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Heat Treating Titanium Alloys

Titanium alloys are heat treated to achieve the following:

Stress relieving, to reduce residual stresses developed during fabrication. Annealing, to achieve an optimum combination of ductility, machinability, dimensional stability and structural stability. Solution treating and aging, to increase strength. Combinations of processes are employed to optimize properties and gain other advantages such as: o Fracture toughness o Fatigue strength o High temperature creep strength o Resistance to preferential chemical attack o Prevent distortion o Condition the forging for subsequent forming and fabricating operations.

There are three principal types of heat treatment. 1. Stress Relieving Titanium alloys can be stress relieved without adversely affecting strength or ductility. The process for forgings takes place at 595 to 705C (1100 to 1300F) for a period of one to two hours, followed by air cooling. It decrease undesirable residual stresses that may result during forging processes. 2. Annealing Mill annealing, which is usually applied to forging bar stock, is not a full anneal, and may leave traces of cold or warm working in some products. Duplex and triplex annealing are used to improve creep resistance and fracture toughness. 3. Solution Treatment and Aging This process consists of heating to a specified temperature for the alloy, quenching at a controlled rate in either oil, air or water, and aging. Aging consists of reheating to a temperature between 425 and 650C (800 to 1200F) for approximately two hours. This process develops higher strengths than are achievable by the other processes.

Heat Treating of Titanium and Titanium Alloys

Titanium and Titanium Alloys are heat treated in order to:

Reduce residual stresses developed during fabrication (stress relieving) Produce an optimum combination of ductility, machinability, and dimensional and structural stability (annealing) Increase strength (solution treating and aging) Optimize special properties such as fracture toughness, fatigue strength, and high-

temperature creep strength

Titanium and titanium alloys are heat treated in order to:

Reduce residual stresses developed during fabrication (stress relieving) Produce an optimum combination of ductility, machinability, and dimensional and structural stability (annealing) Increase strength (solution treating and aging) Optimize special properties such as fracture toughness, fatigue strength, and high-temperature creep strength.

Various types of annealing treatments (single, duplex, (beta), and recrystallization annealing, for example), and solution treating and aging treatments, are imposed to achieve selected mechanical properties. Stress relieving and annealing may be employed to prevent preferential chemical attack in some corrosive environments, to prevent distortion (a stabilization treatment) and to condition the metal for subsequent forming and fabricating operations.

Alloy Types and Response to Heat Treatment

The response of titanium and titanium alloys to heat treatment depends on the composition of the metal and the effects of alloying elements on the - crystal transformation of titanium. In addition, not all heat treating cycles are applicable to all titanium alloys, because the various alloys are designed for different purposes.

Alloys Ti-5Al-2Sn-2Zr-4Mo-4Cr and Ti-6Al-2Sn-4Zr-6Mo are designed for strength in heavy sections. Alloys Ti- 6Al-2Sn-4Zr-2Mo and Ti-6Al-5Zr-0.5Mo-0.2Si for creep resistance. Alloys Ti-6Al-2Nb-1 Ta-1Mo and Ti-6Al-4V, for resistance to stress corrosion in aqueous salt solutions and for high fracture toughness. Alloys Ti-5Al-2.5Sn and Ti-2.5Cu for weldability; and Ti-6Al-6V-2Sn, Ti-6Al-4V and Ti-10V-2Fe-3Al for high strength at low-to-moderate temperatures.

