WO2005098064A2 - Β titanium compositions and methods of manufacture thereof - Google Patents
Β titanium compositions and methods of manufacture thereof Download PDFInfo
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- WO2005098064A2 WO2005098064A2 PCT/US2005/000569 US2005000569W WO2005098064A2 WO 2005098064 A2 WO2005098064 A2 WO 2005098064A2 US 2005000569 W US2005000569 W US 2005000569W WO 2005098064 A2 WO2005098064 A2 WO 2005098064A2
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- 239000000203 mixture Substances 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910001040 Beta-titanium Inorganic materials 0.000 title description 38
- 238000004519 manufacturing process Methods 0.000 title description 5
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 95
- 239000000956 alloy Substances 0.000 claims abstract description 95
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 43
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011733 molybdenum Substances 0.000 claims abstract description 42
- 239000010955 niobium Substances 0.000 claims abstract description 28
- 238000005482 strain hardening Methods 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- 239000010936 titanium Substances 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 23
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 21
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000011084 recovery Methods 0.000 claims description 46
- 230000009467 reduction Effects 0.000 claims description 32
- 230000032683 aging Effects 0.000 claims description 29
- 230000008859 change Effects 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000009466 transformation Effects 0.000 description 19
- 229910000734 martensite Inorganic materials 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 10
- 229910001000 nickel titanium Inorganic materials 0.000 description 10
- 229910001285 shape-memory alloy Inorganic materials 0.000 description 10
- HLXZNVUGXRDIFK-UHFFFAOYSA-N nickel titanium Chemical compound [Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni] HLXZNVUGXRDIFK-UHFFFAOYSA-N 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 230000035882 stress Effects 0.000 description 8
- 238000000137 annealing Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000000879 optical micrograph Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010622 cold drawing Methods 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 238000000844 transformation Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000000399 orthopedic effect Effects 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 230000002792 vascular Effects 0.000 description 2
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 1
- 230000000172 allergic effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004053 dental implant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000005088 metallography Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 206010039722 scoliosis Diseases 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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
-
- 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
- This disclosure relates to superelastic ⁇ titanium alloys, methods for manufacturing these alloys and articles derived therefrom.
- Alloys that undergo a martensitic transformation may exhibit a "shape memory effect".
- the high temperature phase known as "austenite” changes its crystalline structure through a diffusion-less shear process adopting a less symmetrical structure called 'martensite'.
- This process may be reversible as in shape memory alloys and therefore upon heating, the reverse transformation occurs.
- the starting temperature of the cooling or martensitic transformation is generally referred to as the M s temperature and the finishing temperature is referred to as the M f temperature.
- the starting and finishing temperatures of the reverse or austenitic transformation are referred to as A s and A f respectively.
- alloys undergoing a reversible martensitic phase transformation may be deformed in their high temperature austenitic phase through a stress- induced martensitic transformation as well as in their low temperature martensitic phase. These alloys generally recover their original shapes upon heating above the A f temperature and are therefore called "shape memory alloys".
- shape memory alloys At temperatures above the A f , the stress- induced martensite is not stable and will revert back to austenite upon the release of deformation.
- strain recovery associated with the reversion of stress-induced martensite back to austenite is generally referred to as "pseudoelasticity” or “superelasticity” as defined in ASTM F2005, Standard Tenninology for Nickel-Titanium Shape Memory Alloys.
- the two terms are used interchangeably to describe the ability of shape memory alloys to elastically recover large deformations without a significant amount of plasticity due to the mechanically induced crystalline phase change.
- Nitinol is a shape memory alloy comprising a near-stoichiometric amount of nickel and titanium.
- pseudoelastic nitinol When deforming pseudoelastic nitinol, the formation of stress-induced- martensite allows the strain of the alloy to increase at a relatively constant stress. Upon unloading, the reversion of the martensite back to austenite occurs at a constant, but different, stress.
