CN104532056A - High temperature titanium alloy and preparation method thereof - Google Patents
High temperature titanium alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high temperature titanium alloy and a preparation method thereof. Sn element is not added into the alloy provided by the invention, and the tearing tendency in a casting process and the cracking tendency in a welding process that likely to be caused by the brittle phase Ti3Sn can be eliminated, so that the high temperature titanium alloy involved in the invention can have better casting performance, welding performance and product reliability. Nb and Si elements are added at the same time to form Nb-Si high-melting-point compound particles, thus enhancing the high temperature endurance and creep properties of the material. In addition, a certain amount of C element is almost dissolved in the material matrix in the form of solid solution after adding, thus improving the high temperature endurance, creep properties and the like of the material.
Description
[technical field]
The present invention relates to a kind of titanium alloy and preparation method thereof, be specifically related to a kind of high-temperature titanium alloy and preparation method thereof.
[background technology]
Known, in world wide, high-temperature titanium alloy is mainly developed around the application background of aircraft engine, be mainly used in the positions such as aircraft engine wheel disc, low-pressure turbine blade, rotor, drum barrel, product type is mainly forging and sheet material, in view of engine is harsh to the requirement of material, require that it has the coupling of good room-temperature property, hot strength, creep resistance, thermostability, fatigue property and fracture toughness property etc.; Consider that product is mainly forging and sheet material simultaneously, then require that material has good hot and cold processing characteristics simultaneously.
The main application background of high-temperature titanium alloy material is space structure part, the type of product contains foundry goods, forging and sheet material; Different from aerospace component and rotatable parts, high-temperature titanium alloy material is in the technical indicator of material, except requiring to have except good room-temperature property, hot strength, creep resistance, enduring quality, cold and hot working performance, also require that material has good castability and welding property.
For aviation high-temperature titanium alloy material in current world wide, mainly contain two large significantly differences from the aspect analysis of alloying element composition: a large class is the high-temperature titanium alloy material containing Sn; Another kind of is not containing the high-temperature titanium alloy material of Sn.The relative merits of Sn element in high-temperature titanium alloy are as follows: 1) advantage: Sn belongs to neutral element in the alloy, in a-Ti and β-Ti, all have larger solid solubility, add together with other elements, can play the effect supplementing strengthening; Adding of Sn element, β phase content in material can not be increased, therefore while raising alloy material hot strength, can not reduce high temperature creep drag and the enduring quality of material; In addition, adding of Sn element, the susceptibility of material to hydrogen embrittlement can also be reduced.2) shortcoming: the high-temperature titanium alloy material thermostability after life-time service containing Sn has decline in various degree, and reason is: add more Al and Sn in alloy, can cause separating out a large amount of Ti
3x (X=Al, Sn) brittlement phase, makes alloy thermostability decline.Thermostability characterizes the ability that material keeps plasticity and toughness under high temperature long duration of action, is an important mechanical performance index of high-temperature titanium alloy, for ensureing that the high temperature life-time service reliability of high-temperature titanium alloy parts has great importance.Up to now, about the impact of Sn element on cast performance and welding property, there is no research report both at home and abroad.
(1) containing the high-temperature titanium alloy material of Sn
At present, countries in the world aircraft engine is BT18y, BT36, Ti-1100, IMI834, Ti-60 and Ti600 by the exemplary alloy of 600 DEG C of high-temperature titanium alloys, is all to develop on the basis of Ti-Al-Sn-Zr-Mo-Si system.Basic condition is as shown in the table.
Domestic and international 600 DEG C of high-temperature titanium alloy materials
| The trade mark | Country | Nominal composition (wt%) | Maximum operation (service) temperature |
| BT18y | Russia | Ti-6.5Al-2.5Sn-4.0Zr-0.7Mo-1.0Nb-0.25Si | 600℃ |
| BT36 | Russia | Ti-6.2Al-2.0Sn-3.6Zr-0.7Mo-5.0W-0.1Y-0.15Si | 600℃ |
| Ti-1100 | The U.S. | Ti-6.0Al-2.75Sn-4.0Zr-0.4Mo-0.45Si | 600℃ |
| IMI834 | Britain | Ti-5.8Al-4.0Sn-3.5Zr-0.5Mo-0.7Nb-0.35Si-0.06C | 600℃ |
| Ti60 | China | Ti-5.6Al-4.8Sn-2.0Zr-1.0Mo-0.25Si-1Nd | 600℃ |
| Ti6000 | China | Ti-6.0Al-2.8Sn-4.0Zr-0.5Mo-0.4Si-0.1Y | 600℃ |
Muscovite high-temperature titanium alloy development is very perfect and ripe, defines the titanium alloy system of complete set, and 600 DEG C of alloys used have BT18y and BT36.Add W in BT36 alloy, the eutectoid reaction temperature of W is higher (715 DEG C), has better thermostability containing W alloy.But due to the high-melting-point of W element, make conventional vacuum consumable electrode arc furnace melting method be difficult to fully be melted by W and evenly spread, easily form the metal inclusion of W and the β type segregation of rich W.Adding of Rare Earth Y element is an important feature of BT36, and micro-Y can the crystal grain of refining alloy significantly, improves plasticity and the thermostability of alloy.
The development of U.S.'s high-temperature titanium alloy is also comparatively ripe, alloy mainly Ti-6242S and Ti1100 that usage quantity is maximum on the engine at present, but the use temperature of Ti-6242S only has 540 DEG C.United States Patent (USP), the patent of invention of the Ti1100 high-temperature titanium alloy of publication number to be US4738822 be American TI MET company application, by weight percentage, alloying constituent is: Ti-(5.5-6.5) Al-(2.0-4.0) Sn-(3.5-4.5) Zr-(0.3-0.5) Mo-(0.35-0.55) Si, the feature of this alloy is that alloy composition has carried out strict control, as controlled Impurity Fe≤0.03%, O≤0.13%; Mo and Si is limited in a very narrow scope, to obtain the matched well of plasticity after static strength, creep strength and creep.Ti1100 alloy is on the basis of Ti-6242S alloying constituent, by the content of adjustment Al, Sn, Mo and Si element, makes the maximum operation (service) temperature of alloy bring up to 600 DEG C.
