WO2012146650A1 - Alliage pour élément de roulement - Google Patents

Alliage pour élément de roulement Download PDF

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Publication number
WO2012146650A1
WO2012146650A1 PCT/EP2012/057628 EP2012057628W WO2012146650A1 WO 2012146650 A1 WO2012146650 A1 WO 2012146650A1 EP 2012057628 W EP2012057628 W EP 2012057628W WO 2012146650 A1 WO2012146650 A1 WO 2012146650A1
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alloy
temperature
ageing
titanium alloy
phase
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Alexander De Vries
Alejandro Sanz
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SKF AB
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SKF AB
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Priority to EP12718952.0A priority Critical patent/EP2702181B1/fr
Priority to US14/114,628 priority patent/US20140185977A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/30—Parts of ball or roller bearings
    • F16C33/58—Raceways; Race rings
    • F16C33/62—Selection of substances
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C2204/00—Metallic materials; Alloys
    • F16C2204/40—Alloys based on refractory metals
    • F16C2204/42—Alloys based on titanium

Definitions

  • the present invention relates to the field of bearings. More specifically, the present invention relates to a novel titanium alloy for a bearing component, a method of
  • Rolling element bearings comprise inner and outer raceways and a plurality of rolling elements (balls or rollers) disposed therebetween.
  • the bearing components are typically manufactured from a bearing steel.
  • Titanium and its alloys exhibit a low density relative to many other structural metals and alloys, excellent corrosion resistance and high specific proof strengths (strength/density).
  • Alloying elements are classified by whether they stabilise the a (low temperature, hep) or ⁇ (high temperature, bec) crystal forms, o stabilisers, such as aluminium and tin, are typically added in order to increase the creep resistance of a titanium alloy.
  • ⁇ -stabilisers such as vanadium, molybdenum and zirconium, are typically added to increase the strength.
  • JP 1 1 153140 describes a titanium alloy comprising from 1 .0 to 5.0 wt% Cr and the balance Ti. After a' martensite quenching this alloy has high hardness and is used for manufacturing bearing rings. However, this alloy has a low thermal stability due to the presence of 80% metastable a'-martensite, which is problematic since bearings often experience heating during use.
  • US 2004/0231756 describes a titanium alloy comprising from 3.2 to 4.2 wt% Al, from 1 .7 to 2.3 wt% Sn, from 2.0 to 2.6 wt% Zr, from 2.9 to 3.5 wt% Cr, from 2.3 to 2.9 wt% Mo, from 2.0 to 2.6 wt% V, from 0.25 to 0.75 wt% Fe, from 0.01 to 0.08 Si, 0.21 wt% or less O, and the balance Ti. After heat treatment this alloy exhibits both high strength and high ductility. However, since the ductility is so high, the alloy is unable to withstand high contact stresses.
  • CF rolling contact fatigue
  • the present invention provides a titanium alloy for a bearing component comprising:
  • the alloy comprises from 5 to 7 wt% Al, preferably from 5.5 to 6.7 wt% Al, more preferably from 6 to 6.5 wt% Al, still more preferably about 6.4 wt% Al. In combination with the other alloying elements, this provides the desired mechanical properties of the alloy, particularly strength. Higher levels of Al may lead to abrupt decreasing of the alloy's deformability. In addition, for higher Al levels, a 2 -phase (intermetallic compound Ti 3 AI) may be precipitated during heat treatment, which can result in embrittlement of the alloy.
  • the alloy comprises from 3.5 to 4.5 wt% V, preferably from 3.7 to 4.3 wt% V, more preferably from 3.8 to 4.1 wt% V, still more preferably about 4.3 wt% V.
  • V serves to obtain a single-phase ⁇ -condition in the alloy after quenching.
  • V has good solubility not only in the ⁇ phase but also in the a phase.
  • V does not decrease the plasticity of the alloy as strongly as other ⁇ - stabilising elements.
  • the alloy comprises from 0.5 to 1 .5 wt% Mo, preferably from 0.7 to 1.3 wt% Mo, more preferably from 0.9 to 1 .2 wt% Mo, still more preferably about 1.1 wt% Mo. Mo in this amount serves to obtain a single-phase ⁇ -condition in the alloy after quenching and also increases the strength of the alloy.
  • the alloy comprises from 2.5 to 4.5 wt% Fe, preferably from 3 to 4.3 wt% Fe, more preferably from 3.4 to 4.2 wt% Fe, still more preferably about 4.1 wt% Fe.
  • Fe provides solid solution strengthening.
