttrium in compound is 56%) powder (mass percent 0.6%), AlV (mass percent 50% of aluminium and vanadium) master alloy powder (mass percent 7.9%) and aluminium powder (mass percent 2.0%), after it is mixed, utilize press to be pressed into sample (density reaches 90%), pack in the vacuum sintering furnace (commercially available), to the vacuum sintering stove evacuation, the working vacuum degree is 0.01Pa, 1350 ℃ of insulations two hours, last furnace cooling makes the titanium alloy of TiB and rare-earth oxidation yttrium complex intensifying.
Find that through microscopic examination the present embodiment method prepares synthetic TiB and the rare-earth oxidation yttrium is very tiny, the size of yttrium oxide is at nano level, and distributes very evenly.Relatively find with the boracic of powder metallurgy process preparation and the titanium alloy of rare earth, its TiB and rare earth oxide are more more tiny than liquid working method synthetic wild phase, and density is brought up to more than 98% by 95%, and intensity, plasticity all improve more than 12% than the titanium alloy with the traditional method preparation.
Embodiment 3
Present embodiment is implemented under following implementation condition and technical requirements condition:
Utilize vacuum consumable arc-melting method preparation 1.5% (La
2O
3+ Ce
2O
3+ TiB)/the Ti1100 alloy.
Take by weighing titanium sponge (mass percent 84.42%), boronation lucium LaB according to proportioning
6(mass percent of lanthanum in compound is 70%) powder (mass percent 0.26%) and CeB
4(mass percent of cerium in compound is 91%) (mass percent 0.26%), titanium tin master alloy (wherein the tin mass percent is 65%) (mass percent 4.18%), zirconium sponge (mass percent 4.02%), fine aluminium (mass percent 5.61%), aluminium molybdenum master alloy (molybdenum mass percent 50%) (mass percent 0.80%), after it is mixed, utilize press to be pressed into stick electrode (the electrode density reaches 80%), pack into behind the electrode assembly welding in the vacuum consumable electrode arc furnace, vacuum consumable electrode arc furnace is vacuumized, the working vacuum degree is 0.01Pa, utilize vacuum consumable electrode arc furnace to carry out melting then, sample melting secondary, last furnace cooling makes the titanium alloy of TiB and rare earth oxide complex intensifying.
Find that through microscopic examination the present embodiment method prepares synthetic TiB and rare earth cerium oxide, lanthanum trioxide is very tiny, and distributes very evenly.The rare earth oxide size reaches nano level.Because rare earth oxide is very tiny, strengthened matrix alloy effectively, show after tested: room temperature strength, hot strength (high temperature tensile strength, creep, enduring quality) have improved 12% than the titanium alloy with the identical complex intensifying of the composition of traditional method preparation at least, and plasticity has then improved 18%.
Embodiment 4
Present embodiment is implemented under following implementation condition and technical requirements condition:
Utilize vacuum consumable arc-melting method preparation 1.5% (La
2O
3+ Ce
2O
3+ TiB)/the Ti1100 alloy.
In the proportioning, get CeB
4(mass percent of cerium in compound is 83%).Other conditions are with embodiment 3.Find that through microscopic examination the present embodiment method prepares synthetic TiB and rare earth cerium oxide, lanthanum trioxide is very tiny, and distributes very evenly.The rare earth oxide size reaches nano level.Because rare earth oxide is very tiny, strengthened matrix alloy effectively, show after tested: room temperature strength, hot strength (high temperature tensile strength, creep, enduring quality) have improved 15% than the titanium alloy with the identical complex intensifying of the composition of traditional method preparation at least, and plasticity has then improved 20%.
Claims (6)
1. the method for mixed addition of titanium alloy middle-weight rare earths and boron, it is characterized in that, be specially: rare earth and boron are added in the titanium alloy with the boronation rare earth compound or in the mixture mode of boronation rare earth, add fashionable, make the weight percent of rare earth element account for 56%～91% of mixing additive, and utilize the method mix that itself and sponge titanium or ti powder are mixed, utilize press or extrusion machine to make electrode then, the density of electrode is controlled between the 75%-90%, utilize liquid state or solid-state approach to process at last, the final titanium alloy of realizing that preparation TiB and rare earth oxide are strengthened.
2. the method for mixed addition of titanium alloy middle-weight rare earths as claimed in claim 1 and boron is characterized in that, described boronation rare earth compound is meant: hexaboride, four borides or both mixtures.
3. the method for mixed addition of titanium alloy middle-weight rare earths as claimed in claim 1 and boron, it is characterized in that, described liquid method is meant: vacuum consumable arc-melting, vacuum non-consumable arc melting, any method of electron-beam cold bed furnace melting that titanium alloy is commonly used.
4. the method for mixed addition of titanium alloy middle-weight rare earths as claimed in claim 1 and boron is characterized in that, described solid-state approach is meant: powder metallurgy process or mechanical alloying method.
5. the method for mixed addition of titanium alloy middle-weight rare earths as claimed in claim 1 and boron is characterized in that, described rare earth element, its weight percent account for and mix 56%～83% of additive.