- a typical stress-strain curve of pseudoelastic nitinol therefore exhibits both loading and unloading stress plateaus. However, since the stresses are different, these plateaus are not identical, which is indicative of the development of mechanical hysteresis in the nitinol.
- Nitinol Deformations of about 8 to about 10% can thus be recovered in the pseudoelastic nitinol.
- Cold worked Nitinol also exhibits extended linear elasticity.
- Linear Superelasticity to differentiate from transformation induced “Pseudoelasticity” or “Superelasticity”.
- These properties generally make nitinol a widely used material in a number of applications, such as medical stents, guide wires, surgical devices, orthodontic appliances, cellular phone antenna wires as well as frames and other components for eye wear.
- nitinol is difficult to fabricate by forming and/or welding, which makes the manufacturing of articles from it expensive and time-consuming. Additionally, users of nickel containing products are sometimes allergic to nickel.
- a composition comprises about 8 to about 10 wt% molybdenum, about 2.8 to about 6 wt% aluminum, up to about 2 wt% vanadium, up to about 4 wt% niobium, with the balance being titanium, wherein the weight percents are based on the total weight of the alloy composition.
- a composition comprises about 8.9 wt% molybdenum, about 3.03 wt% aluminum, about 1.95 wt% vanadium, about 3.86 wt% niobium, with the balance being titanium.
- a composition comprises about 9.34 wt% molybdenum, about 3.01 wt% aluminum, about 1.95 wt% vanadium, about 3.79 wt% niobium, with the balance being titanium.
- a method for making an article comprises cold working a shape from a composition comprising about 8 to about 10 wt% molybdenum, about 2.8 to about 6 wt% aluminum, up to about 2 wt% vanadium, up to about 4 wt% niobium, with the balance being titanium, wherein the weight percents are based on the total weight of the alloy composition; forming the shape; solution heat treating the shape; and cooling the shape.
- a method comprises cold working a wire having a composition comprising about 8 to about 10 wt% molybdenum, about 2.8 to about 6 wt% aluminum, up to about 2 wt% vanadium, up to about 4 wt% niobium, with the balance being titanium, wherein the weight percents are based on the total weight of the alloy composition; cold working the shape; and heat treating the shape.
- Figure 1 is a graphical representation showing the effect of molybdenum content on elastic recovery
- Figure 2 is a graphical representation of the effect of aging at 350°C on the elastic recovery of Sample 4 from Table 1;
- Figure 3 is a graphical representation of the effect of aging at 350°C on the elastic recovery of Sample 5 from Table 1;
- Figure 4 is a graphical representation showing the effect of aging at 350°C on the elastic recovery of Sample 6 from Table 1;
- Figure 5 is a graphic representation showing the effect of aging at about 250 to about 550°C for 10 seconds on the elastic recovery of Sample 4 from Table 1;
- Figure 6 is a graphic representation showing the effect of aging at about 250 to about 550°C for 10 seconds on the elastic recovery of Sample 5 from Table 1;
- Figure 7 is a graphical representation showing the effect of cumulative cold drawing reduction on the UTS of Sample 11 from Table 2;
- Figure 8 is a graphical representation showing the effect of cumulative cold drawing reduction on the Young's Modulus of Sample 11 from Table 2;
- Figure 9 is a graphical representation showing the effect of tensile stress-strain curve for a wire having the composition of Sample 11 from Table 2 with 19.4% drawing reduction, tested to 2% strain;
- Figure 10 is a graphical representation showing the effect of tensile stress- strain curve for a wire having the composition of Sample 11 from Table 2 with 19.4% drawing reduction, tested to 4% strain;
- Figure 11 is an optical micrograph showing the microstructure of a cold drawn wire having the composition of Sample 10 from Table 2 with a 14% reduction;
- Figure 12 is an optical micrograph showing partially recrystallized microstructure of a cold-drawn wire having the composition of Sample 10 from Table 2 having a 14%> reduction after heat- treating at 816°C for 30 minutes;
- Figure 13 is an optical micrograph showing fully recrystallized microstructure of a cold-drawn wire having the composition of Sample 10 from Table 2 having a 14% reduction after heat- treating at 871°C for 30 minutes;
- Figure 14 is an optical micrograph showing the microstructure of a betatized Sample 10 from Table 2 after aging at 816°C for 30 minutes;
- Figure 15 is an optical micrograph showing the microstructure of a betatized Sample 10 from Table 2 after aging at 788°C for 30 minutes;
- Figure 16 is a graphical representation showing the UTS of betatized Sample 10 from Table 2 after aging at 500-900°C for 30 minutes;
- Figure 17 is a graphical representation showing the ductility of betatized Sample 10 from Table 2 after aging at 500-900°C for 30 minutes;
- Figure 18 is a graphical representation showing a tensile stress-strain curve tested to 4% tensile strain of a wire having the composition of Sample 11 from Table 2 after strand annealing at 871°C;
- Figure 19 is an optical micrograph showing the microstructure of a wire having the composition of Sample 11 from Table 2 after strand annealing at 871°C.