IMI834 alloy develops on the basis of IMI685 alloy, in alloy except the Mo adding 0.5%, also adds the Nb of 0.7%, while guarantee thermostability, improves the intensity of alloy to greatest extent.In order to the heat-resisting ability of β heat-treated sturcture is combined with α/β tissue, fatigue property and thin crystalline substance, effectively control the content of primary alpha phase, in alloy, add C element.Adding of C can reduce the slope that β transforms curve of approximation, and the curve of approximation slope of trend α/β alloy, allows to heat-treat the alloy of nearly β phase composite in the temperature range of the α phase only having 10%-20%.IMI834 alloy adopts bifurcation to organize the thermal treatment process of 1020 DEG C × 2h oil quenching+700 DEG C × 2h air cooling, can obtain tiny silicide particle and orderly Ti3Al phase, containing the primary alpha phase of 12 μm, make alloy have good integral high temperature mechanical property.
The high-temperature titanium alloy development course of China is with similar abroad, and compared with external similar alloy, the maximum feature of Ti-60 alloy is the rare earth element nd adding people about 1% in the alloy, and refinement alloy structure, improves the resistance of oxidation of alloy.Rare earth element internal oxidition in the alloy, makes the oxygen level in alloy substrate reduce and impels the Sn atom in matrix to shift to rare earth oxide, having restrained Ti
3the precipitation of X phase.Simultaneously, the rare earth oxide particles that rare-earth oxidation is formed plays strengthening effect as the dislocation substructure alloy formed around the dispersoid particle of alloy forming core and rare earth oxide particles thereof, makes Ti-60 alloy have good heat resistance and the optimum matching of thermostability at service temperatures.Ti600 alloy is on the basis of Ti1100, with the addition of the rare earth element of 0.1%.Research shows, the internal oxidition effect of Rare Earth Y element, can reduce the susceptibility of alloy to oxygen well, and rare earth oxide can hinder grain growth, crystal grain thinning simultaneously.The thermal treatment process of the solid solution+air cooling more than transformation temperature, obtains having certain thickness Wei Shi body α lamellar structure, makes alloy have good heat resistance and thermostability.
In recent years, along with motor performance promote tight demand, require the use temperature of titanium alloy and performance index more and more higher, therefore, the high-temperature titanium alloy used for a long time for more than 600 DEG C has both at home and abroad carried out studying extensively and profoundly, and creates other high-temperature titanium alloy materials a collection of.Concrete achievement in research is as follows:
The United States Patent (USP) of GE company, publication number is US4906436, it discloses a kind of novel 650 DEG C of anti-oxidant titanium alloys of high strength at high temperature, containing Al, Sn, Zr, Hf, Nb, Ta, Mo, Si and rare earth element (Re) in its alloying constituent, the forming technology that it adopts is quick setting method, recommend heat treating regime then for the above thermal treatment of alpha+beta/beta transformation point, microstructure is complete lamellar structure.This patent is pointed out, Hf and Ta adds high temperature tensile strength, creep strength and the oxidation-resistance that can significantly improve material, in the claim of this patent, Hf content requirement controls between 0.2%-3.0% (atomic percent), and Ta content requirement controls between 0.0%-1.5% (atomic percent).But the room temperature tensile unit elongation of this material only about 3.5%, Fracture of Material coupling is poor.Gigliotti M F X etc. also adopt the method for Rapid Solidification Powder metallurgy, carry out exploratory study (Rapidly solidified titanium alloys containing fine dispersoids " RapidlySolidified Materials " the edited by LEE P W of 650 DEG C of titanium alloys, MOLL J H, Metals Park, OH, 1987:141-151.), the alloy system Ti-Al-Sn-Zr-Nb-Mo-Er-Si that they adopt, 650 DEG C of tensile strengths of two kinds of preferred component bars can reach 700MPa, even if but the stretch percentage elongation at 650 DEG C is also only between 4.1%-6.3%, relative reduction in area is between 8.6%-12.1%, the strength of materials is poor with mating of plasticity.People's (United States Patent (USP)s such as SUZUKI AKIHIRO, publication number is US6284071B1/ European patent, publication number is EP0851036A1/ United States Patent (USP), publication number is, US5922274A/ Japanese Patent, publication number is JPH10195563A) have developed a kind of heat-resistant titanium alloy and preparation method thereof, by weight percentage, alloying constituent is Ti-(5.0-7.0) Al-(3.0-5.0) Sn-(2.5-6.0) Zr-(2.0-4.0) Mo-(0.05-0.8) Si-(0.001-0.2) C-(0.05-0.2) O, can select to add Nb and Ta that total amount is 0.3-2.0%, all the other are Ti and inevitable impurity element.
Chinese patent, publication number is CN101050496, and publication date is on October 10th, 2007, and Xibei Inst. of Non-Ferrous Metals develops a kind of high temperature, solid solution, strengthened, heat-resistant titanium alloy, and by weight percentage, alloying constituent is Al:4.5% ~ 7.5%; Sn:1.0% ~ 5.0%; Zr:2.0% ~ 8.0%; W:0.25% ~ 0.8%; Si:0.2% ~ 0.5%; Surplus is Ti and inevitable impurity element.Material has good over-all properties, and creep-resistant property and thermal stability have better coupling, can under 600 DEG C of conditions life-time service.Chinese patent, publication number is CN101050497, and publication date is on October 10th, 2007, the coloured institute in northwest on the basis of above-mentioned patented material, by adding Y:0.05 ~ 0.5%, the further welding property improving material.
