EP1945827A1 - Alliage de ti forme a froid - Google Patents

Alliage de ti forme a froid

Info

Publication number
EP1945827A1
EP1945827A1 EP06806675A EP06806675A EP1945827A1 EP 1945827 A1 EP1945827 A1 EP 1945827A1 EP 06806675 A EP06806675 A EP 06806675A EP 06806675 A EP06806675 A EP 06806675A EP 1945827 A1 EP1945827 A1 EP 1945827A1
Authority
EP
European Patent Office
Prior art keywords
titanium alloy
temperature
annealing temperature
titanium
cold
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06806675A
Other languages
German (de)
English (en)
Other versions
EP1945827B1 (fr
Inventor
Svetlana Skvortsova
Alexander Ilin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hempel Robert P
Original Assignee
Hempel Robert P
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hempel Robert P filed Critical Hempel Robert P
Publication of EP1945827A1 publication Critical patent/EP1945827A1/fr
Application granted granted Critical
Publication of EP1945827B1 publication Critical patent/EP1945827B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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

Definitions

  • the invention relates to cold-workable ( ⁇ + ⁇ ) titanium alloys and to a heat treatment process for producing cold-workable ( ⁇ + ⁇ ) titanium alloys.
  • the invention further relates to the use of heat-treated ( ⁇ + ⁇ ) titanium alloys for the production of components from the titanium alloy by means of cold forming.
  • titanium alloy components are becoming increasingly attractive in a wide variety of technical fields.
  • the reason for this attractiveness is in particular the low specific density of titanium alloys combined with high strength values and the low corrosion sensitivity of titanium alloys.
  • Titanium alloys can generally be divided into so-called ⁇ -, ⁇ + ⁇ - and ⁇ -titanium alloys according to the phases present at room temperature. Pure titanium at room temperature is in the ⁇ -phase (hexagonal structure) before and transforms at about 890 0 C (beta transus) in a body-centered cubic beta phase by.
  • the transformation temperature of titanium alloys is influenced by the nature and quantity of the alloy constituents and can moreover be determined by a
  • the ⁇ -phase can be stabilized over a wider temperature range (increase of the ⁇ -transus temperature).
  • the addition of other alloying elements produces and stabilizes the ⁇ -phase (lowering the ⁇ -transus temperature). It is therefore possible to subdivide the alloying elements into so-called ⁇ -stabilizers and ⁇ -stabilizers.
  • Technically used ⁇ -stabilizers are, for example, oxygen, nitrogen, carbon or aluminum.
  • technically used ⁇ -stabilizers are e.g. Hydrogen, vanadium, molybdenum, iron, chromium, copper, palladium or silicon.
  • Alloys with a high proportion of the ⁇ -phase regularly have lower strength values than alloys with a high proportion of the ⁇ -phase.
  • the specific gravity of high beta titanium alloys is usually higher than the specific gravity of such high alpha fraction titanium alloys. Due to the greater number of slip planes of the cubic lattice of ⁇ -titanium, the ⁇ -phase is better cold-formable than the ⁇ -phase.
  • Technically used alloys usually represent a compromise in which the proportion of ⁇ -phase and ⁇ -phase is adjusted by alloying the corresponding ⁇ and ⁇ stabilizers, as described e.g. require the desired manufacturing properties, strength values and corrosion properties of the component.
  • Titanium alloys are regularly weldable and heat-moldable only with great effort.
  • technically customary titanium alloys are only cold-deformable to a very limited extent.
  • cold workability is meant the ability of a material to be deformed at room temperature without this deformation results in a considerable loss of strength or cracking.
  • Titanium alloy components are therefore currently used almost exclusively in high-priced products, such as, for example. in the field of aviation, in particular military aviation and medical technology.
  • titanium alloy which comprises 1.5-3.0% by weight of aluminum (all% data are hereinafter referred to as% by weight of information), 4.5-8.0% molybdenum, 1 , 0-3.5% vanadium, 1.5-3.8% iron.
  • This alloy which has been manufactured on the basis of relatively inexpensive alloying elements, can, after heat treatment, achieve a certain ratio of strength and ductile properties and be used for the manufacture of some types of fasteners and springs. The main drawback of this alloy is the costly heat treatment required to achieve these properties.
  • a titanium alloy which contains 1, 2-3.8% aluminum, 5.1-6.5% molybdenum, 4.0-6.5% vanadium, 0.01-0.05% silicon, 0.005 Contains -0.015% hydrogen. Although this alloy has increased ductility during multi-stage deformation and is used to make rivets. However, this alloy does not have sufficiently high strength properties for highly stressed components.
  • the invention therefore an object of the invention to provide a titanium alloy and a method for processing a titanium alloy, which (s) allows more cost-effective processing.
  • This object is achieved with a titanium alloy containing about 2-4 wt% aluminum, about 4-5.5 wt% vanadium, about 4.0-6.0 wt% molybdenum, about 0, 5 - 1, 5 wt .-% zirconium and about 0.5 - 1, 5 wt .-% tin.
