WO2015199769A2

WO2015199769A2 - Nanostructured titanium alloy and method for thermomechanically processing the same

Info

Publication number: WO2015199769A2
Application number: PCT/US2015/020389
Authority: WO
Inventors: Gian COLOMBO; Venkata ANUMALESETTY; Graham MCINTOSH; Yuliya MARDAKHAYEVA
Original assignee: Manhattan Scientifics, Inc.
Priority date: 2014-03-14
Filing date: 2015-03-13
Publication date: 2015-12-30
Also published as: EP3117016A2; JP2017512901A; WO2015199769A3; EP3117016A4; US20160108499A1; CN106460101A

Abstract

A nanostructured titanium alloy article is provided. The nanostructured alloy includes a developed titanium structure having at least 80% of grains of a grain size < 1.0 microns.

Description

NANOSTRUCTURED TITANIUM ALLOY AND METHOD FOR THERMOMECHANICALLY PROCESSING THE SAME

FIELD OF THE INVENTION

[0001] The invention relates to a nanostructured material and, more particularly, a

nanostructured titanium alloy having a developed a-titanium structure with enhanced material properties.

BACKGROUND ART

[0002] It is known that microstructure plays a key role in the establishment of mechanical properties. Depending on the processing method, a material's structure can be developed to enhance material properties. For instance, it is possible to modify the grain or crystalline structure of the material using mechanical, or thermo-mechanical processing techniques.

[0003] United States Patent Application 2011/0179848 discloses a commercially pure titanium product having enhanced properties for biomedical applications. The titanium product has a nanostructure, which provides enhanced properties in relation to the original mechanical properties, including mechanical strength, resistance to fatigue failure, and biomedical properties. It is disclosed that the known titaniu m product is first subject to severe plastic deformation (SPD) using an equal channel angular pressing (ECAP) technique at a temperature no more than 450° C with the total true accumulated strain e≥4, and then subsequently developed using thermomechanical treatment with a strain degree from 40 to 80%. In particular, the thermomechanical treatment includes plastic deformation performed with a gradual decrease of temperature in the range T=450 . . . 350° C. and the strain rate of 10^"2 . . . 10^"4 s^"1.

[0004] While this known technique achieves a higher level of mechanical properties for commercially pure titanium, there is a need to increase the level of tensile and/or shear strength, as well as fatigue properties in titanium alloys for various engineering applications, including but not limited to biomedical, energy, high performance sporting goods, and aerospace applications.

DESCRIPTION OF INVENTION

[0005] In view of these shortcomings, an object of the invention, among others, is to increase the level of strength and fatigue resistance of a titaniu m alloy.

[0006] As a result, a nanostructured titanium alloy article is provided. The nanostructu red alloy includes a developed titanium structure having at least 80% of grains of a size < 1.0 microns.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Exemplary embodiments of the invention will be described with reference to the accompanying drawings, of which:

[0008] Figure 1 is a micrograph of a known commercially pure titanium alloy taken using electron back scatter diffraction;

[0009] Figure 2 is a micrograph of a nanostructured commercially pure titanium alloy accord ing to the invention taken using electron back scatter diffraction;

[0010] Figure 3 is a graphical representation, obtained using electron back scatter diffraction, showing the grain size distribution of the known commercially pure titanium alloy;

[0011] Figure 4 is a graphical representation, obtained using electron back scatter diffraction, showing the grain size distribution of the nanostructured commercially pure titanium alloy according to the invention;

[0012] Figure 5 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of the known commercially pure titanium alloy;

[0013] Figure 6 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of the nanostructured commercially pure titanium alloy according to the invention;

[0014] Figure 7 is a graphical representation, obtained using electron back scatter diffraction, showing the grain shape aspect ratio distribution in the longitudinal plane of the nanostructu red commercially pure titanium alloy accord ing to the invention;