Effects of Alloying Elements on - Transformation. Unalloyed titanium is allotropic. Its close-packed hexagonal structure ( phase) changes to a body-centered cubic, structure (-phase) at 885C (1625F), and this structure persists at temperatures up to the melting point. With respect to their effects on the allotropic transformation, alloyi ng elements in titanium are classified as stabilizers or stabilizers. Alpha stabilizers, such as oxygen and aluminum, raise the -to- transformation temperature. Nitrogen and carbon are also stabilizers, but these elements usually are not added intentionally in alloy formulation. Beta stabilizers, such as manganese, chromium, iron, molybdenum, vanadium, and niobium, lower the -to- transformation temperature and, depending on the amount added, may result in the retention of some phase at room temper ature. Alloy Types. Based on the types and amounts of alloying elements they contain, titanium alloys are classified as , near -, -, or alloys. The response of these alloy types to heat treatment is briefly described below. Alpha and near-alpha titanium alloys can be stress relieved and annealed, but high strength cannot be developed in these alloys by any type of heat treatment (such as aging after a solution beta treatment and quenching). The commercial alloys are, in reality, metastable alloys. When these alloys are exposed to selected elevated temperatures, the retained phase decomposes and strengthening occurs. For alloys, stress-relieving and aging treatments can be combined, and annealing and solution treating may be identical operations. Alpha-beta alloys are two-phase alloys and, as the name suggests, comprise both and phases at room temperature. These are the most common and the most versatile of the three types of titanium alloys. Oxygen and iron levels have significant effects on mechanical properties after heat treatment. It should be realized that:

Oxygen and iron must be near specified maximums to meet strength levels in certain commercially pure grades Oxygen must be near a specified maximum to meet strength levels in solution treated and aged Ti-6Al-4 V

Oxygen levels must be kept as low as possible to optimize fracture toughness. However, the oxygen level must be high enough to meet tensile strength requirements Iron content must be kept as low as possible to optimize creep and stress-rupture properties. Most creepresistant alloys require iron levels at or below 0.05wt%.

Stress Relieving
Titanium and titanium alloys can be stress relieved without adversely affecting strength or ductility. Stress-relieving treatments decrease the undesirable residual stresses that result from first, nonuniform hot forging or deformation from cold forming and straightening, second, asymmetric machining of plate or forgings, and, third, welding and cooling of castings. The removal of such stresses helps maintain shape stability and eliminates unfavorable conditions, such as the loss of compressive yield strength commonly known as the Bauschinger effect. When symmetrical shapes are machined in the annealed condition using moderate cuts and uniform stock removal, stress relieving may not be required. Compressor disks made of Ti-6Al-4V has been machined satisfactorily in this manner, conforming with dimensional requirements. In contrast, thin rings made of the same alloy could be machined at a higher production rate to more stringent dimensions by stress relieving 2 h at 540C (1000F) between, rough and final machining. Separate stress relieving may be omitted when the manufacturing sequence can be adjusted to use annealing or hardening as the stress-relieving process. For example, forging stresses may be relieved by annealing prior to machining.

The annealing of titanium and titanium alloys serves primarily to increase fracture toughness, ductility at room temperature, dimensional and thermal stability, and creep resistance. Many titanium alloys are placed in service in the annealed state. Because improvement in one or more properties is generally obtained at the expense of some other property, the annealing cycle should be selected according to the objective of the treatment. Common annealing treatments are:

Mill annealing Duplex annealing Recrystallization annealing Beta annealing

Mill annealing is a general-purpose treatment given to all mill products. It is not a full anneal and may leave traces of cold or warm working in the microstructures of heavily worked products, particularly sheet. Duplex annealing alters the shapes, sizes, and distributions of phases to those required for improved creep resistance or fracture toughness. In the duplex anneal of the Corona 5 alloy, for example, the first anneal is near the transus to globularize the deformed and to minimize its volume fraction. This is followed by a second, lower -temperature anneal to precipitate new lenticular (acicular) between the globular particles. This formation of acicular is associated with improvements in creep strength and fracture toughness. Recrystallization annealing and annealing are used to improve fracture toughness. In recrystallization annealing, the alloy is heated into the upper end of the - range, held for a time, and then cooled very slowly. In recent years, recrystallization annealing has replaced annealing for fracture critical airframe components. (Beta) Annealing. Like recrystallization annealing, annealing improves fracture toughness. Beta annealing is done at temperatures above the transus of the alloy being annealed. To prevent excessive grain growth, the temperature for annealing should be only slightly higher than the transus. Annealing times are dependent on section thickness and should be sufficient for complete transformation. Time at temperature after transformation should be held to a minimum to control grain growth. Larger sections should be fan cooled or water quenched to prevent the formation of a phase at the grain boundaries. Straightening, sizing, and flattening of titanium alloys are often necessary in order to meet dimensional requirements. The straightening of bar to close tolerances and the flattening of sheet present major problems for titanium producers and fabricators. Unlike aluminum alloys, titanium alloys are not easily straightened when cold because the high yield strength and modulus of elasticity of these alloys result in significant springback. Therefore, titanium alloys are straightened primarily by creep

