CN103710572A - Cast Ti-Si-Al-base high-temperature high-strength alloy - Google Patents
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Abstract
The invention provides a cast Ti-Si-Al-base high-temperature high-strength alloy, which comprises the following components by weight percent: 4.5-8.5% of Si, 2.5-9.5% of Al, 0.1-2.5% of at least one element selected from elements Mo, Nb, Ta, V and Zr, and the balance of Ti, wherein the sum of Mo, Nb, Ta, V and Zr is less than 10%. The tensile strength of the Ti-Si-Al alloy provided by the invention at the room temperature and the tensile strength of the Ti-Si-Al alloy at 500 DEG C are higher than 800MPa and 550MPa, respectively. Compared with the traditional titanium alloy, the alloy provided by the invention also shows excellent abrasion resistance. The cast Ti-Si-Al-base alloy provided by the invention is applicable to high-temperature high-load supporting; for example, the cast Ti-Si-Al-base alloy can be applied to the piston and cylinder parts of a high-compression generator, various pumps, valves and impellers requiring abrasion resistance and corrosion resistance, the air compressor of an aero-engine, and the propeller, water-jet thruster and the like of a ship power propelling system.
Description
Technical field
The present invention relates to a kind of Ti-Si-Al base superalloy that contains intermetallic compound wild phase, more specifically relate to the high-temp and high-strength casting Ti-Si-Al alloy of a kind of Ti of containing, Si, Al, Mo, Nb, Ta, V and Zr.
Background technology
Cast titanium alloy refers to for being cast into the titanium alloy of definite shape foundry goods.At present to be widely used in the fields such as aerospace, naval vessel, chemical industry, automobile, physical culture and medicine equipment.In the cast titanium alloy early stage of development, be mainly to select some wrought titanium alloys to pour into a mould experiment in the world, result shows, most of wrought titanium alloy has comparatively satisfied Production Practice of Casting Technologies.Along with cast titanium alloy range of application constantly expands, the shape of foundry goods becomes increasingly complex, wall thickness is more and more thinner, and traditional cast titanium alloy also more and more exposes the weakness in its castability, as high in fusing point, chemical property is active, freezing range is wide and when casting superheating temperature shortcoming such as low.
The people such as Flower have studied martensite Ti-Si binary alloy and have precipitated (Metallurgical Transactions, 1971, Vol.2, No.12, P3289-3297) containing the silicide in the more complex alloys of zirconium and aluminium.In the titanium composite material containing zirconium and aluminium, the maximum silicone content of research is 1.0%.Recently, Guangxi University's Zhan forever clock etc. has been developed a kind of at room temperature have high strength and oxidation resistant titanium silicon at high temperature, and its feed composition and content are by weight percentage: Ti78.87-88.3, Si7.33-8.2, Al and/or Nb2.8-12.3%.The compressive strength at room temperature of this alloy can reach 1498-1828MPa, and under 800-1000 ℃ of high temperature, the oxidation weight gain of alloy is few, and the oxide film densification that alloy surface forms can play a very good protection by alloy.But the density of Nb is 8.66g/m3, a large amount of Nb add, and have improved on the one hand the density of alloy, increase the difficulty of alloy melting, on the other hand, have also improved the cost of alloy.The crystallisation range of titanium silicon eutectic system alloy is narrow, and good fluidity shrinks littlely, and not only density is little for titanium silicon eutectic alloy, and fusing point is low, easily overheated, can meet well the processing requirement of large-scale complex thin-wall titanium alloy casting.Therefore be considered to the third casting alloy except Fe-C and Al-Si eutectic alloy.But, with respect to Fe-C and Al-Si alloy, fewer about the research of Ti-Si alloy, particularly aspect the strengthening of Ti-Si alloy high-temp, also do not further investigate, also do not form the high strength at high temperature Ti-Si composition system of independent research.
Summary of the invention
The object of patent of the present invention is to provide a kind ofly has high strength, wear-resisting and oxidation resistant casting high temperature Ti-Si alloy above at 500 ℃.For this reason, we are on the basis of ternary Ti-Si-Al alloy, by adding Mo, Nb, Ta, V and Zr element, make alloy obtain good High-Temperature Strengthening, high-temperature oxidation resistant and high-temperature wearable effect, develop a kind of novel light casting alloy, meet the needs in the fields such as automobile, naval vessel, aerospace and the energy.