Chinese patent, publication number is CN1772932, and publication date is on 05 17th, 2006, and Beijing Research Inst. of Aeronautic Material develops the high-temperature titanium alloy of a kind of high creep resistance and high-fatigue strength, and by weight percentage, alloying constituent is Al:3.0% ~ 7.0%; Sn:1.0% ~ 6.0%; Zr:1.0% ~ 6.0%; Nb:0.1 ~ 2.5%; Ta:0.2 ~ 4.0%; Mo:0.0 ~ 3.0%; Si:0.05% ~ 0.7%; C:0.0 ~ 0.1%; Surplus is Ti and inevitable impurity element.Material has good creep-resistant property, fatigue strength and fracture toughness property under 600 DEG C of conditions.
Chinese patent, publication number is CN101074464, and publication date is on November 21st, 2007, and Shanghai Communications University develops a kind of complex intensifying high-temperature titanium alloy, and by weight percentage, alloying constituent is Al:3.0-8.0%; Sn:1.0-6.0%; Zr:1.0-6.0%; Nb:0.5-1.5%; Mo:0.5-2.0%; Si:0.1-0.8%; La:0.3-1.0%; B:0.1-0.5%; Surplus is Ti and inevitable impurity element.Material still has good hot strength, creep-resistant property, thermal stability under 650-700 DEG C of condition.
Chinese patent, publication number is CN101988167A, publication date is on 03 23rd, 2011, the high-temperature titanium alloy that a kind of maximum operation (service) temperature can reach 600 DEG C has been invented by Beijing University of Technology, it is characterized in that main alloy element has done the adjustment of content on existing 600 DEG C of high-temperature titanium alloy bases, add Mo, Nb and rare earth element nd simultaneously.Alloy component range (weight percent) is: Al:6.2-6.5%, Zr:3.5-4.0%, Sn:2.0-2.5%, Mo:0.1-0.3%, Nb:0.6-0.9%, Si:0.3-0.4%, Nd:0.4-0.8%, and surplus is Ti.Alloy has higher heat resistance and good thermostability.
Chinese patent, publication number is CN102952968A, and publication date is on 03 06th, 2013, and Shanghai Aerospace Precision Machinery Inst. develops a kind of particle strengthening heat-resistant titanium alloy, and each component weight percent content is Al:4-7%; Sn:3-6%; Zr:3-6%; Mo:0.6-1.5%; Nb:0.5-1.5%; Si:0.1-0.5%; B:0.1-1.1%; C:0.03-0.3%; Ti is surplus.This material still maintains good hot strength, creep resistance, the over-all properties such as thermally-stabilised at 600-650 DEG C, and heat processing technique window is wide, and melt fills type good fluidity, can casting, and the thermal treatment process window of deformable member and foundry goods is wide.
Chinese patent, publication number is CN103014412A, and publication date is on 04 03rd, 2013, and a kind of Composite heat-resistant titanium alloy has been invented by Shifang City Mingri Space Navigation Industry Co., Ltd., and each component weight percent content is Al:4-8%; Sn:1-7%; Zr:2-8%; W:0.25-4%; Si:0.1-0.5%; Nb:0.2-2.5%, all the other are titanium and inevitable impurity.Material has good over-all properties under 600 DEG C of conditions, especially creep-resistant property and excellent heat stability; This alloy has good weldability simultaneously, and vacuum electron beam or argon arc welding method alloy sheet material can be adopted to carry out welding processing, and welding strength coefficient is greater than 90%.
Chinese patent, publication number is CN104018027A, and publication date is on 09 03rd, 2014, and Metal Inst., Chinese Academy of Sciences develops a kind of heat resistance titanium alloy and machining manufacture thereof.The composition (weight percent) of alloy is Al:5.4-6.3%; Sn:3.0-5.0%; Zr:2.5-6.4%; Mo:0.0-0.96%; Si:0.25-0.5%; Nb:0.2-0.5%; Ta:0.3-3.4%; W:0.2-1.6%; C:0.0-0.07%; O≤0.17%; Fe≤0.03%, surplus is Ti and inevitable impurity element.Alloy, by different hot-work and thermal treatment process combination, can obtain the Different matching of tensile strength and plasticity, lasting and creep strength and thermostability, can be used for making advanced aero engine high temperature position part, use time long within the scope of 600-650 DEG C.
(2) not containing the high-temperature titanium alloy material of Sn
Chinese patent, publication number is CN103409658A, publication date is on November 27th, 2013, No.China Shipbuilding Industry Group Co.ltd. 725 Institute develop a kind of can welding titanium alloy containing resistance to 600 DEG C of high strength at high temperature of Sn element, its chemical composition ranges is Al:6.5-9.5wt%; Mo:1.0-4.0wt%; Nb:2.5-5.5wt%; Zr:1.5-4.5wt%; Nd:0.05-0.36wt%, surplus is Ti.These 600 DEG C of high strength at high temperature can welding titanium alloy, breaches at present tradition 600 DEG C of cold-formed difficulties of high-temperature titanium alloy and welding technological properties difference technical bottleneck both at home and abroad, fills up this field domestic technique void item.But the main drawback of this material is: 1) the Mo equivalent ([Mo] when=%Mo+%Nb/3.6) of this material is more than 1.7, although the room temperature of this material and hot strength are very high, but the high temperature creep property of this material, enduring quality are poor, but not high-temperature titanium alloy truly; The high-temperature titanium alloy Mo equivalent that ripe can be applied to temperature 600 DEG C both at home and abroad substantially all controls near 1.0 or is less than 1.0, and too high Mo equivalent can reduce high temperature creep and the enduring quality of material.2) the Al content 6.5-9.5wt% of this material, ([AL] is as=%Al+%Sn/3+%Zr/6+10% " O " for Al content and Al equivalent, wherein " O "=O+2N+C) all very high, the strengthening mechanism of this material mainly strengthens titanium alloy substrate by separating out Ti3Al brittlement phase, with domestic and international high-temperature titanium alloy mainly through controlling Al equivalent and the Mo equivalent of alloying element, thus the mechanism controlling tissue and Phase Proportion is different.