  • This titanium alloy according to the invention is suitable on the one hand for direct processing by means of cold forming without a preceding separate heat treatment, ie immediately after the production of the semifinished product, for example by hot rolling.
  • the above-described cold-formable ⁇ + ⁇ -titanium alloy is also particularly suitable for achieving higher cold-forming rates with simultaneously high strength of the cold-formed component, also for the application of the heat treatment process according to the invention described below.
  • the combination of the thus alloyed ⁇ + ß-titanium alloy with the heat treatment process according to the invention achieves particularly good results in terms of cold workability and strength of the manufactured components.
  • a ⁇ + ⁇ mixed phase structure which is particularly advantageous for the cold workability of the semifinished product and the strength of the component is achieved at room temperature, in particular if the alloy is treated with the heat treatment process according to the invention.
  • Tin and zirconium are neutral substitutional alloying elements and their addition results in efficient solid solution strengthening.
  • the content of tin and zirconium of less than 0.5% does not result in alloy solidification.
  • the optimum content of tin and zirconium in the alloy is 0.5-1.5% of the mass.
  • concentrations lead to an increase in alloy strength due to solid solution strengthening of the a and / or phases, but with virtually no change in the ductility of the alloy.
  • Increasing the content of tin and zirconium significantly above 1.5% of the mass degrades the ductility of the alloy.
  • the titanium alloy has about 0.1-0.4 wt .-% oxygen.
  • This alloying element has been found to be beneficial for the cold ductility and strength of the heat treated titanium alloy proved.
  • Oxygen is a strong stabilizer.
  • An increase in the oxygen content in the alloy results in an increase of the a-phase content and a strong solidification due to the formation of solid interstitial solution.
  • the optimum oxygen content in the alloy is 0.1-0.4% of the mass. Such an oxygen content does not significantly change the ⁇ -phase content (about 3-5%), but allows to increase its strength, and hence the overall strength level, practically without lowering the ductility.
  • the invention is based on the finding that the alloy class known for example from US Pat. No. 5,679,183 does not achieve growth of existing ⁇ particles by its heat treatment, but instead generates new particles which have a fine-lamellar morphology.
  • a bimodal structure formed in this way has an appreciable breaking strength, it does so at the expense of a considerable reduction in ductility.
  • the following heating in the temperature range of / - - Transus minus 250 0 C to / - Transus minus 120 0 C results in the increase of the distributed precipitates and thus an increase of the ductility.
  • the structure remains bimodal, as it consists of a small amount of? Phase and ⁇ phase particles of different morphology (geometrically uniform and lamellar).
  • Such a structure can not provide a starting point for room temperature ductility.
  • the invention is based on the recognition that globular structures have a good combination of strength and ductility. They can be obtained in ( ⁇ + /?) - Titanium alloys after deformation in the two-phase region near the temperature of /? - Transus.
  • the balance of strength and ductility depends on the structural component size. The finer the a-phase precipitates are geometrically uniform, the higher the strength and the lower the ductility will be. A considerable decrease in strength and fracture resistance with a small increase in ductility will occur with very large globular particles of the ⁇ -phase.
  • the heat treatment process according to the invention provides an ⁇ + ⁇ titanium alloy which, on the one hand, has a high ductility and, on the other hand, has a very low degree of solidification upon deformation.
  • the heating of the titanium alloy down to the lower annealing temperature can take place with different heating rates.
  • a slow heating with a heating rate of less than 20 ° per minute is chosen to avoid the formation of stress cracks.
  • Annealing of the titanium alloy preferably occurs in an inert atmosphere to prevent diffusion of embrittling elements (e.g., oxygen, nitrogen, or carbon) into the titanium alloy.
  • the cooling of the titanium alloy to ambient temperature is preferably also carried out in an inert atmosphere.
  • ⁇ + ⁇ -titanium alloys like many metallic materials, are curable by quenching from an annealing temperature. However, this effect is undesirable if a good cold-formable titanium alloy material to be produced.
  • the cooling rate is therefore preferably to be chosen so low that hardening of the titanium alloy is avoided.
  • the titanium alloy is annealed at the lower annealing temperature for more than five hours, in particular for about seven hours.
  • the duration of annealing largely depends on the dimensions of the components to be annealed. Titanium alloy components typically do not have wall thicknesses above 20mm.
  • the annealing time of more than five hours achieved, in particular, for example, in round rods with a diameter of 10 to 20mm, the desired phase composition and thus leads to the desired cold-workable titanium alloy semi-finished product.