  • higher levels of Fe can reduce the fabricability of the alloy.
  • higher levels of Fe may result in eutectoid
  • the alloy comprises from 0.05 to 2 wt% Cr, preferably from 0.06 to 1.5 wt% Cr, more preferably from 0.07 to 1.2 wt% Cr, still more preferably about 0.07 wt% Cr.
  • Cr As a ⁇ -eutectoid stabiliser, Cr provided a similar effect to Fe, albeit with the precipitation of TiCr 2 at higher Cr levels.
  • the alloy optionally contains up to 2.5 wt% Zr.
  • the alloy may contain from 1 to 2.5 wt% Zr, preferably from 1 .5 to 2.4 wt% Zr, more preferably from 1.7 to 2.2 wt% Zr, still more preferably about 2.4 wt% Zr.
  • the alloy optionally contains up to 2.5 wt% Sn.
  • the alloy may contain from 1 .5 to 2.5 wt% Sn, preferably from 1 .7 to 2.4 wt% Sn, more preferably from 1 .9 to 2.3 wt% Sn, still more preferably about 2.5 wt% Sn.
  • Zr and Sn are substitution neutral alloying elements and their addition in the above amounts, when combined with the other alloying elements, results in solid solution strengthening of the alloy.
  • the alloy optionally contains up to 0.5 wt% C.
  • the alloy may contain from 0.01 to 0.5 wt% C, preferably from 0.015 to 0.35 wt% C, more preferably from 0.018 to 0.2 wt% C, still more preferably about 0.02 wt% C.
  • the presence of C leads to significant a-phase strengthening due to the formation of interstitial solid solution. Higher levels of C reduce the ductility of the alloy.
  • Ti forms the balance of the composition, together with any unavoidable impurities.
  • the alloy for the bearing component comprises:
  • the titanium alloys according to the present invention advantageously exhibit at least one of high hardness and high resistance to rolling contact fatigue.
  • the chemical composition of the alloys according to the present invention should be such that the molybdenum equivalent [Mo] eq is from 10 to 12.
  • [Mo]eq values of 10 or above increase the hardness of the alloy. If [Mo] eq is less than 10, martensite a" will be formed during quenching, and its further decomposition will not give the necessary increase in hardness. Higher values of [Mo] eq will result in a considerable increase in hardness during decomposition of ⁇ -phase. However, such an increase in hardness will only be provided after a long ageing time, typically from 50 to 100 hours.
  • microchemical non-uniformity of the distribution of alloying elements is common for these ⁇ -alloys. Therefore, a-phase precipitation occurs in a non uniform fashion throughout the volume, for example in one ⁇ -grain this process has already started and in a neighbouring one it has not. In that case, two neighbouring grains will have different levels of hardness.
  • the titanium alloy according to the present invention may contain unavoidable impurities, although, in total, these are unlikely to exceed 0.5 wt.%.
  • the alloy contains unavoidable impurities in an amount of not more than 0.3 wt.%, more preferably not more than 0.1 wt.%.
  • the microstructure of the alloy preferably comprises ⁇ -phase grains having precipitates of o phase dispersed therein.
  • the microstructure is preferably essentially homogeneous.
  • the microstructure and resulting mechanical properties lead to high hardness and/or improved rolling contact fatigue performance in a bearing component formed of the alloy.
  • the alloy according to the present invention preferably has a Rockwell hardness (ASTM E 18-02) of at least 48 HRC, more preferably at least 50 HRC, even more preferably at least 52 HRC. Such hardness levels make the alloy particularly suitable for use in a bearing component.
  • the alloy according to the present invention may consist essentially of the recited elements. In addition to those elements that are mandatory, additional non-specified elements may be present in the alloy provided that the essential characteristics of the alloy are not materially affected by their presence.
  • the present invention provides a bearing component formed from a titanium alloy as herein described.
  • the bearing component can be at least one of a rolling element (for example a ball or roller element), an inner ring, and an outer ring.
  • the bearing component could also be part of a linear bearing such as ball and roller screws.
  • the titanium alloy as herein described is particularly suitable for forming an inner ring and/or an outer ring of a bearing.
  • the present invention provides a bearing comprising a bearing component as herein described.
  • a bearing may be used in many different types of machinery to retain and support rotating components. Since the titanium alloys as herein described exhibit low density relative to other structural metals and alloys, excellent corrosion resistance and high specific proof strengths (strength/density), such bearings are particularly suited for use in machinery in which there is a desire to reduce the moving mass, for example racing cars and aeroplanes.