[summary of the invention]
For overcoming the deficiency existed in background technology, the invention provides a kind of high-temperature titanium alloy and preparation method thereof, any Sn element is not added in the present invention, stop crackle tendency in the tearing tendency in the castingprocesses that brittlement phase Ti3Sn easily causes, welding process, made the present invention have better castability, welding property and product reliability; Add while Nb and Si element, define Nb-Si high melting compound particle, improve high-temperature and durable and the creep property of material; In addition, be almost all solid-solubilized in material matrix after the adding of a certain amount of C element, improve the high-temperature and durable and creep property etc. of material.
For realizing goal of the invention as above, the present invention adopts technical scheme as described below:
A kind of high-temperature titanium alloy, its composition comprises by mass percentage:
Al 5.5～7.0 %；
Zr 2.0～5.0 %；
Nb 0.5～2.5%；
Mo 0.2～1.0%；
Si 0.1～0.8 %；
C 0.03～0.15%；
Surplus is Ti and inevitable impurity element.
Described high-temperature titanium alloy, by Ingredient percent, the composition of described high-temperature titanium alloy is preferably: Al, 6.0 ~ 6.6 %; Zr, 3.5 ~ 4.5%; Nb, 1.0 ~ 2.0%; Mo, 0.4 ~ 0.8%; Si, 0.2 ~ 0.7 %; C, 0.06 ~ 0.14%; Surplus is Ti and inevitable impurity element.
Described high-temperature titanium alloy, by Ingredient percent, the composition of described high-temperature titanium alloy is preferably: Al, 6.3%; Zr, 4.0%; Nb, 1.6%; Mo, 0.6%; Si, 0.4%; C, 0.10%; All the other are Ti and inevitable impurity element.
A preparation method for high-temperature titanium alloy, preparation method specifically comprises the steps:
One, material is prepared:
First Ti adopts 0A--1 level titanium sponge, and alloy element Nb, Mo, Si add with master alloy form; Zr and C adds with sponge Zr and carbon dust form respectively; Al part is brought into by master alloy, and insufficient section adds with pure Al;
Two, high-temperature titanium alloy is prepared:
Connect step, master alloy and titanium sponge are through preparing burden, after batch mixing, electrode is pressed into press, then by electrode assembly welding together, melting 2 ~ 3 times in melting equipment, make alloy cast ingot, alloy cast ingot is carried out vacuum pouring mechanics coupon by vacuum consumable electrode arc furnace foundry furnace or vacuum induction casting stove; Cast-on test bar is through hip treatment, remove internal shrinkage, by casting and hip treatment, acquisition room temperature-700 DEG C of tensile strengths and plasticity, in short-term lasting and creep property all meet the service requirements of airspace engine high temperature component, and have the high-temperature titanium alloy of good welds performance.
The preparation method of described high-temperature titanium alloy, described melting equipment is vacuum consumable electrode arc furnace or vacuum induction furnace.
Adopt technical scheme as above, the present invention has superiority as described below:
A kind of high-temperature titanium alloy of the present invention and preparation method thereof, have 1, the alloy system of high-temperature titanium alloy material of the present invention is Ti-Al-Zr-Nb-Mo-Si-C system alloy material system, obviously be different from current Ti-Al-Sn-Zr-Mo-Si alloy material system both domestic and external, any Sn element is not added in this material, stop crackle tendency in the tearing tendency in the castingprocesses that brittlement phase Ti3Sn easily causes, welding process, made this material have better castability, welding property and product reliability; Add while Nb and Si element, define Nb-Si high melting compound particle, improve high-temperature and durable and the creep property of material; In addition, be almost all solid-solubilized in material matrix after the adding of a certain amount of C element, improve high-temperature and durable and the creep property of material; 2, high-temperature titanium alloy material of the present invention, only need to adopt hip treatment just can obtain the high temperature tensile properties of excellent room temperature and 600 ~ 700 DEG C, creep and enduring quality to casting material out, and process without the need to " solid solution aging " that domestic and international patented material adopts usually.Therefore, material of the present invention is simple compared with the preparation section of other patented materials, preparation flow is short, cost is minimum; Meanwhile, due to without the need to through fixation rates, make the good welding performance of this material, not easily occur welding crack; 3, the High-Temperature Strengthening principle mechanism of material of the present invention is mainly by the interaction of the interaction of control Al equivalent, Mo equivalent, elements Si and Nb, elements Si and Zr, and the comprehensive action of C element to these aspects above such as the solution strengthening of superalloy matrix realizes; And the strengthening mechanism of domestic and international most of high-temperature titanium alloy mainly separates out Ti by solid-solution and aging heat treatment
3al phase realizes; 4, after alloy of the present invention adopts casting+hip treatment, metallographic structure is: sheet α+intergranular β+grain boundary α, grain-size≤0.506 μm, this material has good room temperature strength and plasticity, 600 ~ 700 DEG C of hot strengths and plasticity, 600-700 DEG C high temperature creep property and enduring quality simultaneously, and good welding property.
