CN105925842B - A kind of manufacture method of high-quality titanium alloy - Google Patents
A kind of manufacture method of high-quality titanium alloy Download PDFInfo
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- CN105925842B CN105925842B CN201610372929.6A CN201610372929A CN105925842B CN 105925842 B CN105925842 B CN 105925842B CN 201610372929 A CN201610372929 A CN 201610372929A CN 105925842 B CN105925842 B CN 105925842B
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- 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
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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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
Abstract
The invention belongs to rare metal processing technique field, more particularly to a kind of manufacture method of high-quality titanium alloy, aluminium is added in the form of titanium aluminium intermediate alloy and vanadium aluminium intermediate alloy, the preparation of titanium aluminium intermediate alloy, the Adding Way of micro- zirconium, the Adding Way of crystal grain thinning trace element, smelting technology controls, dosing improves the trace element of cold and hot working performance and the trace element of crystal grain thinning, improves its composition tissue, improves its mechanical performance.
Description
Technical field
The invention belongs to rare metal processing technique field, and in particular to a kind of manufacture method of high-quality titanium alloy.
Background technology
Titanium or titanium alloy is divided into α by tissue, and nearly α, alpha+beta, nearly β, beta titanium alloy, the С of В Т 6 are Russia（The former Soviet Union）Board
Number, the Chinese trade mark is TC4ELI, and U.S.'s trade mark is Gr.5；Principal component is Ti-6Al-4V, is organized as alpha+beta diphasic titanium alloy；Such
Alloy is the research and development fifties in last century, is widely used, such alloy usage amount of the whole world because its comprehensive mechanical performance is excellent
Account for the 80% of titanium alloy usage amount；It is mainly used in the structural members such as Aero-Space, offshore oil and gas field and titanium alloy stressed member
On, such titanium alloy also has extensive use as body implanting material.
Such alloy is typical two phase alloy, and principal component scope various countries trade mark difference is little, but trace element and low tone
Gap Control of Impurities scope has obvious difference；Particularly the С of В Т 6 of Russia's production are than Chinese and produced in USA similar titanium
Its mechanical performance of alloy has a clear superiority；The aircraft of Russia is introduced from China in recent years, the service condition of submarine is seen, is domesticized
During China's same type of material mechanical performance it is obvious relatively low and unstable.Its subject matter is：Aluminium content is unstable；Trace element
It particularly can not be dosed with the element of crystal grain thinning or be added without method；O, N, C, Fe Control of Impurities scope are incorrect；China
The traditional processing technology of each titanium alloy production unit is：Titanium sponge+vanadium aluminium intermediate alloy+fine aluminium beans or aluminium foil mend aluminium, big batch mixing
Or add bag intermediate alloy bag --- extruding electrode block --- group weldering consutrode --- secondary or three times vacuum consumable smelting ---
Titanium ingot casting；Wherein, aluminium addition and control be in the form of vanadium aluminium intermediate alloy and fine aluminium；O, N, C, Fe are with titanium sponge and vanadium
Based on aluminium intermediate alloy content, melting factor is considered to control；The trace element of crystal grain thinning is not dosed substantially；In the presence of master
Wanting problem is：Fine aluminium is in melting, because its fusing point is low, there is scaling loss and volatilization in fusion process, middle and later periods smelter before melting
Skill parameter difference extent of deterioration is different, so aluminium content is uneven in the upper, middle and lower portion of ingot casting, aluminium is the stable member of α phases
Element, it is very sensitive to strengthening titanium alloy, although aluminium content, all in critical field, tissue and performance do not have uniformity.
Domestic many production units even ensure its mechanical performance with impurity oxygen and iron is dosed, and are entirely ins and outs to putting；
Titanium alloy component determines tissue, and organization decided performance, Composition Control is the basis of mechanical performance height, therefore we must take
Measure ensures the uniformity of composition；Particularly as body implanting material, grain structure, mechanical performance, there is the mark that comparison is strict
Alignment request.
The content of the invention
For above-mentioned problem, the present invention provides a kind of manufacture method of high-quality titanium alloy.