straightening and/or hot straightening (hand or die), with the former being considerably more prevalent than the latter. Straightening, sizing, and flattening may be combined with annealing by the use of appropriate fixtures. The parts, in bulk or in fixtures, may be charged directly into a furnace operating at the annealing temperature. At annealing temperatures many titanium alloys have a creep resistance low enough to permit straightening during annealing. Creep straightening may be readily accomplished during the annealing and/or aging processes of most titanium alloys. However, if the annealing/aging temperature is below about 540 to 650C (1000 to 1200F), depending on the alloy, the times required to accomplish the desired creep straightening can be extended. Creep straightening is accomplished with rudimentary or sophisticated fixtures and loading systems, depending on part complexity and the degree of straightening required. Creep flattening consists of heating titanium sheet between two clean, flat sheets of steel in a furnace containing an oxidizing or inert atmosphere. Vacuum creep flattening is used to produce stress-free flat plate for subsequent machining. The plate is placed on a large, flat ceramic bed that has integral electric heating elements. Insulation is placed on top of the plate, and a plastic sheet is sealed to the frame. Stability. In - titanium alloys, thermal stability is a function of -phase transformations. During cooling from the annealing temperature, may transform and, under certain conditions and in alloys, may form a brittle intermediate phase known as . A stabilization annealing treatment is designed to produce a stable phase capable of resisting further transformation when exposed to elevated temperatures in service. Alpha-beta alloys that are lean in , such as Ti-6Al-4V, can be air cooled from the annealing temperature without impairing their stability. To obtain maximum creep resistance and stability in the near- alloys Ti-8Al-1 Mo-1 V and Ti-6Al-2Sn-4Zr-2Mo, a duplex annealing treatment is employed. This treatment begins with solution annealing at a temperature high in the - range, usually 25 to 55C (50 to 100F) below the transus for Ti -8Al1Mo-1Vand 15 to 25C (25 to 50F) below the - transus for Ti-6Al-2Sn-4Zr-2Mo.

Solution Treating and Aging

A wide range of strength levels can be obtained in - or alloys by solution treating and aging. With the exception of the unique Ti-2.5Cu alloy (which relies on strengthening from the classic age-hardening reaction of Ti2Cu precipitation similar to the formation of Guinier-Preston zones in aluminum alloys), the origin of heat-treating responses of titanium alloys lies in the instability of the high-temperature phase at lower temperatures. Heating an - alloy to the solution-treating temperature produces a higher ratio of phase. This partitioning of phases is maintained by quenching; on subsequent aging, decomposition of the unstable phase occurs, providing high strength. Commercial alloys generally supplied in the solution-treated condition, and need only to be aged. After being cleaned, titanium components should be loaded into fixtures or racks that will permit free access to the heating and quenching media. Thick and thin components of the same alloy may be solution treated together, but the time at temperature is determined by the thickest section. Time/temperature combinations for solution treating are given in Table 1. A load may be charged directly into a furnace operating at the solution-treating temperature. Although preheating is not essential, it may be used to minimize the distortion of complex parts. Table 1. Recommended solution and aging treatments for titanium alloy


Solution temperature [C]

Solution Aging Cooling time temperature rate [h] [C]

Aging time [h]

or near- alloys Ti-8Al-1Mo-1V Ti-2.5Cu (IMI 230) 980-1010 795-815 1 0,5-1 Oil or water Air or 565-595 390-410