Technical scheme of the present invention is: a kind of casting Ti-Si-Al base superalloy, the weight percent of each component of this alloy: Si4.5-8.5, Al2.5-9.5, in Mo, Nb, Ta, V and Zr element, at least select a kind of, every kind of element 0.1-2.5, and the summation of Mo, Nb, Ta, V and Zr is less than 10, Ti surplus.
Preferably, this alloy comprises weight percent: Si4.5-7.5, Al2.5-5.5, Mo0.1-1.5, Nb0.1-1.5, V0.1-2.5, Zr0.1-2.5, Ti surplus.
Preferably, this alloy comprises weight percent: Si4.5-7.5, Al2.5-5.5, Nb0.1-1.5, V0.1%-2.5, Zr0.1-2.5, Ti surplus.
Preferably, this alloy comprises weight percent: Si4.5-7.5, Al2.5-5.5, Mo0.1-1.5, V0.1%-2.5, Zr0.1-2.5, Ti surplus.
Preferably, this alloy comprises weight percent: Si4.5-7.5, Al2.5-5.5, Mo0.1-1.5, Nb0.1-1.5, V0.1-2.5, Ti surplus.
Preferably, this alloy comprises weight percent: Si4.5-7.5, Al2.5-5.5, Mo0.1-1.5, Nb0.1-1.5, Zr0.1-2.5, Ti surplus.
Preferably, this alloy comprises weight percent: Si4.5-7.5, Al2.5-5.5, Mo0.1-1.5, V0.1-2.5, Ti surplus.
Preferably, this alloy comprises weight percent: Si4.5-7.5, Al2.5-5.5, Nb0.1-1.5, V0.1-2.5, Ti surplus.
Preferably, this alloy comprises weight percent: Si6.5, Al3.2, Mo0.5, Nb0.5, V0.5, Ti surplus.
Preferably, this gold comprises weight percent: Si6.5, Al5, Mo0.42, Nb1.32, V0.22, Zr1.32, Ti surplus.
The effect of these alloying elements and necessity are carried out to brief analysis below:
Al is one of the most frequently used alloying element of strengthening titanium alloy, the adding of Al has not only improved alloy strength and has also reduced alloy density, and this is particularly suitable for aeronautical material.Ti-Si-Al base alloy has the density lower than conventional cast titanium alloy, considerable mechanical property and oxidation-resistance, is the promising structured material of aircraft engine application aspect.Current research to Ti-Si-Al alloy shows, in solidus curve with below 1300 ℃, and Ti
5(Si, Al)
3(Z), with all Ti-Al base phases and deposit, cause wide two-phase region (β+Z, α+Z, γ+Z) and narrow triple-phase region (alpha+beta+Z, α+γ+Z).
The Vickers' hardness of initial Ti crystal grain increases slowly and increases with Aluminum in Alloy content.This is that interatomic distance reduces because less aluminium atom substitutes after larger Ti atom, causes chemical bond to strengthen, thereby causes reducing and the rising of alpha+beta-Ti transition temperature of lattice parameter.In binary Ti-Si system, the microhardness of Ti is also like this.It increases along with Si content in precipitated phase.The research of the fracture toughness property of Ti-Si-Al alloy under certain temperature and rate of deformation shows, single-phase Ti
5(Si, Al)
3alloy, when 1200-1400K, has a fragility to the transformation (BDT) of toughness.At Ti
5(Si, Al)
3in while adding Al to cause BDT to change, produce skew, compare with the silicide of pure Ti, have lower transition temperature, but do not change in intensity.The inventor's early-stage Study shows, the add-on of Al in Ti-Si is controlled at 2.5-9.5%, has both been conducive to improve the hot strength of alloy, can keep certain plasticity again.The interpolation of excess of aluminum easily makes alloy become fragile, thereby causes foundry goods to produce cold cracking.