  • the bearing comprises an inner ring and/or an outer ring formed from the titanium alloy as herein described.
  • the rolling elements may be formed from bearing steel or ceramic.
  • the present invention provides a method for the manufacture of a titanium alloy for a bearing component, the process comprising:
  • the temperature T p is the temperature at which the microstructure of the alloy changes from one comprising both the a-phase and ⁇ -phase to essentially only the ⁇ -phase.
  • the alloy composition is preferably worked before being quenched.
  • the working is preferably carried out by rolling.
  • the alloy is provided with a generally homogeneous microstructure comprising large initial ⁇ -phase grains in which are dispersed a-phase precipitates in the form of plates.
  • Such a microstructure provides the alloy with the desired levels of hardness and/or resistance to rolling contact fatigue.
  • the rolling may comprise multiple rolling stages with intermediate annealing stages. Such stages may help to provide the final alloy with the desired microstructure.
  • the temperature T below the (a+3/3)-transition temperature T p is preferably above the (a/ a+3)-transition temperature T Q , i.e. above the temperature at which the microstructure changes from ophase-only to a microstructure comprising both a-phase and ⁇ -phase.
  • the temperature T below the (a+3/3)-transition temperature T p is such that:
  • T about T p - 15 °C.
  • the temperature T is less than 1000 °C, preferably from 800 to 950 °C, more preferably from 820 to 900 °C, more preferably from 835 to 860 °C, still more preferably about 845 °C. These values of temperature T provide the alloy with high hardness and/or resistance to rolling contact fatigue after ageing.
  • Quenching is preferably carried out in water, more preferably agitated water.
  • the quenching is carried out at a rate of at least 20 °C/s, more preferably at least 25 °C/s, still more preferably at about 30 °C/s.
  • the cooling rate of such quenching is suitable for providing the quenched alloy with the desired microstructure.
  • the quenching is carried out down to a temperature lower than 200 °C, more preferably to 60°C or lower, still more preferably to about room temperature.
  • the alloy preferably has a microstructure comprising from 5 to 30 vol% o phase, more preferably form 5 to 20 vol% a-phase, preferably form 10 to 15 vol% a-phase. This provides the alloy with high hardness and/or resistance to rolling contact fatigue after ageing.
  • the ⁇ -phase therefore typically makes up from 70 to 95 vol% of the microstructure, more typically from 80 to 95 vol%, still more typically from 85 to 90 vol%.
  • the ageing is carried out at a temperature of from 415 to 575 °C, more preferably from 425 to 525 °C. Ageing at these temperatures increases the hardness of the alloy.
  • the ageing is carried out for up to 60 hours, more preferably up to 35 hours, more preferably up to 20 hours, still more preferably from 1 to 15 hours.
  • This provides the alloy with increased hardness. Ageing for greater lengths of time is not cost effective and may also result in the alloy becoming brittle.
  • the ageing is preferably carried out in an inert atmosphere, more preferably argon or a vacuum. This avoids any undesired reactions of the alloy with the atmosphere, such as oxidation.
  • the alloy may be cooled, preferably in an inert atmosphere, until it reaches a temperature of 200 °C or less. This avoids any undesired reaction of the aged alloy in air.
  • the alloy may be cooled at a rate of at least 1 °C/s, preferably from 2 to 10 °C/s, more preferably at about 3 °C/s. Such cooling helps to provide the desired
  • the present invention provides a method of forming a bearing component as herein described, the method comprising: (I) providing an alloy composition as herein described;
  • the ageing step increases the hardness of the alloy. Therefore, the alloy is more easily machined if the machining is carried out between the quenching step and the ageing step.
  • the bearing component is preferably an inner or outer ring component.
  • the bearing component is preferably machined to remove a layer not less than 30 ⁇ in depth, more typically not less than 50 ⁇ . For example, a layer from 50 ⁇ to 100 ⁇ in depth. This ensures that the outer layer enriched with oxygen (and therefore having higher brittleness) is removed.
  • Titanium alloys have a high susceptibility to oxidation, which is increased by having a high ⁇ -phase volume fraction. Since the alloys of the present invention are pseudo- ⁇ titanium alloys having more than 50% ⁇ -phase after annealing, the oxygen enriched outer layer of these alloys is typically up to 50 ⁇ thick.
  • Figure 1 shows a micrograph (a) and hardness distribution along a section (b) of ⁇ -6.4 ⁇ - 4.1 Fe-1.1 Mo-4.3V-2.5Sn-2.4Zr 0 47 alloy mm rod after rolling in the ⁇ -range.
