CN108486410A - A kind of superelevation strength and ductility product low-cost titanium alloy and the preparation method and application thereof - Google Patents
A kind of superelevation strength and ductility product low-cost titanium alloy and the preparation method and application thereof Download PDFInfo
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- CN108486410A CN108486410A CN201810507801.5A CN201810507801A CN108486410A CN 108486410 A CN108486410 A CN 108486410A CN 201810507801 A CN201810507801 A CN 201810507801A CN 108486410 A CN108486410 A CN 108486410A
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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
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/20—Arc remelting
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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
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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
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
Abstract
The present invention relates to a kind of superelevation strength and ductility product low-cost titanium alloy, the titanium alloy includes Ti, Mo, Cr, Al and Fe；Wherein, the quality of titanium elements accounts for 75% or more of titanium alloy gross mass.Invention also provides the preparation methods of the titanium alloy, and in order to reduce the overall cost of the titanium alloy, Mo, Cr, Al and Fe element in the preferably described alloy of the present invention add in the form of the intermediate alloy of Al Mo, Mo Fe and Cr Fe.Superelevation strength and ductility product low-cost titanium alloy provided by the invention has superelevation strength and ductility product, there is ideal yield strength, higher plasticity and good work hardening rate simultaneously, bar, plank and proximate matter etc. can be processed into, and there is lower use cost, it is with a wide range of applications in Aeronautics and Astronautics, seafari, shipbuilding and/or automobile manufacturing field.
Description
Technical field
The invention belongs to technical field of alloy, are related to a kind of low-cost titanium alloy and preparation method of superelevation strength and ductility product.
Background technology
The product between breaking elongation when strength and ductility product refers to room temperature tensile intensity and the fracture of material, frequently as structure gold
Belong to one of the Judging index of material comprehensive performance.But the intensity of metal material usually can not with plasticity (being indicated with elongation percentage)
It gets both, even obtains high intensity, then plasticity reduces；Otherwise plasticity improves, then strength reduction, so as to cause the strength and ductility product of material
It is universal relatively low.In order to obtain the metal material of high strength and ductility, generally more by adjusting the composition of alloy composition and exploitation
Excellent thermal treatment process technology.For example, high strength plastic product steel is after decades of development, in the first generation and second generation high strength plastic product steel
On the basis of, have been developed that manganese high strength plastic product steel in the third generation by adjusting the chemical composition of high strength plastic product steel, cost is lower,
Density smaller and performance are more excellent, and plasticity and accumulation value is high, and receives the concern of automobile industry.
As important structural metallic material, titanium alloy is because its density is low, intensity is high, corrosion resistance is good and temperature in use is wide etc.
Advantage is widely used in the design and manufacture of structural member in aviation, elastic component and connector.But it is existing high-strength
The strength and ductility product of titanium alloy is usually less than 30GPa%, and research related to this is fewer.In recent years with aviation
Development, the usage amount of titanium alloy become increasing；And with the upgrading of aerospace equipment Design theory, warship industry
It grows rapidly, the development of ocean platform, deep diving equipment and automotive light weight technology, all demand to low cost and high strength ductility balance titanium alloy
It further increases.And intensity with plasticity the proportioning property of developed high-strength titanium alloy are poor at present, work hardening rate is relatively low and smaller
Energy absorption capability and limit the application range of titanium alloy.In addition, in most high-strength titanium alloys containing a large amount of vanadium, niobium,
The higher alloying element of the prices such as zirconium, increases the cost of raw material of titanium alloy.Therefore, exploitation one kind having both high strength and ductility, height
The low-cost titanium alloy of work hardening rate can widen the application range of existing high-strength titanium alloy significantly.
Invention content
The purpose of the present invention is overcoming the deficiencies of existing technologies, a kind of superelevation strength and ductility product low-cost titanium alloy, the conjunction are provided
Gold utensil has good tensile strength and yield strength, excellent elongation percentage, strength and ductility product >=45GPa% that can expand significantly existing
There is the use scope of high-strength titanium alloy.
Specifically, superelevation strength and ductility product low-cost titanium alloy provided by the invention includes titanium Ti, molybdenum Mo, chromium Cr, aluminium Al
And iron Fe；Wherein, the quality of titanium elements accounts for 75% or more of titanium alloy gross mass.