  • An annealing temperature of seven hours has proven to be advantageous for reliable reproduction of the result.
  • the process according to the invention can be developed by the following steps before annealing at the lower annealing temperature:
  • the first stage of tempering is chosen at a temperature range of /? - Transus minus 50 0 C to /? - Transus minus 100 0 C.
  • the structure of the alloy is characterized by separate globular particles of the ⁇ -phase, which are arranged at this temperature in a / - matrix. Isothermal holding at this temperature not only provides a solution to the excess (secondary) ⁇ phase and an approximation to the equilibrium state of the ⁇ and / - phases, but also leads to a reduction in structural defects in the course of the realization of a polygonization process , After completion of the isothermal holding the alloy at the temperature / -?
  • Transus minus 16O 0 C to .beta.-transus minus 230 ° C is cooled at a cooling rate of 0:01 to 0:02 ° / s.
  • Such Cooling rate does not allow the formation of new particles of ⁇ -phase from the?-Matrix during cooling, but allows the growth of already existing, primary ⁇ -crystals in the structure. Isothermal holding for 3-6 hours at the second stage of annealing allows completion of the homogenization process. Subsequent cooling to room temperature is carried out at a cooling rate of 2.5-3.5 7s, which is sufficient to prevent precipitation of the secondary ⁇ -phase.
  • the phase composition to be achieved for good cold workability can hereby be further optimized.
  • the upstream annealing steps are again preferably carried out in an inert atmosphere. Again, as before, when cooling the titanium alloy to pay attention to a cooling rate, which avoids stress cracks.
  • this training can be further optimized by the titanium alloy at the upper annealing temperature for more than one hour, in particular for about two hours, annealed.
  • the annealing time depends on the dimensions of the titanium alloy semifinished product. An annealing time of more than one hour, especially two hours, has proven to be reliable for the reproduction of the desired phase composition.
  • the titanium alloy is annealed at the lower annealing temperature more than three hours, preferably three to six, in particular about four hours. Due to the upstream annealing treatment at a higher temperature, the annealing time required for a reliable phase composition to the desired target can be reduced at the lower annealing temperature. More than three hours, especially four hours, have become common dimensions, such as For example, semi-finished in the form of round material in the diameter between 10 to 20mm proved sufficient.
  • the titanium alloy is cooled from the upper annealing temperature in air at a cooling rate of 0.01-0.02 ° C./min to the lower annealing temperature. At this cooling rate, the formation of undesirable phase fractions, internal stresses and the precipitation of alloying elements to an undesirable extent is avoided.
  • the upper annealing temperature is about 770-830 0 C 1, in particular 800 0 C. This temperature range has proven to be practicable for most of the technically common ⁇ + ß-titanium alloys.
  • the process of the present invention can be further developed by cooling the titanium alloy from the lower annealing temperature of air to room temperature at a cooling rate of about 2.5 ° to 3.5 ° C / min. This cooling rate avoids unwanted precipitation of alloying elements as well as unwanted phase formations and achieves an optimum result in terms of the cold workability and the strength of the cold-formed component.
  • the method according to the invention can furthermore be advantageously used if the titanium alloy is processed by a hot rolling method before the heat treatment.
  • the hot rolling process is a process to produce, for example semi-finished profile products or semifinished titanium alloy products.
  • the hot rolling process influences the microstructure.
  • the structure influenced in this way is particularly suitable for the heat treatment steps according to the invention.
  • the lower annealing temperature is about 670-730 0 C, in particular 700 ° C. This annealing temperature has been found to be practicable for most of the commercially used ⁇ + ⁇ -titanium alloys. It is furthermore advantageous for the method according to the invention if the titanium alloy is alloyed with at least one ⁇ -stabilizer and at least one ⁇ -stabilizer. By adding such alloying elements, a titanium alloy can be produced with a proportion of ⁇ -phase and ⁇ -phase optimized for the specific application. The proportions of the stabilizing alloying elements are to be matched to the heat treatment process according to the invention in order to achieve the desired cold workability of the semifinished product and the desired strength of the cold-formed component.
  • the method according to the invention can be further developed by removing a surface layer of the titanium alloy mechanically, in particular by machining, after annealing at the lower annealing temperature and / or after annealing at the upper annealing temperature.