- a ⁇ titanium alloy composition having pseudoelastic properties and linear-superelastic properties that can be used for medical, dental, sporting good and eyewear frame applications.
- the ⁇ titanium alloy composition has linear elastic properties and/or pseudoelastic properties after solution treatment, hi another embodiment, the ⁇ titanium alloy composition has pseudoelastic properties that are improved with heat treatment, h yet another embodiment, the ⁇ titanium alloy composition displays linear-superelastic properties after being cold worked.
- the composition advantageously can be welded to other metals and alloys.
- the articles manufactured from the ⁇ titanium alloy can also be deformed into various shapes at ambient temperature and generally retain the high spring back characteristics associated with superelasticity. It is to be noted that all ranges disclosed herein are inclusive and combinable.
- Pure titanium has an isomorphous transformation temperature at 882°C.
- the body centered cubic (bcc) structure which is called /3-titanium, is stable above the isomorphous transformation temperature, and the hexagonal close packed (hep) structure, which is called a titanium is generally stable below this temperature.
- bcc body centered cubic
- hep hexagonal close packed
- the resulting alloys have an increased ⁇ phase stability at temperatures less than or equal to about 882°C ( ⁇ transus temperature).
- the temperature range of the stable a phase is increased above the isomorphous transformation temperature.
- Elements which have the effect of increasing the ⁇ phase temperature range are called the ⁇ stabilizers, while those capable of extending the phase temperature range are called the ⁇ - stabilizers.
- Unalloyed titanium transforms allotropically from body-center-cubic (bcc) ⁇ phase to hexagonal-close-packed (hep) phase upon cooling through the ⁇ transus temperature of 882°C.
- the ultimate microstructure of titanium alloys may have , c& ⁇ , or ⁇ phases.
- the so-called ⁇ alloys contain critical amounts of 3-stabilizing elements and exhibit extended ⁇ stability at high temperatures and a reduction in ⁇ transus temperature to lower temperatures as elemental concentration increases. When a certain concentration level is achieved, the ⁇ phase can be retained upon rapid cooling from the beta phase field, although it is metastable.
- the metastable ⁇ titanium alloys may undergo lattice transformations such as martensitic transformation under applied stress. Hence, titanium alloys at critical range of ⁇ stability may exhibit shape memory effect and superelasticity.
- the /3-stabilizing elements are further classified into ⁇ -isomorphous groups and ⁇ -eutectoid groups. 3-isomorphous elements such as V, Zr, Hf, -Nb, Ta, Mo and Re stabilize the ⁇ phase by forming a simple ⁇ transformation while ⁇ -eutectoid elements such as Cr, Mn, Fe, Co, Ni, Cu, Pd, Ag, W, Pt and Au stabilize the ⁇ phase by forming jS— oH- ⁇ transformations.