[0015] Figure 8 is a graphical representation, obtained using electron back scatter diffraction, showing the grain shape aspect ratio distribution in the transverse plane of the nanostructured commercially pure titanium alloy accord ing to the invention;

[0016] Figure 9 is a micrograph of the commercially pure nanostructured titanium alloy according to the invention having a plurality of equiaxed grains, obtained using transmission electron microscopy;

[0017] Figure 10 is a micrograph of the commercially pure nanostructured titanium alloy according to the invention having a plurality of grains with high dislocation density, obtained using transmission electron microscopy;

[0018] Figure 11 is a micrograph of the commercially pure nanostructured titanium alloy according to the invention showing a plurality of sub-grains, obtained using transmission electron microscopy;

[0019] Figure 12 is a micrograph of a known titanium alloy Ti6AI4V taken using electron back scatter diffraction;

[0020] Figure 13 is a micrograph of a nanostructured titanium alloy Ti6AI4V according to the invention taken using electron back scatter diffraction;

[0021] Figure 14 is a graphical representation, obtained using electron back scatter diffraction, showing the grain size distribution of the nanostructured titanium alloy Ti6AI4V according to the invention;

[0022] Figure 15 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of a known titanium alloy Ti6AI4V;

[0023] Figure 16 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of the nanostructured titanium alloy Ti6AI4V according to the invention;

[0024] Figure 17 is a micrograph of a known titanium alloy Ti6AI4V ELI taken using electron back scatter diffraction;

[0025] Figure 18 is a micrograph of a nanostructured titanium alloy Ti6AI4V ELI according to the invention taken using electron back scatter diffraction; and

[0026] Figure 19 is a graphical representation, obtained using electron back scatter diffraction, showing the grain size distribution of the nanostructured titanium alloy Ti6AI4V ELI according to the invention;

[0027] Figure 20 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of a known titanium alloy Ti6AI4V ELI.

[0028] Figure 21 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of the nanostructured titanium alloy Ti6AI4V ELI according to the invention.

MODES FOR CARRYING OUT THE INVENTION AN D INDUSTRIAL APPLICABILITY

[0029] The invention is a nanostructu red titanium alloy that can be used in different industries for production of various useful articles, such as orthopedic implants, medical and aerospace fasteners, aerospace structural components, and high performance sporting goods. In an exemplary embodiment of the invention, a composition of commercially pure titanium, having an a-titaniu m matrix that may contain retained β-titanium particles, is processed to develop the structure to achieve a nanostructure with at least 80% of the grains being < 1 micron. As a result, the nanostructured titanium alloy exhibits various material property changes such as an increase in tensile strength and/or shear strength and/or fatigue endurance limit. In particular, the nanostructured titanium alloy structure is developed using a combination of thermomechanical processing steps according to the invention. This process provides a developed microstructure having a preponderance of ultrafine grain and/or nanocrystalline structures.

[0030] Figures 1, 12, and 17 show the starting commercially pure titanium alloy, Ti6AI4V, and Ti6AI4V ELI microstructure, respectively. Figures 2, 13, and 18 show the resulting structure of the nanostructured commercially pure titanium alloy, Ti6AI4V, and Ti6AI4V ELI according to the invention, respectively. Examination of the figures clearly shows the d ifference between the starting and nanostructured titanium alloys.

[0031] The workpiece can be comprised of various commercially available titanium alloys known in the art, such as commercially pure titanium alloys (Gradesl-4), Ti-6AI-4V, Ti-6A1-4V ELI, ΤΪ-6ΑΙ- 7N b, Ti-Zr, or other known alpha, near alpha, and alpha-beta phase titanium alloys.

[0032] Accordingly, in other exemplary embodiments of the invention, an alpha-beta phase titanium alloy is processed from a combination of a severe plastic deformation process type and non-severe plastic deformation type thermomechanical processing steps to develop a nanostructure with at least 80% of the grains being < 1 micron.