The manufacture method of the high-quality titanium alloy of the present invention, is characterized by
1. aluminium, the Adding Way and scope of vanadium；
Aluminium is added in the form of titanium-aluminium intermediate alloy and vanadium-aluminium intermediate alloy；
The preparation of titanium aluminium intermediate alloy；
Because the fusing point of aluminium is low, aluminium is mended in the form of fine aluminium, scaling loss and volatilization in fusion process, so must prepare titanium-
Aluminium intermediate alloy；Titanium aluminium forms intermetallic compound, and raw material is with rafifinal and high purity titanium, using water jacketed copper crucible vacuum induction
Stove melting；Composition range is Al:45-55% (atomic percent), applying argon gas melting after pumping high vacuum, refining are cast after 30 minutes
Intermediate alloy ingot；Come out of the stove after cooling, it is standby after crushing；
It is prepared by vanadium-aluminium alloy
Universal technique is aluminothermic process in vananum producing country, and cost low yield is high, but impurity content is high, and O, N, C contain
Measure it is extremely unstable, per stove it is all different；Therefore refining is had to once；Equally refined using water jacketed copper crucible vaccum sensitive stove；
Smelting technology is the same as titanium aluminium intermediate alloy；Impurity ranges are controlled in O ＜ 0.08%, N ＜ 0.03%, C ＜ 0.05%；
2. the Adding Way of micro- zirconium
Zr addition can significantly improve the cold and hot working performance of titanium alloy, and Adding Way is sponge zirconium and titanium sponge batch mixing
Add, Composition Control scope is Zr:0.1-0.4%；
3. the Adding Way of crystal grain thinning trace element
The С titanium alloys of В Т 6 are a kind of titanium alloys of low gap impurity content；To ensure that it is brilliant that its mechanical performance adds refinement
The element of grain：B（Boron）It is extremely important with RE (rare earth)；But it is typically highly difficult in consumable smelting addition because its chemism is big,
Recovery rate is low, it is not easy to controls；Added indirectly by the way of titanium aluminium intermediate alloy is added to, uniformity is good, and recovery rate is high.Add
Enter B of the amount control in titanium-aluminium alloy total amount:1-3% (atomic percent), RE:5-10% (atomic percent)；
4. smelting technology controls
Fusion process is extremely important for obtaining high-quality titan alloy casting ingot；Take secondary vacuum consumable smelting mode；The
Melting once process takes big suction performance high vacuum mode, the purposeful volatile matter removed in titanium sponge, strict to control O.N impurity
Increase；Applying argon gas after first high vacuum are taken in second of melting, the mode of consumable smelting under argon gas protection, it is therefore an objective to prevent aluminium
With micro- volatilization loss；Adjust ingot structure；Homogenization of composition, prevent from being segregated；
The С titan alloy casting ingot production process technologies of В Т 6：
Titanium sponge（0 grade）+ titanium aluminium intermediate alloy+vanadium aluminium intermediate alloy+sponge zirconium --- batch mixing --- hydraulic press extruding is certainly
--- plasma group welds a consutrode --- vacuum consumable smelting --- secondary vacuum consumable smelting --- titanium to power pole block
Alloy cast ingot；
The Composition Control scope of the С titan alloy casting ingots of В Т 6 is that its unit is weight percentage：
(Al+O+4N):6.30-6.50%
( V+Fe):4.20-4.45%
Zr:0.1-0.4%
(O+4N) ＜ 0.09%
The % of H ＜ 0.008
C ＜ 0.03%
(B+RE):0.01-0.03%。
The beneficial effects of the invention are as follows：Using the titanium sponge of high-quality, titanium aluminium intermediate alloy, vanadium aluminium intermediate alloy is precisely controlled
The alloy content and impurity content of the С titanium alloys of В Т 6 processed, dose the trace element and crystal grain thinning for improving cold and hot working performance
Trace element, improve its composition tissue, improve its mechanical performance.
Embodiment
The present invention will be further described below.