  • Figure 2 shows a micrograph (a) and hardness distribution along a section (b) of ⁇ -6.4 ⁇ - 4.1 Fe-1.1 Mo-4.3V-2.5Sn-2.4Zr 0 22 alloy mm rod after rolling in the (a+P)-range.
  • Figure 3 shows a micrograph (a) and hardness distribution along a section (b) of ⁇ -6.4 ⁇ - 4.1 Fe-1.1 Mo-4.3V-2.5Sn-2.4Zr alloy 0 14 mm rod after rolling in the (a+P)-range.
  • Figure 4 shows micrographs of samples cut from ⁇ -6.4 ⁇ -4.1 Fe-1.1 Mo-4.3V-2.5Sn-2.4Zr alloy rods with 0 20 mm (a, b) and 14 mm (c, d) after quenching from 850°C.
  • Figure 5 shows micrographs of samples 0 20 (a) and 14 (b) mm from Ti-6.4AI-4.1 Fe-1.1 Mo- 4.3V-2.5Sn-2.4Zr alloy after quenching from 850°C and ageing at 475°C for 25 hours.
  • Figure 6 shows micrographs of Ti-6AI-4V-1 Mo-1 Cr-3.5Fe-2Sn-2Zr (a) and Ti-6AI-4V-1 Mo- 1 Cr-3.5Fe-2Sn-2Zr-0.15C (b) after casting.
  • Figure 7 shows micrographs of samples of Ti-6AI-4V-1 Mo-1 Cr-3.5Fe (a), Ti-6AI-4V-1 Mo- 1 Cr-3.5Fe-2Sn-2Zr (b) and Ti-6AI-4V-1 Mo-1 Cr-3.5Fe-2Sn-2Zr-0.15C (c) after forging.
  • Figure 8 shows micrographs of Ti-6AI-4V-1 Mo-1 Cr-3.5Fe after quenching from the ⁇ -area (a), and Ti-6AI-4V-1 Mo-1 Cr-3.5Fe, Ti-6AI-4V-1 Mo-1 Cr-3.5Fe-2Sn-2Zr and Ti-6AI-4V-1 Mo- 1 Cr-3.5Fe-2Sn-2Zr-0.15C after quenching from the (a+3)-area (b, c, d, respectively).
  • Figure 9 shows micrographs of Ti-6AI-4V-1 Mo-1 Cr-3.5Fe (a) and Ti-6AI-4V-1 Mo-1 Cr-3.5Fe- 2Sn-2Zr (b) after ageing at 500 °C for 6 hours.
  • Figure 10 shows micrographs of Ti-6AI-4V-1 Mo-3.5Fe-1 Cr-2Zr-2Sn alloy samples after hot rolling (a) and after additional ageing at 500 °C for 30 hours (b).
  • Figure 1 1 shows micrographs of Ti-6AI-4V-1 Mo-3.5Fe-1 Cr-2Zr-2Sn alloy samples after quenching from 860 °C (a), 855 °C (b), 845 °C (c, d), 830 °C (e) and 800 °C (f).
  • Figure 12 shows the cutting plan for cutting samples from semiproducts for measurements of the hardness at specific depths, and the corresponding hardness values.
  • a 20 kg ingot having the chemical composition Ti-6.4AI-4.1 Fe-1.1 Mo-4.3V-0.07Cr-2.5Sn- 2.4Zr-0.02C was prepared in a vacuum arc furnace with consumable electrode by double remelting. Titanium sponge TG-120 was used to make the electrode. Due to its high melting point, Mo was introduced into the alloy via the ligature AMBTi (32%V-36.8%Mo-14%AI- 0.39%Fe-0.23%Si), rather than in pure form which may lead to the formation of inclusions. V, Fe and Al were partly introduced via ligature and partly in pure form. Zr and Sn were introduced into the alloy in pure form only.
  • Titanium sponge was mixed with ligature and pure elements, which were in the form of small metal pieces or turnings.
  • the resultant mixture was pressed into a matrix using a 2000-ton press.
  • the pressed electrode was melted in a copper crystallizer with diameter 0 125 mm and as a result the ingot of the first remelt was obtained.
  • This ingot was then remelted for the second time in a crystallizer with diameter 0 150 mm at current intensity 2000 A, electric voltage 30 B and vacuum level 5x10 "2 millimeters of mercury (6.7 Pa).