  • the annealing treatment often has some influence on the surface layer of the titanium alloy semi-finished product, even if it is carried out in an inert atmosphere. This influence causes embrittlement and increased crack sensitivity of the semifinished product, which results in lower cold workability and lower strength of the cold-worked component.
  • This disadvantageous effect can be counteracted by removing the affected edge layer of the semifinished product before the cold deformation.
  • a machining production is suitable for this purpose.
  • Another aspect of the invention is the use of a heat treated ⁇ + ⁇ titanium alloy as described above for the production of titanium components by cold working.
  • a heat treated ⁇ + ⁇ titanium alloy as described above for the production of titanium components by cold working.
  • the cost-effective production of large-volume components made of a titanium alloy is possible. This is desirable, for example, for a variety of components in the automotive sector, especially for components that are installed as moving parts in the drive train.
  • the use according to the invention can serve in particular for the production of titanium screws by means of cold heading and / or thread rolling.
  • This use is suitable, for example, for the production of wheel bolts for the automotive sector.
  • the use of titanium alloy wheel bolts has the advantage that, on the one hand, the inertia forces of the wheel are reduced. can be gert and thereby the driving characteristics and the suspension comfort improved and the consumption of the vehicle can be lowered.
  • the use of titanium screws has the further advantage that, especially when used in combination with alloy wheels made of aluminum alloys or magnesium alloys, contact corrosion is avoided, as frequently occurs, for example, when using steel screws.
  • Another aspect of the invention is a method of making titanium screws with the steps
  • titanium bolts achieve and exceed the strength values according to the DIN classification 8.8 and are therefore suitable, for example, for use as wheel bolts.
  • the titanium alloy according to the invention with ⁇ - and ⁇ -phase content is characterized in particular by the fact that the size of the ⁇ -phase particles is about 5-7 ⁇ m.
  • it may preferably contain alloying elements, the one
  • Molybdenum equivalent of [Mo] eq 14-15.
  • the molybdenum equivalent is a value calculated from the type and amount of alloying components and is usually between 0 and 2.5 for ⁇ -titanium alloys, and between 2.5 and 10 for ⁇ + ⁇ -titanium alloys and over 10 for ⁇ -titanium alloys. Particularly preferred embodiments of the invention are described below in the form of exemplary process sequences and alloy compositions.
  • the known alloy Ti - 3.0Al - 4.5V - 5.0Mo is used as the ⁇ + ß-titanium alloy. After the alloy has been produced, a round material, for example 13 mm in diameter, is produced in a hot rolling process. This semi-finished is available in usual lengths.
  • the semi-finished product is subjected to the following heat treatment in an annealing furnace:
  • the semifinished products treated in this way can then be processed further, for example by producing a screw head by means of a cold upsetting process and producing a thread by means of thread rolling at ambient temperature.
  • an edge layer of the semifinished product can be removed by mechanical processing prior to further processing.
  • the alloy was made by double vacuum reflow with sacrificial electrodes. Its chemical composition is as follows: Ti -3.0% Al - 5.0% Mo - 4.5% V - 1, 0% Zr - 1, 0% Sn - 0.25% O (the temperature of /? -Transus is 880 0 C).
  • the obtained ingot with 8kg weight was forged isothermally at a temperature in the range of 90x90mm and then swaged to a height of 45mm. Then the ingot was cut into strips with a rectangular cross section of 45x45mm and forged at a temperature in the ( ⁇ + /?) Area until rods with a diameter of 30mm were obtained. The rods were machined using a lathe until a diameter of 25mm was obtained. The blanks then obtained were rolled to a diameter of 16mm at a temperature range of .beta.-transus minus 50 0 C to ß-lransus minus 100 0 C. The first heating to the predetermined temperature was carried out for 30 minutes. Subsequent heating between trains was for 4 minutes. The total reduction rate was 65%.
  • the 16mm-diameter rod was subjected to heat treatment in the temperature range from 860 to 780 0 C for 2 hours followed by cooling at a cooling rate of 0.02K / s to a temperature of 700 0 C (/? - transus minus 190 0 C) and isothermal hold for 4 hours. Cooling to room temperature was carried out at a cooling rate of 3K / s. The rods were turned to 13mm diameter using a lathe.
  • a 16mm diameter rod was produced by the same method as in the second embodiment. After rolling, the 16mm
  • the rod was then heated to the temperature of 700 0 C (beta-transus minus 19O 0 C) and held for 4 hours. Cooling to room temperature was carried out in air.
  • the rods were turned to 13mm diameter using a lathe.
  • Cooling to the second stage was carried out at a cooling rate of 0.02 degrees / s.
  • Cooling after completion of the heat treatment was carried out at a cooling rate of 3Grad / s.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Forging (AREA)