water 465-485 Ti-6Al-2Sn-4Zr-2Mo Ti-6Al-5Zr-0.5Mo0.2Si (IMI 685) Ti-5.5Al-3.5Sn-3Zr1Nb-0.3Mo-0.3Si (IMI 829) Ti-5.8Al-4Sn-3.5Zr0.7Nb-0.5Mo-0.3Si (IMI 834) - alloys Ti-6Al-4V 955-970 955-970 Ti-6al-6V-2Sn (Cu+Fe) Ti-6Al-2Sn-4Zr-6Mo Ti-4Al-4Mo-2Sn-0.5Si (IMI 550) Ti-4Al-4Mo-4Sn-0.5Si (IMI 551) Ti-5Al-2Sn-2Zr-4Mo4Cr Ti-6Al-2Sn-2Zr-2Mo2Cr-0.25Si or near- alloys Ti-13V-11Cr-3Al Ti-11.5Mo-6Zr-4.5Sn (Beta III) Ti-3Al-8V-6Cr-4Mo775-800 1/4-1 Air or water Air or water Water 425-480 885-910 845-890 890-910 1 1 1 1 0.5-1 Water Water Water Air Air 480-595 705-760 480-595 580-605 490-510 955-980 1040-1060 1 0,5-1 Air Oil 595 540-560

(step 1) 8 (step2) 8 24



Air or oil





4-8 2-4 4-8 4-8 24















690-790 815-925

1/8-1 1

480-595 455-540

8-32 8-24

4Zr (Beta C) Ti-10V-2Fe-3Al Ti-15V-3Al-3Cr-3Sn 760-780 790-815 1 1/4 Water Air 495-525 510-595 8 8-24

Solution treating of titanium alloys generally involves heating to temperatures either slightly above or slightly below the transus temperature. The solution-treating temperature selected depends on the alloy type and practical considerations briefly described below. (Beta) alloys are normally obtained from producers in the solution-treated condition. If reheating is required, soak times should be only as long as necessary to obtain complete solutioning. Solution-treating temperatures for alloys are above the transus; because no second phase is present, grain growth can proceed rapidly. - (Alpha-beta) alloys. Selection of a solution-treatment temperature for - alloys is based on the combination of mechanical properties desired after aging. A change in the solution-treating temperature of - alloys alters the amounts of phase and consequently changes the response to aging. To obtain high strength with adequate ductility, it is necessary to solution treat at a temperature high in the - field, normally 25 to 85C (50 to 150F) below the transus of the alloy. If high fracture toughness or improved resistance to stress corrosion is required, annealing or solution treating may be desirable. However, heat treating - alloys in the range causes a significant loss in ductility. These alloys are usually solution heat treated below the transus to obtain an optimum balance of ductility, fracture toughness, creep, and stress rupture properties.

I know the Greek alphabet well, exclaimed the heat treater. Alpha, beta, alpha-beta, gamma and so on.

Oh, you must process titanium alloys, surmised the scholar. How did he know? Lets learn more. Titanium has many attributes that are useful in todays modern society. It is a relatively lightweight, corrosion-resistant structural material that can be strengthened dramatically through alloying and, in some cases, by heat treatment. Among its many advantages for aerospace, military and commercial: good strength-to-weight ratio, low density, low coefficient of thermal expansion, good corrosion resistance, good oxidation resistance at intermediate temperatures, good toughness and (relatively) low heat-treatment temperatures.

Alloy Classification
Titanium alloys are typically classified as pure titanium, alpha, beta and alpha-beta alloys. There are also so-called near-alpha-phase and near-beta-phase (i.e. metastable beta) alloys. Under equilibrium conditions, pure titanium and alpha (a) phase have hexagonal-closedpacked (HCP) structures up to 882C (1620F). Above this temperature, they transform to beta (b) phase having a body-centered-cubic (BCC) structure up to the alloys melting point. Near-alpha alloys typically have a small amount of beta-phase (1-2%) stabilizing elements. In