  • Chemical analysis certified by TUV has shown that the chemical composition of the alloy corresponds to that of Ti-6.4AI-4.1 Fe-1.1 Mo-4.3V-
  • the ingot was rolled on a screw-shaped rolling press at a temperature of about 1050°C (corresponding to the ⁇ -range) from a diameter of 140 mm to a diameter of 0 55 mm in one gate, and then machined to a diameter of 0 47 mm for the removal of cinder and a-modified layers.
  • the rod's microstructure after rolling in the ⁇ -range was
  • rods with diameter 0 22 mm were then used for sample production (herein Rolf Samples).
  • Rods with a diameter of 0 20 mm were then rolled to 014 mm in one gate on a screw-shaped rolling mill also at a temperature of about 850°C. Additional deformation and dynamic
  • the starting semiproducts especially the rod with diameter 0 14 mm, exhibited high hardness values. Accordingly, an attempt was made to obtain the desired hardness level (preferably ⁇ 52 HRC) by ageing the hot-rolled semiproducts without intermediate quenching. However a significant increase in hardness was not observed.
  • the hardness of the 0 14 mm rod increased on average by 1 unit, while that of the 0 20 mm rod increased on average by about 5-6 HRC units. However, the increase in hardness was not sufficient.
  • the polymorphic transformation temperature ⁇ ⁇ the temperature of the (a+P)/p-transition, was determined for the new alloy using a trial quenching method. Samples were quenched in water in temperature intervals of about 20°C between about 800-960°C. With the use of metallographic and X-ray analysis it was shown that for the alloy investigated the polymorphic transformation temperature ⁇ ⁇ was equal to about 880°C. Therefore, the quenching temperature was chosen to be about 850°C.
  • samples cut from rods 0 14 mm and 20 mm have practically identical microstructures consisting of small amounts of a-phase and ⁇ -phase (see Figure 4).
  • the hardness of these rods also was similar and equal to about 36-37 HRC.
  • the primary a-phase In samples with diameter 0 14 mm, the primary a-phase has a predominantly globular shape (see Figure 4c, d), while in ones with diameter 0 20 mm the primary a-phase has a predominantly lamellar shape (see Figure 4 a, b).
  • the difference in primary a-phase morphology is explained by the difference in the degree of deformation during the manufacturing of the semiproducts. However, investigations have shown that this difference does not have significant effect on the subsequent strengthening.
  • Table 1 Hardness of samples of Ti-6.4AI-4.1 Fe-1.1 Mo-4.3V-2.5Sn-2.4Zr alloy after ageing at 530°C and 500°C for various lengths of time
  • the ageing temperature determines the diffusive mobility of the alloying element atoms, as well as the rate of nucleation and growth of secondary a-phase particles.
  • the higher the ageing temperature the higher the diffusive mobility of the atoms and, therefore, the more rapidly the precipitation process begins and finishes.
  • growth rate predominates over nucleation rate and therefore the precipitated a-phase particles will be larger. Consequently, the level of strengthening will be lower.
  • the precipitation process at about 530°C is complete after about 8-10 hours (see Table 1 ), but the required hardness is not achieved.
  • ageing at about 500°C the precipitation process is complete after 18 hours. It is noted that the lowest required hardness level is obtained on the 0 14 mm rod.
  • the ageing temperature was decreased to about 475°C. While this required an ageing time of about 25-27 hours, a hardness of about 53-54 HRC was obtained (see Table 2).
  • the rings were assembled into bearings with a polymer L-shaped cage and ceramic balls.
  • the rolling contact fatigue characteristics of the bearings were investigated under the following conditions:
  • Test rig TLE G19.08 (R2)
  • any "suspended" test is a successful one, i.e. it is suspended without failure or spalling.
  • the Polymet Samples feature a longer bar than the Rolf Samples.
  • the Polymet Samples are in contact with two rotating discs of hardened steel (AISI 52100 at 62 HRc).
  • AISI 52100 at 62 HRc two rotating discs of hardened steel
  • the resulting ingots had a height of approximately 14 mm and a diameter of approximately 40 mm.
  • Visual inspection of the ingots and analysis of their microstructures allowed selection of three alloy compositions for further investigation. Structures of alloys containing more than 4.5% ⁇ -eutectoid stabilizers had a large microchemical heterogeneity, which was difficult to eliminate by homogenization annealing. This phenomenon is very widespread for alloys containing a large quantity of ⁇ -eutectoid stabilisers (therefore their typical content does not exceed 4.4-5% in ⁇ -titanium alloys). It was not possible to eliminate microchemical heterogeneity under fivefold remelting.