- Titanium alloys having a high enough concentration of ⁇ stabilizers generally are sufficiently stable to have a meta-stable ⁇ phase structure at room temperature.
- the alloys showing such a property are called ⁇ titanium alloys.
- Martensite transformations are generally present in ⁇ titanium alloys.
- the martensitic transformation temperature in ⁇ titanium alloys generally decreases with an increasing amount of ⁇ stabilizer in the alloy, while increasing the amount of stabilizer generally raises the martensitic transformation temperature. Therefore, depending on the extent of stabilization, ⁇ titanium alloys may exhibit a martensitic transformation when cooled rapidly from temperatures greater than those at which the ⁇ phase is the single phase at equilibrium.
- the ⁇ titanium alloy generally comprises an amount of about 8 to about 10 wt% of molybdenum, about 2.8 to about 6 wt% aluminum., up to about 2 wt% vanadium, up to about 4 wt%> niobium, with the balance being titanium. All weight percents are based on the total weight of the alloy. Within the aforementioned range for molybdenum, it is generally desirable to have an amount of greater than or equal to about 8.5, preferably greater than or equal to about 9.0, and more preferably greater than or equal to about 9.2 wt% molybdenum.
- Also desirable within this range is an amount of less than or equal to about 9.9, preferably less than or equal to about 9.8, preferably less than or equal to about 9.75, preferably less than or equal to about 9.65, and more preferably less than or equal to about 9.5 wt% molybdenum, based on the total weight of the alloy.
- niobium Within the aforementioned range for niobium, it is generally desirable to have an amount of greater than or equal to about 2, preferably greater than or equal to about 3, and more preferably greater than or equal to about 3.5 wt% niobium, based on the total weight of the alloy.
- the ⁇ titanium alloy it is generally desirable for the ⁇ titanium alloy to comprise 8.9 wt% molybdenum, 3.03 wt% aluminum, 1.95 wt% vanadium, 3.86 wt% niobium, with the balance being titanium.
- the ⁇ titanium alloy prefferably comprises 9.34 wt%> molybdenum, 3.01 wt% aluminum, 1.95 w % vanadium, 3.79 wt% niobium, with the balance being titanium.
- the ⁇ titanium alloy may be solution treated and/or thermally aged, h solution treating the ⁇ titanium alloy, the alloy is subjected to a temperature greater than or equal to about 850°C, the ⁇ transus temperature for the alloy.
- the solution treatment of the alloy is normally carried out in either vacuum or inert gas environment at a temperature of about 850 to about 1000°C, preferably about 850 to about 900°C, for about 1 minute or longer in duration depending on the mass of the part.
- the heating is followed by a rapid cooling at a rate greater than or equal to about 5°C/second, preferably greater than or equal to about 25°C/second, and more preferably greater than or equal to about 50°C/second, by using an inert gas quench or air cooling to retain a fully recrystallized single phase ⁇ grain structure.
- a rapid cooling at a rate greater than or equal to about 5°C/second, preferably greater than or equal to about 25°C/second, and more preferably greater than or equal to about 50°C/second, by using an inert gas quench or air cooling to retain a fully recrystallized single phase ⁇ grain structure.
- the quenched alloy is subsequently subjected to an ageing treatment at about 350 to about 550°C for about 10 seconds to about 30 minutes to adjust the amount of a fine precipitate of the ⁇ phase.
- the alloy may be subsequently subjected to an ageing treatment for up to about 8 hours at a temperature of about 350 to about 550°C.
- the ⁇ titanium alloy may be solution treated at a temperature below the ⁇ transus temperature of about 750 to about 850°C, preferably about 800 to about 850°C, for about 1 to about 30 minutes to induce a small amount of ⁇ precipitates in the recrystallized ⁇ matrix.
- the amount of the ⁇ precipitates is preferably less than or equal to about 15 volume percent and more preferably less than or equal to about 10 volume percent, based on the total volume of the composition. This improves the tensile strength to an amount of greater than or equal to about 140,000 pounds per square inch (9,846 kilogram/square centimeter).