The manufacture method of the high-quality titanium alloy of the present invention：
1. aluminium, the Adding Way and scope of vanadium
Aluminium is added in the form of titanium-aluminium intermediate alloy and vanadium-aluminium intermediate alloy
The preparation of titanium aluminium intermediate alloy
Because the fusing point of aluminium is low, aluminium is mended in the form of fine aluminium, scaling loss and volatilization in fusion process, so must prepare titanium-
Aluminium intermediate alloy；Titanium aluminium forms intermetallic compound, and raw material is with rafifinal and high purity titanium, using water jacketed copper crucible vacuum induction
Stove melting；Composition range is Al:45-55% (atomic percent), applying argon gas melting after pumping high vacuum, refining are cast after 30 minutes
Intermediate alloy ingot；Come out of the stove after cooling, it is standby after crushing；
It is prepared by vanadium-aluminium alloy
Universal technique is aluminothermic process in vananum producing country, and cost low yield is high, but impurity content is high, and O, N, C contain
Measure it is extremely unstable, per stove it is all different；Therefore refining is had to once；Equally refined using water jacketed copper crucible vaccum sensitive stove；
Smelting technology is the same as titanium aluminium intermediate alloy；Impurity ranges are controlled in O ＜ 0.08%, N ＜ 0.03%, C ＜ 0.05%；
2. the Adding Way of micro- zirconium
Zr addition can significantly improve the cold and hot working performance of titanium alloy, and Adding Way is sponge zirconium and titanium sponge batch mixing
Add, Composition Control scope is Zr:0.1-0.4%；
3. the Adding Way of crystal grain thinning trace element
The С titanium alloys of В Т 6 are a kind of titanium alloys of low gap impurity content；To ensure that it is brilliant that its mechanical performance adds refinement
The element of grain：B（Boron）It is extremely important with RE (rare earth)；But it is typically highly difficult in consumable smelting addition because its chemism is big,
Recovery rate is low, it is not easy to controls；Added indirectly by the way of titanium aluminium intermediate alloy is added to, uniformity is good, and recovery rate is high；Add
Enter B of the amount control in titanium-aluminium alloy total amount:1-3% (atomic percent), RE:5-10% (atomic percent)；
4. smelting technology controls
Fusion process is extremely important for obtaining high-quality titan alloy casting ingot；Take secondary vacuum consumable smelting mode；The
Melting once process takes big suction performance high vacuum mode, the purposeful volatile matter removed in titanium sponge, strict to control O.N impurity
Increase；Applying argon gas after first high vacuum are taken in second of melting, the mode of consumable smelting under argon gas protection, it is therefore an objective to prevent aluminium
With micro- volatilization loss；Adjust ingot structure；Homogenization of composition, prevent from being segregated；
The С titan alloy casting ingot production process technologies of В Т 6：
Titanium sponge（0 grade）+ titanium aluminium intermediate alloy+vanadium aluminium intermediate alloy+sponge zirconium --- batch mixing --- hydraulic press extruding is certainly
--- plasma group welds a consutrode --- vacuum consumable smelting --- secondary vacuum consumable smelting --- titanium to power pole block
Alloy cast ingot；
The Composition Control scope of the С titan alloy casting ingots of В Т 6 is that its unit is weight percentage：
(Al+O+4N):6.30-6.50%
( V+Fe):4.20-4.45%
Zr:0.1-0.4%
(O+4N) ＜ 0.09%
The % of H ＜ 0.008
C ＜ 0.03%
(B+RE):0.01-0.03%。
Production technology by taking the С optical wand materials of В Т 6 as an example：Above-mentioned titan alloy casting ingot, skin is pulled out by turning, remove ingot casting end to end
After carry out hot-working, by the processes such as hot forging, reconditioning carry out hot forging（Hot rolling）Into blank rod, through Overheating Treatment, after alignment
Che Guang（Thick rod）；Blank rod is through supercooling（Temperature）Draw, be heat-treated, alignment, polished after stripping off the skin（Thin rod）；
Production technology is：
Titan alloy casting ingot --- hot forging --- hot forging（Hot rolling）--- oxidation is taken off in heat treatment --- alignment ---
Skin --- car（Mill）Light --- defect detecting test --- finished product；
Finished product bar annealed condition mechanical performance scope is：σb:900-980MPa;δ:12-16%;Ψ ＞ 30%, dose and change
The trace element of kind cold and hot working performance and the trace element of crystal grain thinning, improve its composition tissue, improve its mechanical performance.