  • Alloy 1 Ti-6A1 -4V-1 Mo-1 Cr-3.5Fe (basic alloy)
  • Alloy 2 Ti-6A1 -4V-1 Mo-1 Cr-3.5Fe-2Sn-2Zr
  • Alloy 3 Ti-6A1 -4V-1 Mo-1 Cr-3.5Fe-2Sn-2Zr-0.15C
  • the cast structure of these alloys is uniform and characterized by large ⁇ -grains and fine particles of a-phase precipitating from the ⁇ -phase during cooling of the ingots to room temperature ( Figure 6).
  • the amount of a-phase precipitation depends on the chemical composition of an alloy.
  • a rather large amount of a-phase is precipitated in the Ti-6A1 -4V-1 Mo-1 Cr-3.5Fe alloy (not shown).
  • Sn and Zr Alloy 2 results in stabilisation of the ⁇ -phase and reduction of the critical cooling rate (rate under cooling with which the diffusion of component atoms is suppressed).
  • Alloy 2 has a minimal hardness because in this case the hardness is caused by solid solution strengthening of the ⁇ -phase.
  • the higher values of hardness are caused by precipitated a-phase particles.
  • smaller particles give higher hardness.
  • Ingots of the three chosen compositions were divided in half and were then forged at about 900°C. On average the initial blanks were approximately 20 x 14mm in cross-section. They were then deformed to obtain a square cross section. The final size of samples with approximate section 12 x 1 1 mm and length 100 mm were obtained by forging in the longitudinal direction. The reduction ratio was about 2, which is determined as a ratio of the cross sectional area before and after deformation. This indicates than during forging the materials was deformed to only a small degree.
  • the obtained 100 mm billets were cut up into samples with heights of 1 to 15 mm for conducting structure studies in the initial state and after extra thermal treatment, and also hardness measurements.
  • Microstructures of Alloys 1 , 2 and 3 after forging are represented in Figure 7. It can be seen that, in particular for Alloys 1 and 3, the deformation degree during forging was small and that in the two-phase (a+3)-area the sample structure was similar to the structure of the cast alloys (see, for example, Figures 6b and 7c for Alloy 3). The main difference concerns alloy 2. In the cast state, it has almost only ⁇ -phase in the structure ( Figure 6a), whereas after forging its structure changes (Figure 7b) and becomes similar to the structure of Alloy 1 ( Figure 7a). However, because of additional alloying by Zr and Sn, which reduces the critical cooling rate, Alloy 2 is characterized by more disperse precipitations of a-phase after forging (Figure 7b).
  • the temperatures of the ⁇ + ⁇ / ⁇ transformation (T p ) for each of alloys 1 , 2 and 3 were determined using test quenches. For Alloy 1 , it was about 940°C, for Alloy 2 it was about 900°C, and for Alloy 3 it was aboutl 000°C. A part of each sample was quenched from the ⁇ - area, and a part was quenched from the ( ⁇ + ⁇ )- area from temperatures 50° below T p , namely 890°, 850° and 950°C for Alloys 1 , 2 and 3, respectively. All alloys quenched from the ⁇ -area had the same structure consisting of ⁇ -grains (Figure 8a), and after quenching from the (c ⁇ )-area the structure was almost the same as in the state after forging ( Figure 8).
  • the hardness of alloys after quenching depends on the heating temperature. After quenching from the ⁇ -area, hardness is minimal and it is determined only by the alloying level of the solid solution, which is increased from Alloy 1 to Alloy 3 (see Table 6). After quenching from the (c ⁇ )-area, hardness is also determined by the degree of dispersion of primary a-phase particles.
  • Table 6 Hardness of pilot titanium alloys after quenching in ⁇ - and ( ⁇ + ⁇ )- areas Since the cooling rate under quenching is faster than the cooling rate after forging, the alloying level of ⁇ -phase will be different: the higher the heating temperature and cooling rate, the lower the alloying level of ⁇ -phase will be and all of the conditions being equal, the effect of strengthening should be greater.
  • the alloying level of ⁇ -phase could be estimated by the change of its lattice parameter calculated from X-ray analysis data. Values of a p are given in Table 7.