[embodiment]
Can explain the present invention in more detail by the following examples, the present invention is not limited to the following examples;
A kind of high-temperature titanium alloy of the present invention, its composition comprises by mass percentage:
Al 5.5～7.0 %； Zr 2.0～5.0 %；
Nb 0.5～2.5%； Mo 0.2～1.0%；
Si 0.1～0.8 %； C 0.03～0.15%；
Surplus is Ti and inevitable impurity element.
Wherein the present invention presses Ingredient percent, and the composition of described high-temperature titanium alloy is preferably: Al, 6.0 ~ 6.6 %; Zr, 3.5 ~ 4.5%; Nb, 1.0 ~ 2.0%; Mo, 0.4 ~ 0.8%; Si, 0.2 ~ 0.7 %; C, 0.06 ~ 0.14%; Surplus is Ti and inevitable impurity element.
Wherein the present invention presses Ingredient percent, and the composition of described high-temperature titanium alloy is preferably: Al, 6.3%; Zr, 4.0%; Nb, 1.6%; Mo, 0.6%; Si, 0.4%; C, 0.10%; All the other are Ti and inevitable impurity element.
A preparation method for high-temperature titanium alloy, preparation method specifically comprises the steps:
One, material is prepared:
First Ti adopts 0A--1 level titanium sponge, and alloy element Nb, Mo, Si add with master alloy form; Zr and C adds with sponge Zr and carbon dust form respectively; Al part is brought into by master alloy, and insufficient section adds with pure Al;
Two, high-temperature titanium alloy is prepared:
Connect step, master alloy and titanium sponge, through preparing burden, after batch mixing, are pressed into electrode with press, then by electrode assembly welding together, melting 2 ~ 3 times in melting equipment, described melting equipment is vacuum consumable electrode arc furnace or vacuum induction furnace; Make alloy cast ingot, alloy cast ingot is carried out vacuum pouring mechanics coupon by vacuum consumable electrode arc furnace foundry furnace or vacuum induction casting stove; Cast-on test bar is through hip treatment, remove internal shrinkage, by casting and hip treatment, acquisition room temperature-700 DEG C of tensile strengths and plasticity, in short-term lasting and creep property all meet the service requirements of airspace engine high temperature component, and have the high-temperature titanium alloy of good welds performance.
The selection of heat-resistant titanium alloy alloy system of the present invention, alloying element kind and composition range thereof, is through further investigation for many years and repeatedly tests and draw, its design philosophy is respectively described below:
1) the present invention is not designed to containing the alloy system of the high-temperature titanium alloy material of Sn: Ti-Al-Zr-Nb-Mo-Si-C system alloy material system, any Sn element is not added in material, and with the addition of a certain amount of Nb element and C element, this is also that material alloys system of the present invention is different from the past containing the maximum feature of the high-temperature titanium alloy material system (Ti-Al-Sn-Zr-Mo-Si system) of Sn.As described in foregoing Background, (if Chinese patent, publication number are CN101050496, publication date is 2007.10.10 to the domestic and international patent high-temperature titanium alloy material of 600 DEG C of high-temperature titanium alloys (as BT18y, BT36, Ti-1100, IMI834 and Ti-60 and Ti600) that countries in the world are developed for aircraft engine application background and more than 600 DEG C; Chinese patent, publication number are CN101074464, and publication date is 2007.11.21; Chinese patent, publication number are CN104018027A, publication date is 2014.09.03 etc.) be all the high-temperature titanium alloy material developed on the basis of Ti-Al-Sn-Zr-Mo-Si system, all with the addition of the Sn element of more than 2.0%, other elemental compositions also have obvious difference with material of the present invention in addition.
The present invention does not add any Sn element, mainly based on different application backgrounds and up-to-date result of study: material requirements of the present invention realizes the high temperature tensile properties of excellent room temperature and 600 ~ 700 DEG C, excellent short creep and enduring quality, and good casting and welding property.Sn belongs to weak α stable element in high-temperature titanium alloy, adds Sn and can form brittlement phase Ti in the high-temperature titanium alloy of higher Al content
3sn.Found by our research in recent years: brittlement phase Ti
3sn can significantly improve the tearing tendency in high-temperature titanium alloy castingprocesses, very easily occurs crackle in process of cooling; Meanwhile, brittlement phase Ti
3the appearance of Sn, high-temperature titanium alloy product can be made very easily to occur in welding process, and crackle is inclined to, and causes part needs to carry out repeatedly repair welding outside the Technology of Welding of national regulations requires, this reduces the reliability of product.
Add while Nb and Si element in material of the present invention, define Nb-Si high melting compound particle, improve high-temperature and durable and the creep property of material; In addition, be almost all solid-solubilized in material matrix after the adding of a certain amount of C element, also significantly improve high-temperature and durable and the creep property of material.
Therefore, material of the present invention, compared with the high-temperature titanium alloy material reported in background technology, except having good room temperature and high-temperature behavior equally, also has more excellent castability, welding property and product reliability in addition.
2) high-temperature titanium alloy material of the present invention, only need to adopt hip treatment just can obtain excellent room temperature and 600 ~ 700 DEG C of high temperature tensile properties, creep and enduring qualities to casting material out, simultaneously material has good welding property, and without the need to " solid solution aging " treatment process that domestic and international patented material adopts usually.As: the United States Patent (USP) of GE company, publication number are US4906436, recommend heat treating regime then for the above thermal treatment of alpha+beta/beta transformation point; Chinese Academy of Sciences's metal Chinese patent, publication number be CN104018027A, publication date is 2014.09.03, (technique is the above 10-30 of alpha+beta/beta transformation point DEG C solid solution, air cooling or air-cooled or oil quenching to adopt cast form+hip treatment+solid-solution and aging heat treatment, then at 700-750 DEG C of timeliness 2-8h, air cooling or stove cold); The Chinese patent of Shanghai Communications University, publication number are CN101074464, and publication date is 2007.11.21, and thermal treatment process is 1100 DEG C of solid solutions 1 hour, air cooling, then at 650 DEG C of timeliness 2h, air coolings.Therefore, material of the present invention is simple compared with the preparation section of other patented materials, preparation flow is short, minimization of cost; Meanwhile, because material of the present invention is without the need to through fixation rates, so the good welding performance of this material, not easily there is welding crack.