[0033] In an exemplary embod iment of the invention, a coarse grain commercially pu re titaniu m alloy is used for the workpiece, which has the following composition by weight percent: nitrogen (N ) 0.07% maximum, carbon (C) 0.1% maximu m, hydrogen (H) 0.015% maximum, iron (Fe) 0.50% maximu m, oxygen (O) 0.40% maximum, total of other trace impurities is 0.4% maximu m, and titanium (Ti) as the balance.

[0034] Other titanium alloys may be used, including but not limited to other commercially pure titanium alloys, Ti-6AI-4V, Ti-6A1-4V ELI, Ti-6AI-7Nb, and Ti-Zr. Standard chemical compositions of these titanium alloys can be fou nd in Tables 1-3, which identify the standard chemical compositions by wt% max. (ASTM B348-11, Standard specification for Titanium and Titanium Alloy Bars and Billets; ASTM F1295 - 11 Standard Specification for Wrought Titanium-6Alu minum-7Niobium Alloy for Surgical Implant Applications; ASTM F136 - 12a Standard Specification for Wrought Titanium- 6Aluminu m-4Vanadium ELI (Extra Low Interstitial) Alloy for Surgical Implant Applications; and Titanium Alloy Ti-Zr, U.S. Patent No. 8, 168,012).

TABLE 2 Ti-6AI-4V, Ti-6A1-4V ELI, Ti-6AI-7Nb - Chemical Compositions, wt% max

Total of Ti

Designation N C H Fe O Al V other

elements

Ti-6AI-4V 0.05 0.08 0.015 0.40 0.2 5.5-6.75 3.5-4.5 0.4 balance

Ti-6A1-4V balance

0.05 0.08 0.012 0.25 0.13 5.5-6.5 3.5-4.5 0.4 ELI

Designation N C H Fe O Al Nb Ta Ti

5.50- 6.50- balance

Ti-6AI-7Nb 0.05 0.08 0.009 0.25 0.20 0.5

6.50 7.50

[0035] The workpiece, for instance a rod or bar, is subjected to severe plastic deformation ("SPD") and thermomechanical processing. The combined processing steps induce a large amount of shear deformation that significantly refines the initial structure by creating a large number of high angle grain boundaries (misorientation angle > 15°) and high dislocation density.

[0036] In particular, in the exemplary embodiment, the workpiece is processed using an equal channel angular pressing - conform (ECAP-C) machine, which consists of a revolving wheel having a circumferential groove and two stationary dies that form a channel that intersect at a defined angle. However, it is also possible in other embodiments to subject the workpiece to severe plastic deformation using other known process types, including equal-channel angular pressing, equal channel angular extrusion, incremental equal channel angular pressing, equal channel angular pressing with parallel channels, equal channel angular pressing with multiple channels, hydrostatic equal channel angular pressing, cyclic extrusion and compression, dual roll equal channel angular extrusion, hydrostatic extrusion plus equal channel angular pressing, equal channel angular pressing plus hydrostatic extrusion, continuous high pressure torsion, torsional equal channel angular pressing, equal channel angular rolling or equal channel angular drawing.

[0037] Firstly, using the ECAP-C machine, the workpiece is pressed into the wheel groove and is driven through the channel by frictional forces generated between the workpiece and the wheel. A commercially pure titanium alloy workpiece is processed through the ECAP-C machine at temperatures below 500°C, preferably 100-300°C. Other titanium alloys: Ti6AI4V, Ti6AI4V ELI, and Ti6Al7N b are processed through the ECAP-C machine at a temperature below 650°C, preferably 400- 600°C. The workpiece passes through the ECAP-C machine between 1 and 12 times, preferably 4 to 8 times. The die is set at an angle of channel intersection between ψ=75° and ψ=135°, 90° to 120°, and 100° to 110°. To enable comparable structural evolution, a lower channel intersection angle will require fewer passes and/or higher temperature, and a higher channel intersection angle will require more passes and/or lower temperature. The workpiece is rotated around its longitudinal axis by an angle of 90° between each pass through the ECAP-C machine, which provides homogeneity in the developed structure. This method of rotation is known as ECAP route B_c. However, in other embodiments, the ECAP route may be changed, including but not limited to known routes A, C, B_A, E, or some combination thereof.