The present invention has ideal yield strength in order to ensure titanium alloy, has fully considered alloying element in titanium alloy
Solution strengthening ability (i.e. Δ σ=1.5n [Fe+Mn]+1.3n [Cr]+n [Al+Mo]+0.7n [V+W]+0.5n [Sn]+0.4n [Zr]
+ 0.3n [Nb], n are constant)；Meanwhile the present invention refers to Titanium Alloy Design d electron theories, makes itWithNumerical value difference
It is (described in the range of 2.32~2.39 and 2.76~2.80WithThe horizontal line at top represents average contain
Justice) so that alloy possesses higher plasticity and good work hardening rate；According to traditional molybdenum equivalent (i.e. [Mo] eq=
+ 1.6 (%Cr) -1.0 of 1.0 (%Mo)+0.67 (%V)+0.44 (%W)+0.28 (%Nb)+0.22 (%Ta)+2.9 (%Fe)
(%Al)) design method, alloy has higher intensity when [Mo] eq=8~16；According to multi-element alloyed theory, β is had chosen
Isomorphous elements (Mo), β eutectoid types element (Cr, Fe) are to enhance the solution strengthening ability of alloy, and addition α stable type elements
(Al) to adjust alloyWithNumerical value.On this basis, the present invention has taken into account the cost of each metallic element, is not added with
Alloying Element Vanadium, niobium, zirconium and rare earth element, and finally molybdenum, chromium, aluminium and iron are had chosen from a great selection of metallic element selected
Totally four kinds of elements are as the main alloy element for stating titanium alloy, under the premise of ensureing alloy design concept, with maximum
The low-alloyed prices of raw materials are dropped, by selecting specific metallic combination, can make gained titanium alloy that there is superelevation strength and ductility product, low
The advantages such as cost.
The present invention further carries out preferably the relative usage of each element, to ensure to play synergistic effect between each element,
Improve the whole plasticity and accumulation value of material.Specifically：
The mass ratio of Mo, Cr, Al and Fe are 6~9 in the preferably described titanium alloy of the present invention：3~6：3~6：0.5~3,
More preferably 6~8：3~4：3~4：1~2.
Contain Mo 6~9%, Cr 3~6%, Al 3~6%, Fe 0.5~3% in the preferably described titanium alloy of the present invention,
Further preferably Mo 6~8%, Cr 3~4%, Al 3~4%, Fe 1~2%.
Contain Mo 6~9%, Cr 3~6%, Al 3~6%, Fe 0.5~3% in the preferably described titanium alloy of the present invention, it is remaining
Amount is Ti；Further preferably Mo 6~8%, Cr 3~4%, Al 3~4%, Fe 1~2%, surplus Ti.
In the actual production process, the inevitable impurity of minute quantity can be mixed in titanium alloy, the content of the impurity exists
In the allowable range of this field.
Titanium alloy provided by the invention has superelevation strength and ductility product and good plasticity.The preferably described titanium alloy of the present invention it is strong
Mould product >=45GPa%, yield strength >=850Mpa of the further preferably described titanium alloy of the present invention.
Present invention simultaneously provides the preparation methods of the low-cost titanium alloy of the superelevation strength and ductility product, specifically include following step
Suddenly：The raw material containing each element is taken, ingot casting is smelted into after mixing, after homogenization is heat-treated, forging or roll forming, then consolidated
Molten processing or aging strengthening model.
In order to reduce the overall cost of the titanium alloy, Mo, Cr, Al and Fe element in the preferably described alloy of the present invention are equal
It is added in the form of the intermediate alloy of Al-Mo, Mo-Fe and Cr-Fe.Specifically, sponge Ti can be selected in the raw material containing Ti elements
Intermediate alloy Al-Mo or Mo-Fe can be selected in particle, the raw material containing Mo elements, and intermediate close can be selected in the raw material containing Cr elements
Golden Cr-Fe, the raw material containing Al elements can be selected the intermediate alloy Al-Mo, the raw material containing Fe elements can be selected it is described in
Between alloy Mo-Fe or described intermediate alloys Cr-Fe.
Raw material is first pressed into consutrode block, then to electrode by the present invention after mixing preferably before melting
It is welded between block.The welding can be used tungsten electrode Asia arc-welding method, when welding use high-purity (99.99% with
On) argon gas.
Present invention preferably employs vacuum consumable electrode arc furnaces to carry out melting to the electrode block after the welding.The melting can
It carries out twice or thrice, to form ingot casting.