3) the present invention does not have remarkable difference containing high-temperature titanium alloy material alloys element design criterias of Sn containing the high-temperature titanium alloy material alloys element design criteria of Sn with domestic and international other.Element in material of the present invention and content design as follows:
Aluminium (Al): 5.5 ~ 7.0wt%.Al is the most frequently used a kind of strengthening element of heat-resistant titanium alloy, has stable alpha phase and improves the effect of phase transition temperature.Al content can significantly improve the room temperature of titanium alloy, high temperature, creep and creep rupture strength, but has disadvantageous effect to titanium alloy plasticity and thermostability.The Al equivalent of design of material of the present invention ([AL] when=%Al+%Sn/3+%Zr/6+10% " O ", wherein " O "=O+2N+C) interval range is 8-9, while making material have excellent room temperature, high temperature, creep and creep rupture strength, takes into account the plasticity of material.Ti3Al fragility ordered phase can be caused to separate out when Al equivalent is greater than 9, material plasticity, toughness especially thermostability can significantly reduce, and finally cause material cannot meet the service requirements of Aeronautics and Astronautics engine structure.In titanium alloy component system of the present invention, Al constituent content is strict controlled between 5.5-7.0wt%, the high heat resistance that the present invention advocates can be obtained, ensure that there is higher plasticity simultaneously.
Chinese patent, publication number that the design of Al content of the present invention and No.China Shipbuilding Industry Group Co.ltd. 725 Institute declare are CN103409658A, publication date is 2013.11.27, there is obvious difference: the Al content of contrast patented material is 6.5 ~ 9.5wt%, ([AL] is as=%Al+%Sn/3+%Zr/6+10% " O " for Al content and Al equivalent, wherein " O "=O+2N+C) all very high, the strengthening mechanism of material mainly strengthens titanium alloy substrate by separating out Ti3Al brittlement phase; And Al content of the present invention is 5.5-7.0wt%, without the precipitation of Ti3Al brittlement phase, strengthening mechanism is obviously different.
Zirconium (Zr): 2.0 ~ 5.0wt%.Zr belongs to neutral element in high-temperature titanium alloy, in α phase and β phase, all have higher solid solubility, adds the effect can played and supplement and strengthen together with the element such as Al, Si; In the titanium alloy adding Si element, add Zr also help the even precipitation promoting silicide, form (Ti, Zr) 5Si or (Ti, Zr) 6Si disperse educt phase, improve high temperature creep and the enduring quality of material.Although the strengthening effect of Zr is obvious, Zr content, when more than 5wt%, can significantly fall low-alloyed antioxidant property.Therefore Zr add-on limits by titanium alloy oxidation-resistance, and design of material of the present invention is within 5.0wt%.Meanwhile, material of the present invention is when practical application, and Zr content needs to mate with Al, O, N, C element content, and the Al equivalent interval range meeting design of material of the present invention is the requirement of 8-9, thus ensures high temperature creep and enduring quality requirement.
Molybdenum (Mo): 0.2 ~ 1.0wt%.Mo is strong beta stable element the most frequently used in titanium alloy, is also effective strengthening element.Adding a small amount of Mo in heat-resistant titanium alloy can make it while having alpha+beta titanium alloys high strength, also has high creep and the enduring quality of α type alloy.Room in Mo element and alloy attracts each other, On Dislocation Motion plays inhibition, is therefore favourable to creep and enduring quality in theory.The Mo equivalent of design of material of the present invention ([Mo] when=%Mo+%Nb/3.6) interval range is 0.3-1.2, makes material have excellent high temperature creep and creep rupture strength; High temperature creep and creep rupture strength performance can be caused significantly to reduce when Mo equivalent is greater than 1.2.In titanium alloy component system of the present invention, Mo constituent content is strict controlled between 0.2 ~ 1.0wt%, the high heat resistance that the present invention advocates can be obtained, ensure that there is higher plasticity simultaneously.
Chinese patent, publication number that the design of Mo content of the present invention and No.China Shipbuilding Industry Group Co.ltd. 725 Institute declare are CN103409658A, publication date is that 2013.11.27 has obvious difference: the Mo content of contrast patented material is 1.0 ~ 4.0wt%, Mo equivalent ([Mo] when=%Mo+%Nb/3.6) is more than 1.7, and the Mo content of design of material of the present invention is 0.2 ~ 1.0wt%, Mo equivalent interval range is 0.3 ~ 1.2.
Niobium (Nb): 0.5 ~ 2.5wt%.Nb is a kind of weak beta stable element, all has certain strengthening effect to α and β; In addition, add while Nb and Si element in material of the present invention, define Nb-Si high melting compound particle, improve high-temperature and durable and the creep property of material.Meanwhile, material of the present invention is when practical application, and Nb content needs to mate with Mo constituent content, and the Mo equivalent interval range meeting design of material of the present invention is the requirement of 0.3 ~ 1.2, thus ensures high temperature creep and enduring quality requirement.
Chinese patent, publication number that the design of Nb content of the present invention and No.China Shipbuilding Industry Group Co.ltd. 725 Institute declare are CN103409658A, publication date is that 2013.11.27 has obvious difference: the Nb content of contrast patented material is 2.5 ~ 5.5wt%, and the Nb content of design of material of the present invention is 0.5 ~ 2.5wt%.