Abstract

L'invention concerne un procédé de fabrication à froid à faible coût de pièces en alliage de titane. Il est rendu possible par l'utilisation d'un alliage en (a+ß) titane contenant environ 2 à 4,0 % en poids d'aluminium, environ 4 à 5,5 % en poids de vanadium et environ 4,5 à 6,0 % en poids de molybdène, l'ajout d'éléments supplémentaires dans l'alliage, constitués d'environ 0,5 à 1,5 % en poids de zirconium et d'environ 0,5 à 1,5 % en poids d'étain, permettant d'obtenir une formabilité à froid de la pièce finie présentant une solidité adéquate. La formabilité à froid est obtenue selon l'invention par un procédé de traitement à chaud, ledit procédé comprenant les étapes suivantes : recuire l'alliage de titane à une température de recuit inférieure comprise entre 160 et 230 °C sous la température de transformation (transition bêta) et refroidir l'alliage de titane à température ambiante. L'alliage de titane est de préférence recuit au préalable à une température de recuit supérieure comprise entre 50 et 100 °C sous la température de transformation (transition bêta).
EP06806675A 2005-11-03 2006-11-03 Alliage de ti forme a froid Not-in-force EP1945827B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200510052918 DE102005052918A1 (de) 2005-11-03 2005-11-03 Kaltverformbare Ti-Legierung
PCT/EP2006/010569 WO2007051637A1 (fr) 2005-11-03 2006-11-03 Alliage de ti forme a froid

Publications (2)

Publication Number Publication Date
EP1945827A1 true EP1945827A1 (fr) 2008-07-23
EP1945827B1 EP1945827B1 (fr) 2012-05-30

Family

ID=37556272

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06806675A Not-in-force EP1945827B1 (fr) 2005-11-03 2006-11-03 Alliage de ti forme a froid

Country Status (5)

Country Link
EP (1) EP1945827B1 (fr)
JP (1) JP5210874B2 (fr)
DE (1) DE102005052918A1 (fr)
ES (1) ES2387684T3 (fr)
WO (1) WO2007051637A1 (fr)

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CN108893631B (zh) * 2018-08-03 2020-11-13 燕山大学 一种高强钛合金及其制备方法
CN110396622A (zh) * 2019-07-30 2019-11-01 中国船舶重工集团公司第七二五研究所 一种中强超高韧性钛合金及其制备方法

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Also Published As

Publication number Publication date
DE102005052918A1 (de) 2007-05-16
JP2009515047A (ja) 2009-04-09
WO2007051637A1 (fr) 2007-05-10
EP1945827B1 (fr) 2012-05-30
ES2387684T3 (es) 2012-09-28
JP5210874B2 (ja) 2013-06-12

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