The present invention preferably carries out homogenization heat treatment under the conditions of vacuum, 1000 DEG C~1100 DEG C to the ingot casting, described
The time of heat treatment is preferably 10~15 hours.Before heat treatment, it can first strip off the skin to ingot casting, and cut off riser and bottom.
The present invention forges the ingot casting after carrying out the homogenization heat treatment.The method of the forging or rolling is preferred
For：First on beta transus temperature 50 DEG C~100 DEG C progress cogging forging, then below beta transus temperature 60 DEG C~100 DEG C into
Row repeatedly forge or roll repeatedly by (such as 3 times).
In order to obtain high strength and ductility titanium alloy product, the present invention further 10 DEG C~20 DEG C progress on beta transus temperature
The solution treatment of 15~40min obtains the perfect recrystallization tissue of homogeneous grain size, i.e. high strength and ductility titanium alloy.The present invention
Also aging strengthening model (conventional method for using this field) can be carried out to the product after the forging or roll forming, can be obtained
To high strength and ductility titanium alloy of the present invention.
Since titanium alloy provided by the invention has superelevation strength and ductility product, while there is ideal yield strength, higher modeling
Property and good work hardening rate, can be processed into bar, plank and proximate matter etc., in seawater such as naval vessel, deep diving equipment, ocean platforms
The manufacturing fields such as environment and Aeronautics and Astronautics, automobile have extremely strong application value.The present invention protects the iron content low simultaneously
Application of the cost high-strength titanium alloy in Aeronautics and Astronautics, seafari, shipbuilding and/or automobile manufacturing field.
The present invention refers to the market price of each metallic element, is based on d electron theories and multi-element alloyed principle, passes through selection
It the alloying elements of different solution strengthening abilities and adjusts its and adds content, so that design alloyWithNumerical value fall
In suitable range.The present invention further optimizes the content of each metallic element by selecting specific metallic combination,
Gained titanium alloy has superelevation strength and ductility product, and has lower use cost, in Aeronautics and Astronautics, seafari, shipbuilding
And/or it is with a wide range of applications in automobile manufacturing field.
Description of the drawings
Fig. 1 is room temperature tensile curve synoptic diagram of the alloy that provides of embodiment 1 after β is dissolved.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
A kind of superelevation strength and ductility product low-cost titanium alloy is present embodiments provided, chemical composition mass percentage composition is Mo
7%, Cr 4%, Al 4%, Fe 1%, surplus Ti.
Superelevation strength and ductility product low-cost titanium alloy provided in this embodiment is prepared with the following method：
(1) according to each composition by weight percent, sponge Ti particle, intermediate alloy Al-Mo, intermediate alloy Mo- are weighed respectively
Fe and intermediate alloy Cr-Fe；
(2) raw material weighed is stirred and is pressed into consutrode block after evenly mixing, welded using the arc-welding of tungsten electrode Asia
It connects method to weld between electrode block, welding grade argon gas purity is 99.99%；Three are carried out using vacuum consumable electrode arc furnace
Secondary melting is prepared into ingot casting；
(3) after being stripped off the skin to the ingot casting, cutting off riser and bottom, 1050 are carried out to ingot casting in vacuum heat treatment furnace
DEG C homogenization heat treatment 12 hours；
(4) to the ingot casting after the homogenization heat treatment, first 60 DEG C of progress cogging forgings on beta transus temperature, then
3 forging or rollings repeatedly are carried out below beta transus temperature for 80 DEG C；
(5) 15 DEG C of solution treatment for carrying out 30min on beta transus temperature, obtain tying again completely for homogeneous grain size
Crystalline substance tissue, obtains final high strength and ductility titanium alloy.
Titanium alloy provided in this embodiment is Ti-7Mo-4Cr-4Al-1Fe alloys,WithNumerical value be respectively
2.36 and 2.77, molybdenum equivalent [Mo] eq are 12.3, which belongs to metastable beta titanium alloy.
For high strength and ductility low-cost titanium alloy provided in this embodiment after β solution treatment water coolings, tensile strength is reachable
1090MPa, yield strength can reach 870MPa, and elongation percentage is up to 42%, strength and ductility product 45.8GPa%.The alloy state
Room temperature tensile curve it is as shown in Figure 1.
From the metal price of the Changjiang river non-ferrous metal net and Chinese price of steel product net (in May, 2018) shown in reference table 1
It is calculated, titanium alloy raw material price provided in this embodiment is relatively low, and good competitiveness is possessed in following use.