Silicon (Si): 0.1 ~ 0.8wt%.Si is very important micro-alloying elements in high-temperature titanium alloy, and domestic and international more than 500 DEG C high-temperature titanium alloys all add the element silicon of 0.1 ~ 0.5wt% at present, to ensure creep and the enduring quality of alloy.There is strong attracting each other in room in Si element and alloy, and forms solute atoms-room air mass, hinders dislocation motion, puies forward heavy alloyed high temperature tensile strength and creep property.The present invention studies discovery: add the even precipitation being conducive to promoting silicide while Zr, Si element, add a certain amount of Si content and can form (Ti, Zr) 5Si or (Ti, Zr) 6Si disperse educt phase, improves high temperature creep and the enduring quality of material; In addition, add while Nb and Si element, define Nb-Si high melting compound particle, improve high-temperature and durable and the creep property of material.Si constituent content is strict controlled in 0.1 ~ 0.8wt%, too high Si content, and alloy plasticity, toughness can be caused to reduce; And Si content is lower than 0.1wt%, alloy then can not get efficient hardening.
Carbon (C): 0.03 ~ 0.15wt%.The present invention studies discovery: 0.03 ~ 0.15wt%C can all be solid-solubilized in material matrix, can significantly improve high-temperature and durable and the creep property of material, and 0.03 ~ 0.15wt%C remains on acceptable level to material plasticity, toughness disadvantageous effect simultaneously.
The present invention is found by research: brittlement phase Ti
3sn can significantly improve the tearing tendency in high-temperature titanium alloy castingprocesses, very easily occurs crackle in process of cooling; Meanwhile, brittlement phase Ti
3the appearance of Sn, high-temperature titanium alloy product can be made very easily to occur in welding process, and crackle is inclined to, and causes part needs to carry out repeatedly repair welding outside the Technology of Welding of national regulations requires, this reduces the reliability of product.
Specific embodiments of the invention are as follows:
The preparation technology of following examples 1# ~ 7# high-temperature titanium alloy material is: starting material adopt 0A--1 level titanium sponge, and alloy element Nb, Mo, Si are respectively with AlNb, AlMo, and AlSi master alloy form adds; Zr and C adds with sponge Zr and carbon dust form respectively; Al part is brought into by master alloy, and insufficient section adds with pure Al; Master alloy and titanium sponge, through preparing burden, after batch mixing, are pressed into electrode with press; By electrode melting 2 times in vacuum induction furnace, make alloy cast ingot; By alloy cast ingot by vacuum induction casting stove cast precision-investment casting shell mould, finally obtain attached casting mechanics coupon; Cast-on test bar, through hip treatment (temperature 920 DEG C, argon pressure 120MPa, soaking time 2.5 hours, cool to 300 DEG C with the furnace come out of the stove), removes internal shrinkage.
The chemical content (wt%) of embodiment 1# ~ 7# high-temperature titanium alloy material, shown in seeing the following form.
The chemical content (wt%) of embodiment 1# ~ 7# high-temperature titanium alloy material
| Al | Zr | Nb | Mo | Si | C | |
| Embodiment 1 | 6.3 | 4.0 | 1.6 | 0.6 | 0.4 | 0.10 |
| Embodiment 2 | 6.2 | 4.0 | 1.6 | 0.6 | 0.3 | 0.06 |
| Embodiment 3 | 6.6 | 3.9 | 1.7 | 0.6 | 0.3 | 0.08 |
| Embodiment 4 | 6.0 | 4.5 | 1.0 | 0.8 | 0.2 | 0.14 |
| Embodiment 5 | 6.6 | 3.5 | 2.0 | 0.4 | 0.7 | 0.06 |
| Embodiment 6 | 5.5 | 5.0 | 0.5 | 1.0 | 0.1 | 0.15 |
| Embodiment 7 | 7.0 | 2.0 | 2.5 | 0.2 | 0.8 | 0.03 |
The room temperature tensile properties of embodiment 1# ~ 7# high-temperature titanium alloy material, shown in seeing the following form.
Embodiment 1# ~ 7# room temperature tensile properties
| R P0.2（MPa） | R m（MPa） | A（%） | |
| Embodiment 1 | 905 | 990 | 9.0 |
| Embodiment 2 | 900 | 980 | 12.0 |
| Embodiment 3 | 930 | 995 | 10.5 |
| Embodiment 4 | 900 | 970 | 8.5 |
| Embodiment 5 | 910 | 980 | 10.0 |
| Embodiment 6 | 905 | 985 | 8.0 |
| Embodiment 7 | 910 | 990 | 9.5 |
600 DEG C of tensile properties of embodiment 1# ~ 7# high-temperature titanium alloy material, shown in seeing the following form.
Embodiment 1# ~ 7# 600 DEG C of tensile properties
650 DEG C of tensile properties of embodiment 1# ~ 7# high-temperature titanium alloy material, shown in seeing the following form.
Embodiment 1# ~ 7# 650 DEG C of tensile properties
700 DEG C of tensile properties of embodiment 1# ~ 7# high-temperature titanium alloy material, shown in seeing the following form.
Embodiment 1# ~ 7# 700 DEG C of tensile properties
600 DEG C, 650 DEG C, 700 DEG C high temperature endurance performances of embodiment 1# ~ 7# high-temperature titanium alloy material, shown in seeing the following form.