In the alloy element of Ti, Mo, Nb, Ta, V are the elements identical with β-Ti lattice, can infinitely dissolve each other with β-Ti, and have limited solubility in α-Ti.Because Mo, Nb, Ta, V are identical with β-Ti lattice, so these elements can dissolve in β-Ti in a large number with substitute mode, produce less lattice distortion, therefore, these alloying elements, when producing strengthening effect, also can keep higher plasticity.These elements also have an important feature, and they not eutectoid or peritectoid reaction occur and generate fragility phase with Ti, so the structure stability of alloy is good, vital when this alloy is at high temperature used.
Zr is the same with the outermost electron structure of Ti, and their lattice structures are identical, all have two kinds of structures of intensive six sides and body-centered cubic, and the axial ratio of Ti and two kinds of elements of Zr is very approaching, and lattice parameter is also close, and a and c value differ and be respectively Δ a (Zr, Ti)/a
ti=9.51%, Δ c (Zr, Ti)/c
tithe Atomic radiuses difference of=10.02%, Zr and Ti is Δ r (Zr, Ti)/a
ti=8.99%, therefore, Ti and Zr can infinitely dissolve each other, and form sosoloid, and Zr adds in Ti, and the two is solution strengthening each other.There are some researches show, compare with the Ti-Si eutectic alloy without Zr alloying, when the Zr that functional quality mark is less than 1wt% carries out alloying, the compressive strength of material improves 9%, plasticity reaches 3.6%, continues to add Zr and carries out alloying, finds that intensity is maximum when Zr content is 2wt%, be about 1440MPa, than undressed eutectic alloy, improved approximately 17%; The compression plasticity of alloy changes comparatively obvious, reaches 7.2%.
In sum, the present invention adds Mo, Nb, Ta, V and Zr element on the basis of Ti-Si-Al alloy, has not only played the effect that improves alloy mechanical property.Meanwhile, appropriate Si, Al coordinate with Mo, Nb, Ta, V and Zr element, can also make Ti-Si-Al base alloy have good high-temperature oxidation resistance and high-temperature stability.
Accompanying drawing explanation
The scanning electron microscope image schematic diagram of Fig. 1 Ti-6.5Si-3.2Al-M1.
The X-ray diffraction schematic diagram of Fig. 2 Ti-6.5Si-3.2Al-M1.
The room temperature compression curve schematic diagram of Fig. 3 Ti-6.5Si-3.2Al-M1.
The room temperature tensile curve synoptic diagram of Fig. 4 Ti-6.5Si-3.2Al-M1.
The room temperature tensile fracture apperance schematic diagram of Fig. 5 Ti-6.5Si-3.2Al-M1.
The scanning electron microscope image schematic diagram of Fig. 6 Ti-6.5Si-5Al-M2.
The X-ray diffractogram schematic diagram of Fig. 7 T Ti-6.5Si-5Al-M2.
The room temperature compression curve schematic diagram of Fig. 8 Ti-6.5Si-5Al-M2.
The room temperature tensile curve synoptic diagram of Fig. 9 Ti-6.5Si-5Al-M2.
The room temperature tensile fracture apperance schematic diagram of Figure 10 Ti-6.5Si-5Al-M2.
The Changing Pattern schematic diagram of the friction coefficient load of Figure 11 Ti-6.5Si-5Al-M2 alloy.
The wear weight loss of Figure 12 Ti-6.5Si-5Al-M2 alloy is with the Changing Pattern schematic diagram of load.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further described.
The present invention selects the component of new Ti-Si-Al base alloy, has prepared Ti-Si-Al-M (M=Mo, Nb, Ta, V, Zr) alloy.Experimental technique of the present invention is as follows:
Castmethod 1: prepare the raw metal that mother alloy adopts and be the pure metal simple substance element that purity is greater than 99.9%, according to designed alloy, form batching, to take raw material is placed in suspension smelting furnace and carries out melting, crucible is water jacketed copper crucible, melting vacuum tightness is 0.01-1Pa, the frequency of shower furnace is 8000Hz, and melting electric current is 100-500A, and voltage is 100-380V.After band alloy melting, pouring into diameter is 45mm, in the long copper-made mould for 300mm, forms the casting Ti-Si-Al base alloy that intermetallic compound strengthens.