Table 1：The price analysis of titanium and its alloying element
| Element | Ti | Mo | Cr | Al | Fe | V |
| Price (ten thousand yuan/ton) | 5.6 | 24.4 | 6.8 | 1.4 | 0.4 | 270 |
| Element | Nb | Zr | Mo-Fe intermediate alloys | Cr-Fe intermediate alloys | ||
| Price (ten thousand yuan/ton) | 65 | 23.7 | 11.1 | 0.87 |
Embodiment 2
A kind of superelevation strength and ductility product low-cost titanium alloy is present embodiments provided, chemical composition mass percentage composition is Mo
6%, Cr 4%, Al 4%, Fe 2%, surplus Ti.
The preparation method is the same as that of Example 1.
The alloyWithNumerical value is respectively 2.35 and 2.77, and [Mo] eq is 14.2, which belongs to metastable beta titanium
Alloy.After testing it is found that titanium alloy provided in this embodiment has excellent tensile strength and an elongation percentage, strength and ductility product >=
45GPa%.
Embodiment 3
A kind of superelevation strength and ductility product low-cost titanium alloy is present embodiments provided, chemical composition mass percentage composition is Mo
7%, Cr 3%, Al 3%, Fe 1%, surplus Ti.
The preparation method is the same as that of Example 1.
The alloyWithNumerical value is respectively 2.38 and 2.78, and [Mo] eq is 11.7, which belongs to metastable beta titanium
Alloy.After testing it is found that titanium alloy provided in this embodiment has excellent tensile strength and an elongation percentage, strength and ductility product >=
45GPa%.
Embodiment 4
A kind of superelevation strength and ductility product low-cost titanium alloy is present embodiments provided, chemical composition mass percentage composition is Mo
7%, Cr 3%, Al 4%, Fe 2%, surplus Ti.
The preparation method is the same as that of Example 1.
The alloyWithNumerical value is respectively 2.36 and 2.77, and [Mo] eq is 13.6, which belongs to metastable β types
Titanium alloy.After testing it is found that titanium alloy provided in this embodiment has excellent tensile strength and an elongation percentage, strength and ductility product >=
45GPa%.
Embodiment 5
A kind of superelevation strength and ductility product low-cost titanium alloy is present embodiments provided, chemical composition mass percentage composition is Mo
8%, Cr 3%, Al 4%, Fe 1.5%, surplus Ti.
The preparation method is the same as that of Example 1.
The alloyWithNumerical value is respectively 2.36 and 2.77, and [Mo] eq is 13.15, which belongs to metastable β types
Titanium alloy.After testing it is found that titanium alloy provided in this embodiment has excellent tensile strength and an elongation percentage, strength and ductility product >=
45GPa%.
Although above having used general explanation, specific implementation mode and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of superelevation strength and ductility product low-cost titanium alloy, which is characterized in that including Ti, Mo, Cr, Al and Fe；Wherein, titanium elements
Quality account for 75% or more of titanium alloy gross mass.
2. titanium alloy according to claim 1, which is characterized in that the mass ratio of Mo, Cr, Al and Fe in the titanium alloy
It is 6~9：3~6：3~6：0.5~3, preferably 6~8：3~4：3~4：1~2.
3. titanium alloy according to claim 1, which is characterized in that in the titanium alloy contain Mo 6~9%, Cr 3~
6%, Al 3~6%, Fe 0.5~3% preferably comprises Mo 6~8%, Cr 3~4%, Al 3~4%, Fe 1~2%.
4. titanium alloy according to claim 1, which is characterized in that in the titanium alloy contain Mo 6~9%, Cr 3~
6%, Al 3~6%, Fe 0.5~3%, surplus Ti preferably comprise Mo 6~8%, Cr 3~4%, Al 3~4%, Fe 1
~2%, surplus Ti.
5. according to the titanium alloy described in Claims 1 to 4 any one, which is characterized in that strength and ductility product >=45 of the titanium alloy
GPa%；Preferably, the Mpa of the yield strength of the titanium alloy >=850.
6. iron content high strength and low cost titanium alloy described in Claims 1 to 5 any one, which is characterized in that include the following steps：It takes
Raw material containing each element is smelted into ingot casting after mixing, after homogenization is heat-treated, forging or roll forming, then carry out at solid solution
Reason or aging strengthening model.