[0038] After the workpiece has been processed using severe plastic deformation from the ECAP-C processing steps, the workpiece is then subjected to additional thermomechanical processing using non-SPD type metal forming techniques. In particular, the thermomechanical processing further evolves the structu re of the workpiece, more than the ECAP-C alone. In the exemplary embodiment, one or more thermomechanical processing steps may be carried out, including but not limited to drawing, rolling, extrusion, forging, swaging, or some combination thereof. In the exemplary embodiment, the thermomechanical processing for commercially pure titanium alloy is carried out at temperatures T < 500°C, preferably room temperatu re to 250°C. Thermomechanical processing of titanium alloys: Ti6AI4V, Ti6AI4V ELI, and Ti6Al7N b is carried out at temperatures not greater than 550°C, preferably 400-500°C. Thermomechanical processing provides a cross-sectional area reduction of > 35%, preferably > 65%.

[0039] The combination of severe plastic deformation and thermomechanical processing substantially refines the initial structure, which consists of an a-titaniu m matrix that may contain retained β-titanium particles, to a predominantly submicron grain size. In the exemplary embodiment of the invention, the ECAP-C process fragments the starting grain structure by introducing large numbers of twins and dislocations that organize to form dislocation cells with walls having a low misorientation angle < 15°.

[0040] During thermomechanical processing, dislocation density increases, and some of the low angle cell walls evolve into high angle subgrain boundaries, enhancing strength while retaining usable ductility levels for industrial applications.

[0041] In the exemplary embodiment, the resulting nanostructured titanium alloy includes an a- titanium matrix that may contain retained β-titanium particles.

[0042] Figure 3 is a histogram showing the grain size distribution in the starting commercially pure titanium alloy. Figures 4, 14, and 19 are histograms showing the grain size distribution in the nanostructured commercially pure titanium alloy, nanostructu red Ti6AI4V, and nanostructured Ti6AI4V ELI, respectively, according to the invention. The average grain size of the nanostructured titanium alloys is red uced from the starting titanium alloys. Figure 5 shows that the starting commercially pure titanium alloy has 90%-95% of the grain boundaries with misorientation angle > 15°, while Figure 6 shows that the nanostructured commercially pure titanium alloy retains 20%- 40% of the grain boundaries with misorientation angle > 15°. Figures 15 and 20 show that the starting titanium alloys: Ti6AI4V and Ti6AI4V ELI has 40-55% of the grain boundaries with misorientation angle > 15°, and Figures 16 and 21 show that the nanostructured Ti6AI4V and Ti6AI4V ELI retains 20-40% of the grain boundaries with misorientation angle > 15°. These distributions contribute to the retention of useful ductility levels.

[0043] Figures 7 and 8 show the grain aspect ratio distribution in the longitudinal and transverse planes of the nanostructured commercially pure titanium alloy, which demonstrates an increased proportion of lower grain shape aspect ratio grains in the longitudinal plane compared to the transverse plane. The similar aspect ratio is observed in nanostructured Ti6AI4V and Ti6AI4V ELI alloys.

[0044] The size of these dislocation cells and subgrains can be measu red by a variety of techniques including but not limited to transmission electron microscopy (TEM) and x-ray diffraction (XRD), in particular the extended-convolutional multi whole profile fitting procedure as applicable to XRD. For instance, Figures 9-11 are TEM micrographs showing equiaxed grains, high dislocation density, and a high number of sub-grains in the nanostructured commercially pure titanium alloy, according to the invention. In Figure 9, the eq uiaxed grains are highlighted by continuous lines, while in Figure 10 the high dislocation density regions are highlighted with continuous lines. In Figure 11, the grains are highlighted with continuous lines and the sub-grains are highlighted with dotted lines.