  • Table 7 Change of lattice spacing ⁇ -phase (a p ) in different states It can be seen from the data presented in the Table 7 that a minimum alloying level of ⁇ - phase corresponds to quenching from the ⁇ -area, and maximum alloying levels correspond to the state after forging. Based on the alloying level of ⁇ -phase for the same alloy, one can indirectly estimate the amount of a-phase in the structure. The smaller the a p lattice parameter, the more a-phase in the structure. In other words, there is more a-phase in the forging state in the structure, which is a reason for the higher values of hardness (see Tables 5 and 6). Of course, higher hardness after forging is also caused by deformation
  • Samples of Alloys 1 and 2 were quenched from the (a+&)-area and aged at about 500°C for about 6 hours. The structure of these samples is represented in Figure 9 (a, b). Samples of Alloys 1 and 2 have hardnesses of 52-52.5 HRC. Hardness measurements were carried out on a Vickers hardness testing machine with a load of 30 kg, and were then converted into units of HRC in a conventional manner. Hardness is connected with precipitation of very dispersed a-phase, which provides a grey background in the microstructure images ( Figure 9). Dispersed precipitations not only increase material hardness but they also create a high level of stresses. Measuring the hardness of such samples using a diamond cone with a load of 150 kg caused destruction.
  • Forged semiproducts were prepared having the composition set out in Table 9 below.
  • the Forged semiproducts were cut into billets 120x12x40 mm size.
  • a number of billets were cut into small samples 15x15x20 mm size for further investigation.
  • microstructure of the semiproduct after hot rolling was investigated (see Figure 10a).
  • This microstructure comprises large initial ⁇ -grains with dispersive a-phase particles formed during hot deformation and subsequent cooling to room temperature.
  • the hot-rolled semiproduct had a relatively high hardness of 43-44 HRC. Following low- temperature ageing the hardness only increased up to 47 HRC (see Figure 10b), in spite of the fact that plastic deformation increases the crystalline defects density, which should contribute to hardening. Such low hardness values are explained by a rather large amount of primary a-phase after rolling.
  • T p ⁇ - transition temperature
  • the Ti-6A1 -4V-1 Mo-3.5 Fe-1 Cr-2Zr-2Sn alloy belongs to the pseudo- ⁇ group of titanium alloys. This group is characterized by micro-chemical heterogeneity inside ⁇ -phase grains, i.e. there is some difference in chemical composition in adjoining ⁇ -grains. This is why reducing the temperature down to about 855°C results in heterogeneous microstructure formation: some grains are presented by ⁇ -phase only while others also contain primary a-phase (see Figure 1 1 b). Heat treatment at about 845°C results in a rather homogeneous microstructure which contains around 10-15 vol% primary a-phase (see Figures 1 1 c, d). Reducing the temperature to about 830°C or less leads to an increase in a-phase (see Figures 1 1 e, f). The hardness characteristics after quenching relate to the quantity of primary a-phase (see Table 10).
  • a single-phase ⁇ -microstructure after quenching provides only minimal levels of hardness (32 HRC).
  • Heterogeneous microstructure formation quenching from 855°C causes the hardness to fluctuate between 32 and 36 HRC. Reducing the quenching temperature leads to a gradual increase in hardness, which is explained by an increase in the amount of primary a-phase (see Table 10).
  • the level of hardness obtained did not exceed 49 HRC.
  • ageing for more than 120 hours at the chosen temperatures results in abrupt material brittleness: hardness indentation causes the appearance of small cracks on the surface. It appears that the a-phase, which is formed during low-temperature ageing, has a semicoherent boundary with the matrix, which results in high internal stresses.
  • Table 1 1 Influence of ageing temperature and its duration on Ti-6A1 -4V-1 Mo-3.5 Fe-1 Cr- 2Zr-2Sn alloy hardness Ageing at 525°C also does not provide the optimum result due to an increase of diffusion processes. As a result, a-phase particles have a larger size in comparison with ones which are formed at lower temperatures. The results indicate that the optimum ageing temperature is approximately 500°C. Ageing at this temperature for up to 30 hours resulted in hardness values of 52 HRC for the samples that were previously quenched from 845°C (see Table 1 1 ).
  • the results indicate that particularly high hardness levels can be achieved by quenching from a temperature that is 15-20°C lower than T p .
  • a quench typically provides 10-15% volume fracture of primary a-phase in the microstructure.
  • Quenching from temperatures that are lower than T p allows partial retention of crystalline defects (for example dislocations) accumulated during plastic deformation and in this way contributes to strengthening of the alloy after subsequent ageing.
  • the presence of a small quantity of a-phase particles allows partial retention of the toughness and the prevention of spontaneous crack formation.
  • Samples of Ti6A1-4V-1 Mo-3.5 Fe-1 Cr-2Zr-2Sn alloy after quenching have average levels of strength and ductility, whereas after aging they have high strength and practically zero ductility.