7. according to the method described in claim 6, it is characterized in that, the raw material of Mo, Cr, Al and Fe element is equal in the titanium alloy
For the intermediate alloy containing at least one above-mentioned element；
Preferably, the raw material containing Mo elements is intermediate alloy Al-Mo or Mo-Fe, and the raw material containing Cr elements is intermediate alloy
Cr-Fe, the raw material containing Al elements are the intermediate alloy Al-Mo, and the raw material containing Fe elements is the intermediate alloy Mo-Fe
Or the intermediate alloy Cr-Fe.
8. the preparation method described according to claim 6 or 7, which is characterized in that before the melting, first mix raw material equal
It is pressed into consutrode block after even, is then welded between electrode block；
And/or homogenization heat treatment is carried out to the ingot casting under the conditions of vacuum, 1000 DEG C~1100 DEG C；
And/or the method for the forging or rolling is：First 50 DEG C~100 DEG C progress cogging forgings on beta transus temperature, so
60 DEG C~100 DEG C progress are repeatedly forged or are rolled repeatedly below beta transus temperature afterwards.
9. according to the method described in claim 6~8 any one, which is characterized in that the solution treatment is specially：Turn in β
The solution treatment of 10 DEG C~20 DEG C 15~40min of progress, obtains the perfect recrystallization tissue of homogeneous grain size on temperature.
10. the iron content high strength and low cost titanium alloy described in Claims 1 to 5 any one is in Aeronautics and Astronautics, seafari, ship
Application in oceangoing ship manufacture and/or automobile manufacturing field.
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Cited By (7)
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| CN110484772A (en) * | 2019-08-13 | 2019-11-22 | 洛阳双瑞精铸钛业有限公司 | A kind of preparation process of high-performance and low-cost titanium alloy |
| CN111349815A (en) * | 2020-04-13 | 2020-06-30 | 新疆湘润新材料科技有限公司 | Ti-1300Z novel high-strength high-toughness titanium alloy and preparation method thereof |
| CN112877566A (en) * | 2021-01-11 | 2021-06-01 | 复旦大学附属中山医院 | Low-clearance medical titanium alloy TC4ELI and preparation method thereof |
| CN112899522A (en) * | 2021-01-15 | 2021-06-04 | 西安稀有金属材料研究院有限公司 | Ultralow-elastic-modulus ultrahigh-work-hardening-rate Ti-Al-Mo-Cr series beta titanium alloy and heat treatment process thereof |
| CN113462928A (en) * | 2021-06-29 | 2021-10-01 | 中南大学 | Low-cost high-strength near-beta-Ti alloy and preparation method thereof |
| CN114045413A (en) * | 2021-11-25 | 2022-02-15 | 成都先进金属材料产业技术研究院股份有限公司 | High-strength near-beta titanium alloy and smelting method thereof |
| CN114657417A (en) * | 2022-05-07 | 2022-06-24 | 北京航空航天大学 | High-strength plastic titanium alloy suitable for cold deformation processing and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484772A (en) * | 2019-08-13 | 2019-11-22 | 洛阳双瑞精铸钛业有限公司 | A kind of preparation process of high-performance and low-cost titanium alloy |
| CN111349815A (en) * | 2020-04-13 | 2020-06-30 | 新疆湘润新材料科技有限公司 | Ti-1300Z novel high-strength high-toughness titanium alloy and preparation method thereof |
| CN112877566A (en) * | 2021-01-11 | 2021-06-01 | 复旦大学附属中山医院 | Low-clearance medical titanium alloy TC4ELI and preparation method thereof |
| CN112899522A (en) * | 2021-01-15 | 2021-06-04 | 西安稀有金属材料研究院有限公司 | Ultralow-elastic-modulus ultrahigh-work-hardening-rate Ti-Al-Mo-Cr series beta titanium alloy and heat treatment process thereof |
| CN113462928A (en) * | 2021-06-29 | 2021-10-01 | 中南大学 | Low-cost high-strength near-beta-Ti alloy and preparation method thereof |
| CN114045413A (en) * | 2021-11-25 | 2022-02-15 | 成都先进金属材料产业技术研究院股份有限公司 | High-strength near-beta titanium alloy and smelting method thereof |
| CN114657417A (en) * | 2022-05-07 | 2022-06-24 | 北京航空航天大学 | High-strength plastic titanium alloy suitable for cold deformation processing and preparation method thereof |
| CN114657417B (en) * | 2022-05-07 | 2022-12-23 | 北京航空航天大学 | High-strength plastic titanium alloy suitable for cold deformation processing and preparation method thereof |
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