[0045] Table 4 shows typical room temperature mechanical property levels of the starting titanium alloys and the nanostructured titanium alloys accord ing to the invention that can be achieved because of structure development.

TABLE 4

Mechanical Properties Cantilever-

Axial Rotating

Ultimate Tensile Ultimate

Total Area

Fatigue Beam Tensile Yield Shear

Elongation Reduction

Material Endurance Fatigue

Strength Strength Strength

Limit* Endurance

(%) (%)

(MPa) (MPa) (MPa)

(MPa) Limit*

(MPa)

Known 784 629 27 50 510 575 450 Commercially

Pure Titanium

Alloy

Nanostructured 1200 1050 10 25 650 700 650 Commercially

Pure Titanium

Alloy

Known 1035 908 15 44 645 850 650 Titanium Alloy

Ti6AI4V

Nanostructured 1450 1250 10 25 740 950 700 Titanium Alloy

Ti6AI4V

Known 1015 890 18 46 625 Titanium Alloy

Ti6AI4V ELI

Nanostructured 1400 1250 10 25

Titanium Alloy

Ti6AI4V ELI

*Fatigue endurance limit measured at 10⁷ cycles

[0046] Table 4 clearly demonstrates that the resulting nanostructured titanium alloys exhibit various material property changes, such as increased tensile strength and/or shear strength and/or fatigue endu rance limit. In particular, the nanostructured titanium alloys according to the exemplary embodiment of the invention have a total tensile elongation greater than 10% and a reduction of area greater than 25%. In addition, the nanostructured titanium alloys have at least 80% of the grains with a size < 1.0 microns, with approximately 20-40% of all grains having high angle grain boundaries, and > 80% of all grains have a grain shape aspect ratio in the range 0.3 to 0.7. Additionally, the nanostructured titanium alloy articles have grains with an average crystallite size below 100 nanometers and a dislocation density of > 10¹⁵ m^"2.

[0047] Thus, the invention provides a nanocrystalline structure having enhanced properties from the starting workpiece, as a result of severe plastic deformation and thermomechanical processing.

[0048] Titaniu m alloys that may be used in accordance with the present invention include commercially pure titanium alloys (Grades 1-4), Ti-6AI-4V, Ti-6A1-4V ELI, Ti-Zr, or Ti-6AI-7Nb. The nanostructured titanium alloy in accordance with the present invention can be used to produce useful articles with enhanced material properties, includ ing aerospace fasteners, aerospace structural components, high performance sporting goods, as well as articles for medical applications, such as spinal rods, screws, intramedullary nails, bone plates and other orthopedic implants. For example, the invention may provide aerospace fasteners comprised of nanostructured Ti alloy having increased ultimate tensile strength, such as above 1200 M Pa, and increased shear strength, such as above 650 M Pa.

[0049] The foregoing illustrates some of the possibilities for practicing the invention. Many other embodiments are possible within the scope and spirit of the invention. It is, therefore, intended that the foregoing description be regarded as illustrative rather than limiting, and that the scope of the invention is given by the appended claims together with their full range of equivalents.

Claims

WHAT IS CLAIMED IS:

1. A nanostructured titanium alloy article, comprising:

a developed titanium structure having > 80% of grains being of a size < 1.0 micron.

2. The nanostructured titanium alloy article according to claim 1, wherein the developed titanium structure is a developed a-titanium structure.

3. The nanostructured titanium alloy article according to claim 1, wherein the grains are a phase grains.

4. The nanostructured titanium alloy article according to claim 1, wherein the developed titanium structure has a dislocation density > 10¹⁵ m^"2.

5. The nanostructured titanium alloy article according to claim 1, wherein 20-40% of the grains include high angle grain boundaries with a misorientation angle > 15°.