Castmethod 2, prepare the raw metal that mother alloy adopts and be the pure metal simple substance element that purity is greater than 99.9%, according to designed alloy, form batching, to take after raw material evenly mixes and be pressed into electrode, then in vaccum consumable electrode electric arc furnace, carry out vacuum melting, now melting vacuum tightness 0.01-1Pa, arc voltage 32-36V, arc current 5000-8000A, then at vacuum consumable electrode skull crucible vacuum tightness 0.1-1Pa, arc voltage 30-40V, carries out Ti-Si-Al base alloy casting under arc current 20000-50000A.The wild phase of titanium alloy forms when eutectic reaction, or separates out from molten metal or solid phase by subsequent reactions, forms the casting Ti-Si-Al base alloy that intermetallic compound strengthens.
Embodiment 1
In preferred embodiment of the present invention, a kind of Ti-6.5Si-3.2Al-M with high strength at high temperature performance
1(M1=Mo+Nb+V) alloy, the chemical composition of tested alloys, in Table 1, adds raw material in 3Kg vacuum melting furnace according to this proportioning, according to method 1 molten alloy and be cast into ingot casting.Adopt X-ray diffraction, scanning electronic microscope and universal testing machine to carry out analytical test.According to the alloy scanning electron microscope image of method 1 preparation as shown in Figure 1.Visible, alloy structure is typical hypoeutectic structure, by black matrix and white herring-bone form phase composite.Herring-bone form has again particulate state and corynebacterium, particle size to be less than 5 μ m mutually, and corynebacterium is slightly less than 3 μ m mutually, and length is less than 100 μ m.Fig. 2 is Ti-6.5Si-3.2Al-M1 alloy X-ray diffractogram.As can be seen from Figure 2, tissue is by α-Ti, Ti
5si
3form mutually with TiSi, this explanation black matrix is α-Ti phase, and white herring-bone form is Ti mutually
5si
3phase and TiSi phase.Due to Ti
5si
3compare α-Ti and there is mutually higher hardness, so Ti
5si
3in this alloy, play the effect of wild phase.
The composition of table one Ti-6.5Si-3.2Al-M1
| Element | Si | Al | Mo | Nb | V | Ti |
| Composition | 6.5 | 3.2 | 0.5 | 0.5 | 0.5 | Surplus |
Fig. 3 is the room temperature compression curve of Ti-6.5Si-5Al-M1 alloy.Visible, the yield strength of this alloy reaches 1171MPa, and breaking tenacity has reached 1835MPa, and before fracture, plastix strain is 11.55%.Fig. 4 is the room temperature tensile curve of Ti-6.5Si-5Al-M1 alloy.Just there is fracture in recoverable deformation part in visible this alloy, breaking tenacity has reached 903MPa, and before fracture, recoverable strain is 0.73%.From curve, this alloy only has recoverable deformation, almost there is no viscous deformation.Fig. 5 is Ti-6.5Si-5Al-M
1the stretching fracture pattern of alloy.Visible this Alloy Fracture presents obvious cleavage feature, and cleavage fracture is the feature of alloy brittle rupture.From fracture, it can also be seen that, part fracture demonstrates a small amount of little dimple, illustrates that this alloy, in fracture, a small amount of viscous deformation has occurred, and these features and stress strain curve match.
Table two has been listed according to the Ti-6.5Si-5Al-M of test method 1 preparation
1the tensile property of alloy under differing temps.Visible, the high temperature tensile properties of this alloy is very excellent.At 400 ℃, the intensity of alloy reaches 685MPa, and higher than the hot strength of other Ti alloy systems, this lays a good foundation as the application of the pump of the piston of high compression generator, cylinder part, wear resistant corrosion resistant, valve and impeller etc. at high temperature member for this alloy.
Ti-6.5Si-5Al-M under table two differing temps
1the tensile property of alloy.