- the ⁇ titanium alloy in the solution treated condition may exhibit pseudoelasticity.
- the solution treated ⁇ titanium alloy generally exhibits a pseudoelastic recovery of greater than or equal to about 75% of the initial strain when elastically deformed to a 2% initial strain, and greater than or equal to about 50% of the initial strain when elastically deformed to a 4% initial strain.
- the initial strain is the ratio of the change in length to the original length of the alloy composition.
- the ⁇ titanium alloy in the solution treated condition may exhibit linear elasticity.
- the solution treated ⁇ titanium alloy generally exhibits a linear elastic recovery of greater than or equal to about 75% of the initial strain when elastically deformed to a 2% initial strain, and greater than or equal to about 50% of the initial strain when elastically deformed to a 4% initial strain.
- the initial strain is the ratio of the change in length to the original length of the alloy composition.
- the ⁇ titanium alloy may be hot worked or cold worked.
- the ⁇ titanium alloy may be cold worked by processes such as cold rolling, drawing, swaging, pressing, and the like, at ambient temperatures.
- the ⁇ titanium alloy may preferably be cold worked to an amount of about 5 to about 85% as measured by the reduction in cross-sectional area based upon the original cross sectional area. " Within this range it is desirable to have a cross sectional area reduction of greater than or equal to about 10, preferably greater than or equal to about 15% of the initial cross sectional area. Also desirable within this range is a reduction in cross sectional area of less than or equal to about 50, more preferably less than or equal to about 30%) based on the initial cross-sectional area.
- the ⁇ titanium alloy in the cold worked state exhibits linear superelasticity where greater than or equal to about 75 > of the initial strain is elastically recoverable after deforming to a 2% initial strain, and greater than or equal to about 50% of the initial strain is elastically recoverable after deforming to a 4% initial strain.
- the elastic modulus of the ⁇ titanium alloy is reduced through cold working by an amount of greater than or equal to about 10, preferably greater than or equal to about 20 and more preferably greater than or equal to about 25 % based upon the elastic modulus, after the alloy is heat treated.
- the ⁇ titanium alloy having linear elastic, linearly superelastic, pseudoelastic or superelastic properties may be used in the manufacturing of various articles of commerce. Suitable examples of such articles are eyewear frames, face inserts or heads for golf clubs, medical devices such as orthopedic prostheses, spinal correction devices, fixation devices for fracture management, vascular and non-vascular stents, minimally invasive surgical instruments, filters, baskets, forceps, graspers, orthodontic appliances such as dental implants, arc wires, drills and files, and a catheter introducer (guide wire).
- the stability of the ⁇ phase can be expressed as the sum of the weighted averages of the elements that comprise the alloy, often known as the molybdenum equivalent (M ⁇ e q.).
- Mo eq. molybdenum equivalent
- Mo molybdenum
- Nb niobium
- Ta tantalum
- V vanadium
- Co cobalt
- Cr chromium
- Cu copper
- Fe iron
- Mn manganese
- TNTi nickel
- W tungsten
- Al aluminum and wherein the respective chemical symbols represent the amounts of the respective elements in weight percent based on the total ⁇ veight of the alloy. It is to be noted that aluminum can be substituted by gallium, carbon, germanium or boron.
- Hf (hafnium), Sn (tin) and Zr (zirconium) exhibit similarly weak effects on the ⁇ stability. Although they act to lower the ⁇ transus, th-ese elements are considered neutral additions.
- US Air Force Technical Report AFML-TR-75-41 has suggested that Zr has a small Mo equivalent of 0.25 while Al is an ⁇ stabilizer h-aving a reverse effect to that of Mo.
- the Mo equivalent in weight percent is calculate according to the following equation (2) which is a modified form of the equation (1):
- a shape memory alloy that displays superelasticity and/or pseudoelasticity, which has a molybdenum equivalent of about 7 to about 11 wt%, based upon the total weight of the alloy.