  • the alloys were compared with steels used for bearings manufacturing (Indian alloy Fe-1.0C- 0.25Si-0.3Mn-1.45Cr). After quenching and annealing, steel has higher hardness (61-64 HRC) and strength (2100 MPa) level, but the impact toughness of bearing steel (50 kJ/m 2 ) is rather close to that of the titanium alloy of the present invention (42 kJ/m 2 ).
  • Fracture surfaces of destroyed samples were studied. Large facets caused by intergranular failure were observed on the fracture surface of quenched samples. However, it should be noted that all facets have tracks of micro plastic deformation, which can be concluded from their pit structure. Secondary cracks formation as well as flat facets with small pits could also be observed on the fracture surfaces.
  • the fracture surface of quenched and subsequently aged samples has a brittle character of failure.
  • the fracture surface is also characterised by facets having feebly marked relief. Secondary cracks were almost not observed. Some facets have "river” features, while others have dispersive pit destruction due to precipitation of dispersive a-phase particles inside the grains.
  • Bearing rings are typically manufactured from quenched material when its hardness is not too high. To achieve the required hardness level (preferably ⁇ 52 HRC) it is desirable to conduct ageing at about 500°C for up to about 30 hours.
  • Titanium alloys have high oxidation susceptibility.
  • increasing the volume fraction of ⁇ -phase results in intensification of the oxidation processes.
  • This layer was revealed to be about 50 microns thick, as indicated by a drop in harness of from around 6000 MPa at the surface to around 4000 MPa at a depth of 50 microns, after which the hardness remained fairly constant down to 200 microns in depth. Accordingly, final machining of the rings after ageing should preferably remove a layer not less than about 50 microns in depth.

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Abstract

L'invention concerne un alliage en titane pour élément de roulement comprenant: (a) 5 à 7 % en poids d'Al, (b) 3,5 à 4,5 % en poids de V, (c) 0,5 à 1,5 % en poids de Mo, (d) 2,5 à 4,5 % en poids de Fe, (e) 0,05 à 2 % en poids de Cr, (f) et éventuellement un ou plusieurs des éléments suivants: jusqu'à 2,5 % en poids de Zr, jusqu'à 2,5 % en poids de Sn, et 0,01 à 0,5 % en poids de C, (g) le solde étant constitué de Ti ainsi que d'inévitables impuretés.
PCT/EP2012/057628 2003-06-24 2012-04-26 Alliage pour élément de roulement Ceased WO2012146650A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012146653A3 (fr) * 2011-04-29 2013-11-21 Aktiebolaget Skf Traitement thermique d'un alliage pour élément de roulement
CN108004431A (zh) * 2017-12-14 2018-05-08 西北有色金属研究院 一种可冷成型的高强高塑β钛合金材料
CN110106395A (zh) * 2019-05-29 2019-08-09 西北有色金属研究院 一种海洋工程用高强高韧可焊接钛合金

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01115314A (ja) 1987-10-29 1989-05-08 Katsuya Inada 炊飯器のしゃもじに御飯粒が残らない炊飯器の内釜
EP1225353A1 (fr) * 2000-07-18 2002-07-24 Nsk Ltd., Appareil roulant
US20040231756A1 (en) 2003-05-22 2004-11-25 Bania Paul J. High strength titanium alloy
EP1582756A2 (fr) * 2004-03-31 2005-10-05 Minebea Co., Ltd. Palier spérique à surface de contact du type métal sur métal

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01115314A (ja) 1987-10-29 1989-05-08 Katsuya Inada 炊飯器のしゃもじに御飯粒が残らない炊飯器の内釜
EP1225353A1 (fr) * 2000-07-18 2002-07-24 Nsk Ltd., Appareil roulant
US20040231756A1 (en) 2003-05-22 2004-11-25 Bania Paul J. High strength titanium alloy
EP1582756A2 (fr) * 2004-03-31 2005-10-05 Minebea Co., Ltd. Palier spérique à surface de contact du type métal sur métal

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012146653A3 (fr) * 2011-04-29 2013-11-21 Aktiebolaget Skf Traitement thermique d'un alliage pour élément de roulement
US9732408B2 (en) 2011-04-29 2017-08-15 Aktiebolaget Skf Heat-treatment of an alloy for a bearing component
CN108004431A (zh) * 2017-12-14 2018-05-08 西北有色金属研究院 一种可冷成型的高强高塑β钛合金材料
CN110106395A (zh) * 2019-05-29 2019-08-09 西北有色金属研究院 一种海洋工程用高强高韧可焊接钛合金

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