Claims (1)
- A kind of 1. manufacture method of high-quality titanium alloy, it is characterised in that：Aluminium, the Adding Way and scope of vanadiumAluminium is added in the form of titanium-aluminium intermediate alloy and vanadium-aluminium intermediate alloyThe preparation of titanium aluminium intermediate alloyBecause the fusing point of aluminium is low, aluminium is mended in the form of fine aluminium, scaling loss and volatilization in fusion process, so must prepare in titanium-aluminium Between alloy；Titanium aluminium forms intermetallic compound, and raw material is with rafifinal and high purity titanium, is melted using water jacketed copper crucible vaccum sensitive stove Refining；Composition range is Al:45-55% atomic percents, applying argon gas melting after pumping high vacuum, refining cast after 30 minutes among close Ingot；Come out of the stove after cooling, it is standby after crushing；It is prepared by vanadium-aluminium alloyUniversal technique is aluminothermic process in vananum producing country, and cost low yield is high, but impurity content is high, O, N, C content pole It is unstable, it is all different per stove；Therefore refining is had to once；Equally refined using water jacketed copper crucible vaccum sensitive stove；Melting Technique is the same as titanium aluminium intermediate alloy；Impurity ranges are controlled in O ＜ 0.08%, N ＜ 0.03%, C ＜ 0.05%；The Adding Way of micro- zirconiumZr addition can significantly improve the cold and hot working performance of titanium alloy, and Adding Way is that sponge zirconium and titanium sponge batch mixing add Enter, Composition Control scope is Zr:0.1-0.4%；The Adding Way of crystal grain thinning trace elementThe С titanium alloys of В Т 6 are a kind of titanium alloys of low gap impurity content；To ensure that its mechanical performance adds crystal grain thinning Element：B（Boron）It is extremely important with RE (rare earth)；But it is typically highly difficult in consumable smelting addition because its chemism is big, receive Rate is low, it is not easy to controls；Added indirectly by the way of titanium aluminium intermediate alloy is added to, uniformity is good, and recovery rate is high；Addition Control the B in titanium-aluminium alloy total amount:1-3% atomic percents, RE:5-10% atomic percents；Smelting technology controlsFusion process is extremely important for obtaining high-quality titan alloy casting ingot；Take secondary vacuum consumable smelting mode；For the first time Fusion process takes big suction performance high vacuum mode, the purposeful volatile matter removed in titanium sponge, the strict increasing for controlling O.N impurity Add；Applying argon gas after first high vacuum are taken in second of melting, the mode of consumable smelting under argon gas protection, it is therefore an objective to prevent aluminium and micro- Secondary element volatilization loss；Adjust ingot structure；Homogenization of composition, prevent from being segregated；The С titan alloy casting ingot production process technologies of В Т 6：Titanium sponge+titanium aluminium intermediate alloy+vanadium aluminium intermediate alloy+sponge zirconium --- batch mixing --- hydraulic press extruding consutrode --- plasma group welds a consutrode --- vacuum consumable smelting --- secondary vacuum consumable smelting --- titanium alloy casting to block Ingot；The Composition Control scope of the С titan alloy casting ingots of В Т 6 is that its unit is weight percentage：(Al+O+4N):6.30-6.50%( V+Fe):4.20-4.45%Zr:0.1-0.4%(O+4N) ＜ 0.09%The % of H ＜ 0.008C ＜ 0.03%(B+RE):0.01-0.03%。
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| CN109161707A (en) * | 2018-02-09 | 2019-01-08 | 沈阳中核舰航特材科技（常州）有限公司 | A kind of manufacturing method of biological medical titanium alloy TC4ELI stick/wire rod |
| CN109161724A (en) * | 2018-02-09 | 2019-01-08 | 沈阳中核舰航特材科技（常州）有限公司 | A kind of manufacturing method of biological medical titanium alloy TC20 stick/wire rod |
| CN109082560A (en) * | 2018-08-29 | 2018-12-25 | 江苏沃钛有色金属有限公司 | A kind of titanium alloy sheet of stretch-proof and preparation method thereof |
| CN109259878A (en) * | 2018-09-28 | 2019-01-25 | 江阴金泰克生物技术有限公司 | One-part form Immediate prosthesis dental implant of copper-bearing antibacterial titanium alloy and preparation method thereof |
| CN109402433B (en) * | 2018-12-29 | 2020-06-26 | 宝鸡长征金属材料有限公司 | Preparation method of vacuum melting TiAlCr target material |
| CN110487834A (en) * | 2019-07-24 | 2019-11-22 | 北京科技大学 | It is a kind of for measuring the sample frame and its application method of Surface Segregation volatile quantity |
| CN112626372B (en) * | 2019-10-08 | 2022-06-07 | 大田精密工业股份有限公司 | Titanium alloy sheet material and method for producing same |
| CN110983079A (en) * | 2019-12-18 | 2020-04-10 | 西安西工大超晶科技发展有限责任公司 | Preparation method of titanium alloy ingot containing volatile elements |
| CN112746176B (en) * | 2020-12-29 | 2024-03-22 | 常州中钢精密锻材有限公司 | Method for controlling trace element distribution in ESR cast ingot and application thereof |
| CN113637871A (en) * | 2021-07-09 | 2021-11-12 | 宝鸡安钛泽科技金属有限公司 | Method for manufacturing hot-forming titanium alloy for golf tool |
| CN115369286B (en) * | 2022-08-29 | 2023-04-18 | 沈阳中核舰航特材科技有限公司 | Alpha + beta type titanium alloy for fastener, preparation method and preparation method of bar thereof |
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| CN104073684A (en) * | 2014-03-31 | 2014-10-01 | 上海大学 | Titanium alloy containing Cr and Mn elements and preparation method thereof |
| CN104018028B (en) * | 2014-06-23 | 2016-06-29 | 北京科技大学 | A kind of high alumina height silicon cast titanium alloy |
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