- a shape memory alloy that displays superelasticity and/or pseudoelasticity which has a molybdenum equivalent of about 7.5 to about 10.5 wt° o, based upon the total weight of the alloy.
- a shape memory alloy that displays superelasticity and/or pseudoelasticity which has a molybdenum equivalent of about 8 to about 10 wt%, based upon the total weight of the allo y.
- the elements that may be present in the composition in addition to titanium are molybdenum, vanadium, chromium, aluminum, and/or niobium
- the superelastic ⁇ titanium alloy generally provides an adequate spring-back for eyewear applications. It is generally desired to use superelastic ⁇ titanium alloy having a minimum recovery of about 50% of the initial strain, when the allo s is deformed to an outer fiber initial strain of about 4% in a bend test. It is preferable to have a minimum recovery of greater than or equal to about 75% of the initial strain when t?t ⁇ e alloy composition is deformed to about 4%. of the outer fiber initial length in a bend test. It is also generally desirable for the superelastic ⁇ titanium alloy to have a minimum recoverable strain of about 50% of the initial strain, when the alloy composition is strained to> about 4% initial tensile strain.
- a minimum recovery of greater than or equal to about 75% of the initial tensile strain when the alloy is strained to about 4% initial strain in a tensile test.
- the strain recovery is measured as a function of the initial bending strain and the initial bending strain is expressed as a percentage of the ratio of the change in length to the original length.
- Tensile strain recovery was measured by tensile elongation to a strain of 4% followed by unloading to zero stress. Tensile specimens with a cross sectional dimension of 0.90 mm x 2.0 mm were used and the strain was monitored using an extensometer. An environmental chamber with electrical heating and CO 2 cooling capabilities provided a testing capability from -30°C to 180°C.
- the optimal elastic strain recovery after heat aging at 350°C for 10 seconds for the alloy having about 9 wt% molybdenum is approximately 90% of the applied 4% bend strain. Alloys with a molybdenum content less than 8.4 wt% exhibit a different aging characteristic. Aging at 350°C may degrade elastic strain recovery as for alloy 2 having about 8.03 wt% molybdenum, or has no significant effect as for alloy 1 having about 7.63 wt% molybdenum. [0055]
- the percent of the elastic recovery to the total deformation during thermal aging at 350°C for Samples 4, 5 and 6 respectively, are plotted in the Figures 2, 3 and 4 respectively. From the Figures 2, 3 and 4 it may be seen that the elastic recoveries of all three alloys reach a maximum after aging for about 10 to about 60 seconds. Aging beyond 15 minutes (900 seconds) degrades the elastic recovery.
- the alloys shown in Table I also exhibit linear superelasticity after cold working with a reduction of greater than or equal to about 30%. in the cross-sectional area.
- a wire fabricated from an ingot having a composition of 11.06 wt% molybdenum, 3.80 wt% niobium, 1.97 wt% vanadium, 3.07 wt% aluminum with the remainder being titanium exhibited an elastic recovery strain of 3.5% after bending to a total deformation of 4% outer fiber strain, when the reduction in the cross sectional area after cold working was 84%.
- the ⁇ titanium alloys were manufactured by double vacuum arc melting. Chemistries of the alloys were analyzed using inductively coupled plasma optical emission spectrometry (ICP-OE). The results are tabulated in Table 2. The ingot was hot-forged, hot-rolled and finally cold-drawn to wire of various diameters in the range of about 0.4 to about 5 mm. Inter-pass annealing between cold reductions was carried out at 870°C in a vacuum furnace for wires having a diameter of larger than 2.5 mm or by strand annealing under inert atmosphere for the smaller diameters. Tensile properties were determined using an Instron model 5565 material testing machine equipped with an extensometer of 12.5 mm gage length. Microstructures were studies by optical metallography using a Nikon Epiphot inverted metallurgical microscope.