In preferred embodiment of the present invention, selection has the Ti-6.5Si-5Al-M2(M2=Mo+Nb+V+Zr of eutectic wild phase) titanium alloy, the chemical composition of tested alloys is in Table three, raw material is added in 3Kg vacuum melting furnace according to this proportioning, according to method 1 molten alloy and be cast into ingot casting.Adopt X-ray diffraction, scanning electronic microscope, wear testing machine and universal testing machine to carry out analytical test.The Ti-6.5Si-5Al-M2 alloy scanning electron microscope image of preparation as shown in Figure 6.Visible, although the content of Si only has 6.5% in this alloy, but because Aluminum in Alloy content has reached 5%, and added and surpassed 1% Nb and the alloy of Zr content, alloy structure approaches eutectic structure very much, by black matrix and white fiber shape phase, fibrous phase diameter is less than 5 μ m, the longest 100 μ m that surpass of length.Fig. 7 is Ti-6.5Si-5Al-M2 alloy X-ray diffractogram.As can be seen from Figure 2, tissue is by α-Ti and Ti
5si
3form mutually, this explanation black matrix is α-Ti phase, and white herring-bone form is Ti mutually
5si
3phase.Due to Ti
5si
3compare α-Ti and there is mutually higher hardness, so Ti
5si
3in this alloy, play the effect of wild phase.
The composition of table three Ti-6.5Si-5Al-M2
| Element | Si | Al | Mo | Nb | V | Zr | Ti |
| Composition | 6.5 | 5 | 0.42 | 1.32 | 0.22 | 1.32 | Surplus |
Fig. 8 is Ti-6.5Si-3.2Al-M
2the room temperature compression curve of alloy.Visible, the yield strength of this alloy reaches 1263MPa, and breaking tenacity has reached 1775MPa, and before fracture, plastix strain is 7.27%.Fig. 9 is the room temperature tensile curve of Ti-6.5Si-5Al-M alloy.Visible this alloy fracture intensity has reached 960MPa, and before fracture, recoverable strain is about 0.74%.Contrast Ti-6.5Si-3.2Al-M1 alloy, compressive strength and the compression plasticity of Ti-6.5Si-5Al-M2 are lower, and while still compressing, yield strength and tensile break strength are higher.The reason that room temperature lower compression intensity and compression plasticity are lower, is mainly to make alloy form eutectic structure because Si, Al in alloy and other elements increase, and that is to say that in alloy, fragility increases mutually, causes alloy to become fragile.Also can find out, due to increasing of intermetallic compound wild phase, yield strength and the tensile strength of alloy have improved, so alloy at high temperature has better hot strength.Figure 10 is the stretching fracture pattern of Ti-6.5Si-5Al-M alloy.Visible this Alloy Fracture presents more obvious cleavage feature, and fracture is smooth, and dimple seldom, illustrates that this alloy, in fracture, viscous deformation has seldom occurred.
Table four has been listed the tensile property under differing temps according to the Ti-6.5Si-5Al-M2 alloy of test method 1 preparation.Visible, the high temperature tensile properties of this alloy is very excellent.At 300 ℃, the intensity of alloy reaches 760MPa, and at 600 ℃, the intensity of alloy reaches 660MPa, hot strength higher than some Ti alloy system, this be this alloy at high temperature member as the piston of high compression generator, cylinder part, the application of the pump of various requirement wear resistant corrosion resistant, valve and impeller etc. is laid a good foundation.
The tensile property of Ti-6.5Si-5Al-M2 alloy under table four differing temps.
Wear resistance is the key property of structural composite material.The quality of wear resisting property, directly affects life cycle and the security of product.To having carried out wear-resistant test according to the Ti-6.5Si-5Al-M2 alloy of test method 1 preparation.Test adopts Ti-6Al-4V alloy as the standard test block of wearing and tearing.Figure 11 and Figure 12 are respectively Ti-6.5Si-5Al-M
2the frictional coefficient of alloy and wear weight loss.Result shows, titanium alloy component wear resistance of the present invention is more better than business titanium alloy, and frictional coefficient reduces approximately 10%, and under load 500N condition, the wear weight loss of material has reduced more than 18%.In addition, from wearing and tearing variation tendency, the wear weight loss of Ti-6Al-4V alloy is linear increasing along with the increase of load, and alloy of the present invention presents parabola shaped variation tendency, illustrates that alloy of the present invention is expected to have better wear resisting property under high-load.