6. the method for mixed addition of titanium alloy middle-weight rare earths as claimed in claim 5 and boron is characterized in that, described rare earth element comprises all cerium groups and yttrium group element, or mixed rare-earth elements.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962721A (en) * | 2010-11-02 | 2011-02-02 | 中南大学 | Powder metallurgy titanium alloy and preparation method thereof |
| CN102921928A (en) * | 2012-10-26 | 2013-02-13 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing titanium or titanium alloy castings by using titanium sponges |
| CN110479989A (en) * | 2019-08-19 | 2019-11-22 | 安徽省含山县兴建铸造厂 | A kind of processing method of high temperature resistant titanium alloy casting |
| CN110625112A (en) * | 2019-10-25 | 2019-12-31 | 西北有色金属研究院 | Titanium or titanium alloy spherical powder with rare earth oxide distributed on surface and preparation method thereof |
| CN112553618A (en) * | 2020-12-02 | 2021-03-26 | 江西省科学院应用物理研究所 | Method for repairing surface pits of cathode titanium roller for electrolytic copper foil forming machine |
| WO2021066142A1 (en) * | 2019-10-03 | 2021-04-08 | 東京都公立大学法人 | Heat-resistant alloy, heat-resistant alloy powder, heat-resistant alloy molded article, and method for producing same |
| CN114406282A (en) * | 2022-01-26 | 2022-04-29 | 西安交通大学 | High-plasticity cold spraying titanium sediment body based on particle interface oxygen element distribution regulation and control and preparation method thereof |
| CN116716501A (en) * | 2023-08-07 | 2023-09-08 | 成都先进金属材料产业技术研究院股份有限公司 | Titanium alloy for aerospace and smelting process thereof |
| CN116837239A (en) * | 2022-03-21 | 2023-10-03 | 中国科学院金属研究所 | Preparation method of marine microorganism corrosion resistant titanium alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962721A (en) * | 2010-11-02 | 2011-02-02 | 中南大学 | Powder metallurgy titanium alloy and preparation method thereof |
| CN102921928A (en) * | 2012-10-26 | 2013-02-13 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing titanium or titanium alloy castings by using titanium sponges |
| CN102921928B (en) * | 2012-10-26 | 2016-04-20 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method of titanium sponge production titanium or titanium alloy casting |
| CN110479989A (en) * | 2019-08-19 | 2019-11-22 | 安徽省含山县兴建铸造厂 | A kind of processing method of high temperature resistant titanium alloy casting |
| CN110479989B (en) * | 2019-08-19 | 2020-10-30 | 安徽省含山县兴建铸造厂 | Processing method of high-temperature-resistant titanium alloy casting |
| WO2021066142A1 (en) * | 2019-10-03 | 2021-04-08 | 東京都公立大学法人 | Heat-resistant alloy, heat-resistant alloy powder, heat-resistant alloy molded article, and method for producing same |
| US11846006B2 (en) | 2019-10-03 | 2023-12-19 | Tokyo Metropolitan Public University Corporation | Heat-resistant alloy, heat-resistant alloy powder, heat-resistant alloy structural component, and manufacturing method of the same |
| CN114466943A (en) * | 2019-10-03 | 2022-05-10 | 东京都公立大学法人 | Heat-resistant alloy, heat-resistant alloy powder, heat-resistant alloy molded body, and method for producing same |
| CN110625112A (en) * | 2019-10-25 | 2019-12-31 | 西北有色金属研究院 | Titanium or titanium alloy spherical powder with rare earth oxide distributed on surface and preparation method thereof |
| CN110625112B (en) * | 2019-10-25 | 2020-11-03 | 西北有色金属研究院 | Titanium or titanium alloy spherical powder with rare earth oxide distributed on surface and preparation method thereof |
| CN112553618A (en) * | 2020-12-02 | 2021-03-26 | 江西省科学院应用物理研究所 | Method for repairing surface pits of cathode titanium roller for electrolytic copper foil forming machine |
| CN114406282A (en) * | 2022-01-26 | 2022-04-29 | 西安交通大学 | High-plasticity cold spraying titanium sediment body based on particle interface oxygen element distribution regulation and control and preparation method thereof |
| CN114406282B (en) * | 2022-01-26 | 2023-07-04 | 西安交通大学 | High-plasticity cold spray titanium deposit based on particle interface oxygen element distribution regulation and control and preparation method thereof |
| CN116837239A (en) * | 2022-03-21 | 2023-10-03 | 中国科学院金属研究所 | Preparation method of marine microorganism corrosion resistant titanium alloy |
| CN116716501A (en) * | 2023-08-07 | 2023-09-08 | 成都先进金属材料产业技术研究院股份有限公司 | Titanium alloy for aerospace and smelting process thereof |
| CN116716501B (en) * | 2023-08-07 | 2023-10-31 | 成都先进金属材料产业技术研究院股份有限公司 | Titanium alloy for aerospace and smelting process thereof |
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