- the strand-annealed wires generally have a higher ultimate tensile strength (UTS) around 1055 mega Pascals (?MPa) than vacuum annealed wires and sheets, the typical UTS of which is about 830 MPa.
- UTS ultimate tensile strength
- Figure 7 plots the UTS of wires drawn from an annealed 1.0 mm diameter Sample 11 wire stock as a function of reduction in cross-section area. After a 49%) reduction, the UTS was elevated from 1055 ?MPa to only 1172 MPa indicating a fairly weak strain hardening effect. Young's Modulus was determined by tensile testing the wire to 1% strain and measuring the linear slope of the stress-strain curve.
- cold-drawn wires generally have a lower modulus than does annealed wire.
- the modulus of approximately 65.9 gigapascals (GPa) for the annealed wire, decreases with increasing accumulative amount of reduction and stabilizes at approximately 50 GPa after cold drawing with a cumulative reduction greater than 20%.
- a micrograph in Figure 11 reveals the cold-worked microstructure of the Sample 10 wire after a 14% cold working reduction in cross sectional area.
- the recrystallized microstructures of the wire after heat-treatments at 816°C and 871°C for 30 minutes are shown in Figures 12 and 13, respectively. It is apparent that the material was not fully betatized after the heat-treatment at 816°C as ⁇ "phase was present in the microstructure. As may be seen in Figure 11, a fully recrystallized ⁇ grain structure was obtained after the heat-treatment at 871°C for 30 minutes.
- the Sample 11 composition in solution treated condition exhibits pseudoelasticity. Their mechanical properties are highly sensitive to solution heat treatment and subsequent aging at a temperature of about 350 to about 550°C. It was discovered that Sample 11 wires after strand annealing at 870°C exhibit well-defined pseudoelasticity.
- An example is presented in Figure 18, which shows a 4% tensile stress-strain curve of a strand- annealed, 0.4mm diameter Sample 11 wire. After deforming to a 4% elongation, the wire specimen was able to go through a pseudoelastic recovery recovering a 3.4% tensile strain and leaving a residual strain of only 0.6%> after unloading.
- a transverse cross-sectional view of the wire microstructure is shown in a micrograph of Figure 19.
- the microstructure consists of equiaxial ⁇ precipitates in ⁇ matrix. It appears that the short duration of strand annealing did not allow the wire to fully recrystallize into the ⁇ grain structure. Without being limited by theory, it is believed that this may explain why strand-annealed wire generally has a higher UTS when compared to that of a fully betatized material.
- the ⁇ titanium alloys can display an elastic strain recovery of 88.5%>, when subjected to an initial bending strain of 4%>.
- the strain recovery is measured as a function of the initial bending strain and the initial bending strain is expressed as a percentage of the ratio of the change in length to the original length.
- These alloys may be advantageously used in a number of commercial applications such as eyewear frames, face insert and heads for golf clubs, orthodontic arch wires, orthopedic prostheses and fracture fixation devices, spinal fusion and scoliosis correction instruments, stents, a catheter introducer (guide wire) and the like.
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Abstract
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JP2006549445A JP2007520630A (en) | 2004-01-08 | 2005-01-07 | Beta titanium composition and method for producing the same |
EP05761999A EP1706517A2 (en) | 2004-01-08 | 2005-01-07 | B titanium compositions and methods of manufacture thereof |
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US10/755,034 US20040168751A1 (en) | 2002-06-27 | 2004-01-08 | Beta titanium compositions and methods of manufacture thereof |
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US9000296B2 (en) | 2013-06-21 | 2015-04-07 | Baker Hughes Incorporated | Electronics frame with shape memory seal elements |
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US20040168751A1 (en) | 2004-09-02 |
JP2007520630A (en) | 2007-07-26 |
WO2005098064A3 (en) | 2006-01-19 |
EP1706517A2 (en) | 2006-10-04 |
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