Embodiment 1# ~ 7# 600 DEG C, 650 DEG C, 700 DEG C high temperature endurance performances
| 600 DEG C lasting | 650 DEG C lasting | 700 DEG C lasting | |
| Embodiment 1 | >1.5h | >1.5h | 59 minutes |
| Embodiment 2 | >1.5h | >1.5h | 53 minutes |
| Embodiment 3 | >1.5h | >1.5h | >1.0h |
| Embodiment 4 | >1.5h | >1.5h | >1.0h |
| Embodiment 5 | >1.5h | >1.5h | >1.0h |
| Embodiment 6 | >1.5h | >1.5h | >1.0h |
| Embodiment 7 | >1.5h | >1.5h | >1.0h |
Remarks: 600 DEG C of persistence technologies require: lasting under 600 DEG C of * 400Mpa >=1 hour;
650 DEG C of persistence technologies require: lasting under 650 DEG C of * 340Mpa >=1 hour;
700 DEG C of persistence technologies require: lasting under 700 DEG C of * 290Mpa >=50 minutes.
600 DEG C, 650 DEG C, 700 DEG C high temperature creep properties of embodiment 1# ~ 7# high-temperature titanium alloy material, shown in seeing the following form.
Embodiment 1# ~ 7# 600 DEG C, 650 DEG C, 700 DEG C high temperature creep properties
| 600 DEG C of creep residual elongation rates (%) | 650 DEG C of creep residual elongation rates (%) | 700 DEG C of creep residual elongation rates (%) | |
| Embodiment 1 | 0.40 | 0.72 | 4.96 |
| Embodiment 2 | 0.72 | 0.96 | 5.68 |
| Embodiment 3 | 0.60 | 0.85 | 5.26 |
| Embodiment 4 | 0.32 | 0.45 | 1.90 |
| Embodiment 5 | 0.35 | 0.51 | 1.86 |
| Embodiment 6 | 0.38 | 0.49 | 1.73 |
| Embodiment 7 | 0.43 | 0.62 | 2.68 |
Remarks: 600 DEG C of creep conditions: 600 DEG C/400Mpa/0.5h;
650 DEG C of creep conditions: 650 DEG C/340Mpa/0.5h;
700 DEG C of creep conditions: 700 DEG C/290Mpa/0.5h.
Visible by above embodiment 1# ~ 7#: the present invention has good room temperature strength and plasticity, 600-700 DEG C hot strength and plasticity, 600 ~ 700 DEG C of high temperature creep properties and enduring quality, meet the service requirements of space structure part, and can as the candidate materials of aerospace component.
Part not in the detailed description of the invention is prior art.
The embodiment selected in this article in order to open object of the present invention, currently thinks to be suitable for, but it is to be understood that the present invention is intended to comprise all changes belonging to the embodiment in this design and invention scope and improvement.
Claims (5)
1. a high-temperature titanium alloy, is characterized in that: its composition comprises by mass percentage:
Al 5.5～7.0 %；
Zr 2.0～5.0 %；
Nb 0.5～2.5%；
Mo 0.2～1.0%；
Si 0.1～0.8 %；
C 0.03～0.15%；
Surplus is Ti and inevitable impurity element.
2. high-temperature titanium alloy according to claim 1, is characterized in that: by Ingredient percent, and the composition of described high-temperature titanium alloy is preferably: Al, 6.0 ~ 6.6 %; Zr, 3.5 ~ 4.5%; Nb, 1.0 ~ 2.0%; Mo, 0.4 ~ 0.8%; Si, 0.2 ~ 0.7 %; C, 0.06 ~ 0.14%; Surplus is Ti and inevitable impurity element.
3. high-temperature titanium alloy according to claim 1, is characterized in that: by Ingredient percent, and the composition of described high-temperature titanium alloy is preferably: Al, 6.3%; Zr, 4.0%; Nb, 1.6%; Mo, 0.6%; Si, 0.4%; C, 0.10%; All the other are Ti and inevitable impurity element.
4. implement the claims the preparation method of a kind of high-temperature titanium alloy of a kind of high-temperature titanium alloy described in 1 ~ 3 arbitrary claim, it is characterized in that: preparation method specifically comprises the steps:
One, material is prepared:
First Ti adopts 0A--1 level titanium sponge, and alloy element Nb, Mo, Si add with master alloy form; Zr and C adds with sponge Zr and carbon dust form respectively; Al part is brought into by master alloy, and insufficient section adds with pure Al;
Two, high-temperature titanium alloy is prepared:
Connect step, master alloy and titanium sponge are through preparing burden, after batch mixing, electrode is pressed into press, then by electrode assembly welding together, melting 2 ~ 3 times in melting equipment, make alloy cast ingot, alloy cast ingot is carried out vacuum pouring mechanics coupon by vacuum consumable electrode arc furnace foundry furnace or vacuum induction casting stove; Cast-on test bar is through hip treatment, remove internal shrinkage, by casting and hip treatment, acquisition room temperature-700 DEG C of tensile strengths and plasticity, in short-term lasting and creep property all meet the service requirements of airspace engine high temperature component, and have the high-temperature titanium alloy of good welds performance.
5. the preparation method of high-temperature titanium alloy according to claim 4, is characterized in that: described melting equipment is vacuum consumable electrode arc furnace or vacuum induction furnace.
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| CN104878452A (en) * | 2015-05-13 | 2015-09-02 | 南京理工大学 | High-temperature high-strength TiAl-Nb monocrystal and preparation method thereof |
| CN105803256A (en) * | 2016-04-06 | 2016-07-27 | 苏州裕通达特种金属材料有限公司 | High-temperature titanium alloy for automobile engine valve and preparation method and application thereof |
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| CN109926567A (en) * | 2019-04-01 | 2019-06-25 | 洛阳鹏起实业有限公司 | A kind of titanium alloy/bimetal copper-steel composite members and preparation method thereof |
| CN111020290A (en) * | 2019-12-20 | 2020-04-17 | 洛阳双瑞精铸钛业有限公司 | Casting titanium alloy material suitable for 650-plus-750 ℃ high temperature and preparation method thereof |
| CN113481408A (en) * | 2021-07-08 | 2021-10-08 | 中南大学 | Powder metallurgy Ti-Zr alloy for dentistry and preparation method thereof |
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