Claims (10)
1. cast Ti-Si-Al base superalloy for one kind, it is characterized in that, the weight percent of each component of this alloy: Si 4.5-8.5, Al 2.5-9.5, in Mo, Nb, Ta, V and Zr element, at least select a kind of, every kind of element 0.1-2.5, and the summation of Mo, Nb, Ta, V and Zr is less than 10, Ti surplus.
2. casting Ti-Si-Al base superalloy according to claim 1, is characterized in that, this alloy comprises weight percent: Si 4.5-7.5, Al 2.5-5.5, Mo 0.1-1.5, Nb 0.1-1.5, V 0.1-2.5, Zr 0.1-2.5, Ti surplus.
3. casting Ti-Si-Al base superalloy according to claim 1, is characterized in that, this alloy comprises weight percent: Si 4.5-7.5, Al 2.5-5.5, Nb 0.1-1.5, V 0.1%-2.5, Zr 0.1-2.5, Ti surplus.
4. casting Ti-Si-Al base superalloy according to claim 1, is characterized in that, this alloy comprises weight percent: Si 4.5-7.5, Al 2.5-5.5, Mo 0.1-1.5, V 0.1%-2.5, Zr 0.1-2.5, Ti surplus.
5. casting Ti-Si-Al base superalloy according to claim 1, is characterized in that, this alloy comprises weight percent: Si 4.5-7.5, Al 2.5-5.5, Mo 0.1-1.5, Nb 0.1-1.5, V 0.1-2.5, Ti surplus.
6. casting Ti-Si-Al base superalloy according to claim 1, is characterized in that, this alloy comprises weight percent: Si 4.5-7.5, Al 2.5-5.5, Mo 0.1-1.5, Nb 0.1-1.5, Zr 0.1-2.5, Ti surplus.
7. casting Ti-Si-Al base superalloy according to claim 1, is characterized in that, this alloy comprises weight percent: Si 4.5-7.5, Al 2.5-5.5, Mo 0.1-1.5, V 0.1-2.5, Ti surplus.
8. casting Ti-Si-Al base superalloy according to claim 1, is characterized in that, this alloy comprises weight percent: Si 4.5-7.5, Al 2.5-5.5, Nb 0.1-1.5, V 0.1-2.5, Ti surplus.
9. casting Ti-Si-Al base superalloy according to claim 1, is characterized in that, alloy comprises weight percent: Si6.5, Al3.2, Mo0.5, Nb0.5, V0.5, Ti surplus.
10. casting Ti-Si-Al base superalloy according to claim 1, is characterized in that, alloy comprises weight percent: Si 6.5, and Al 5, and Mo 0.42, and Nb 1.32, and V 0.22, and Zr 1.32, Ti surplus.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105908047A (en) * | 2016-05-16 | 2016-08-31 | 西南石油大学 | Titanium-aluminum-silicon-tantalum alloy material and preparation method thereof |
| CN106119604A (en) * | 2016-08-18 | 2016-11-16 | 江苏大学 | A kind of Y2o3ti 8Si 1.4Zr alloy of alloying and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121359A (en) * | 1993-03-02 | 1996-04-24 | I·N·弗兰特塞维奇材料科学研究所 | Titanium matrix composites |
| CN101155936A (en) * | 2005-04-08 | 2008-04-02 | 住友金属工业株式会社 | Ti alloy, ti alloy member and method for producing same |
-
2013
- 2013-12-19 CN CN201310710919.5A patent/CN103710572B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121359A (en) * | 1993-03-02 | 1996-04-24 | I·N·弗兰特塞维奇材料科学研究所 | Titanium matrix composites |
| CN101155936A (en) * | 2005-04-08 | 2008-04-02 | 住友金属工业株式会社 | Ti alloy, ti alloy member and method for producing same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105908047A (en) * | 2016-05-16 | 2016-08-31 | 西南石油大学 | Titanium-aluminum-silicon-tantalum alloy material and preparation method thereof |
| CN106119604A (en) * | 2016-08-18 | 2016-11-16 | 江苏大学 | A kind of Y2o3ti 8Si 1.4Zr alloy of alloying and preparation method thereof |
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