6. The nanostructured titanium alloy article according to claim 1, wherein > 80% of the grains have a grain shape aspect ratio that is in a range of 0.3 to 0.7.

7. The nanostructured titanium alloy article according to claim 1, wherein the developed titanium structure is processed from a combination of a severe plastic deformation process type and non- severe plastic deformation type thermomechanical processing steps.

8. The nanostructured titanium alloy article according to claim 1, wherein the developed titanium structure has an average crystallite size is < 100 nanometers.

9. The nanostructured titanium alloy article according to claim 8, wherein the developed titanium structure has a dislocation density is > 10¹⁵ m^"2.

10. The nanostructured titanium alloy article according to claim 9, wherein 20-40% of the grains have high angle grain boundaries with a misorientation angle > 15°.

11. The nanostructured titanium alloy article according to claim 10, wherein > 80% of the grains have a grain shape aspect ratio in a range from 0.3 to 0.7.

12. The nanostructured titanium alloy article according to claim 11, wherein the developed titanium structure has an ultimate tensile strength > 1200 MPa.

13. The nanostructured titanium alloy article according to claim 12, wherein the ultimate tensile strength > 1400 MPa.

14. The nanostructured titanium alloy article according to claim 12, wherein the developed titanium structure has a total tensile elongation > 10%.

15. The nanostructured titanium alloy article according to claim 14, wherein the developed titanium structure has an area reduction > 25%.

16. The nanostructured titanium alloy article according to claim 15, wherein the developed titanium structure has an ultimate shear strength is > 650 MPa.

17. The nanostructured titanium alloy article according to claim 16, wherein the ultimate shear strength > 740 MPa.

18. The nanostructured titanium alloy article according to claim 16, wherein the developed titanium structure has an axial fatigue endurance limit > 700 MPa measured at 10⁷ cycles.

19. The nanostructured titanium alloy article according to claim 18, wherein the axial fatigue endurance limit > 950 MPa measured at 10⁷ cycles.

20. The nanostructured titanium alloy article according to claim 18, wherein the developed titanium structure has a cantilever-rotating beam fatigue endurance limit > 650MPa measured at 10⁷ cycles.

21. The nanostructured titanium alloy article according to claim 20, wherein the cantilever-rotating beam fatigue endurance limit > 700 MPa measured at 10⁷ cycles.

22. The nanostructured titanium alloy article according to claim 1,

wherein the developed titanium structure includes a-titanium matrix having retained β-titanium particles.

23. The nanostructured titanium alloy article according to claim 1, wherein the developed titanium structure has a composition by weight percent:

nitrogen (N) 0.07% maximum;

carbon (C) 0.1% maximum;

hydrogen (H) 0.015% maximum;

iron (Fe) 0.50% maximum;

oxygen (O) 0.40% maximum;

trace impurities 0.40% maximum; and

a balance of titanium (Ti).

24. The nanostructured titanium alloy article according to claim 23, wherein the developed titanium structure has a composition by weight percent:

Aluminum (Al) 6.75% maximum; and

Vanadium (V) 4.5% maximum.

25. The nanostructured titanium alloy article according to claim 23, wherein the developed titanium structure has a composition by weight percent:

Aluminum (Al) 6.5% maximum;

Niobium (Nb) 7.5% maxium; and

Tantalum (Ta) 0.5% maximum.

26. The nanostructured titanium alloy article according to claim 23, wherein the developed titanium structure has a composition by weight percent:

Zirconium (Zr) 25% maximum; and other elements 1% maximum.

27. A method for making a nanostructured titanium alloy, comprising the steps of:

providing a workpiece of a titanium alloy;

inducing severe plastic deformation to the workpiece using an equal-channel angular pressing-conform machine at temperatures < 650° C and having a die set at a channel angle of intersection between ψ=75° and ψ=135°; and

subjecting the workpiece to thermomechanical processing at temperatures < 550°C to prepare an article having a cross-sectional area reduction > 35%.