near-beta alloys, significant additions of beta stabilizer suppress the Ms temperature to below ambient, and the beta phase is retained at room temperature by rapid cooling or quenching from the alpha-beta phase. The inherent properties of all these structures are quite different. Alloying elements (Fig. 1) generally stabilize one or the other of these phases. The alpha phase is stabilized by aluminum, gallium, germanium, boron, carbon, oxygen and nitrogen, while the beta phase is stabilized by molybdenum, vanadium, tantalum, niobium, iron and hydrogen. The boundary between the alpha and beta phase and the two-phase alpha-beta region (Fig. 2) is called the alpha transus and beta transus respectively. The beta-stabilized system has Ms and Mf temperatures associated with it. The titanium grades most commonly used have compositional specications determined by ASTM E120 (Standard Test Methods for Chemical Analysis of Titanium and Titanium Alloys) for the commercially important alloys. Military specications are found under MILT-9046 and MIL-T-9047, and aerospace material specications for bar, sheet, tubing and wire are under AMS specication numbers 4900-4980. In addition, large aircraft companies have their own set of alloy specications. Because titanium alloys are used in a variety of applications, several different material and quality standards are specied. Among these are ASTM, ASME, AMS, the U.S. military and a number of proprietary sources. Titanium alloys may be divided into two principal categories: corrosion resistant and structural.[3-9] The corrosion-resistant alloys are generally based on a single-phase (alpha) with dilute additions of solid-solution strengthening and alpha-stabilizing elements such as oxygen (interstitial), palladium, ruthenium and aluminum (substitutional). These alloys are used in the chemical, energy, paper and food-processing industries to produce highly corrosion-resistant tubing, heat exchangers, valve housings and containers. The single-phase alpha alloys provide excellent corrosion resistance, good weldability, and easy processing and fabrication but a relatively low strength. The beta phase is stabilized by additions such as molybdenum, vanadium, niobium, iron (substitutional) and hydrogen (interstitial). A dispersion of alpha in the beta matrix along with solid-solution strengthening of both the alpha and beta phases lead to higher-strength alloys referred to as structural alloys. The structural alloys can be divided into four categories: the near-alpha alloys, the alpha-beta alloys, the beta alloys and the titanium aluminide (ordered) intermetallics (based on TixAl where x = 1 or 3). With titanium alloys used in structural applications, optimization of mechanical properties is very important. Therefore, processing and microstructure control are critical.

Heat Treatments
Not all heat treatments are applicable to titanium alloys because of the differences in composition and microstructure. Alpha alloys generally are not heat treatable, having medium strength, good notch toughness and good creep resistance.

The response of titanium alloys to heat treatment depends on their composition and the effect of heat treatment on the alpha-beta phase balance. Strength of annealed alloys increases gradually and linearly with increasing alloy contents. Alloys of the beta type respond to heat treatment, are characterized by higher density than pure titanium and are more easily fabricated. The purpose of alloying to promote the beta phase is either to form an all-beta-phase alloy having commercially useful qualities, to form alloys that have duplex alpha and beta structure to enhance heat-treatment response (i.e. changing the alpha and beta volume ratio) or to use beta eutectoid elements for intermetallic hardening. Quenching from the beta-phase field gives a martensitic transformation with improved strength (depending on composition). Rapid quenching of titanium with relatively few alloying elements from the beta-phase field gives maximum strength at Mf. For highly alloyed titanium, rapid quenching from beta-phase field gives lowest strength, but the maximum strength is obtained after aging. The most important beta alloying element is vanadium.[1] Beta and alpha-beta alloys are heat treated to enhance specific properties. The general classifications for these heat treatments include: Stress relief to reduce residual stress due to fabrication (e.g., forming, machining, welding) or heat treatment Process annealing to optimize microstructure, manufacturability, dimensional stability and service life Solution treat and age for mechanical-property development (e.g., strength, ductility, fracture toughness, creep resistance, fatigue strength)

Heat treatments specific to alpha-beta alloys[1] include stress relief; mill or full anneal; recrystallization annealing (RA); duplex annealing (DA); beta annealing (BA); solution treat and age (STA); solution treat and overage (STOA); beta solution treat and age (T STA); beta solution treat and overage (T STOA); and beta plus alpha-beta solution treat and age (TRIPLEX STA). Heat treatments applicable to metastable beta titanium alloys[1] include solution treating, sub-transus solution treating, supra-transus solution treating, direct aging, solution treat plus single age, solution treat plus duplex age and pre-age solution treat and age (PASTA). In some applications, titanium alloys have been case hardened (nitrided and carburized) to enhance certain surface properties. Laser surface alloying and ion implantation are possible but not commonly used.

In Conclusion

One of the biggest challenges faced by the heat treater is to understand and comply with the large number of specifications applicable to a particular titanium alloy grade. By way of example, some of the common AMS heat-treat specifications for Ti-6Al-4V alloys (including legacy specifications) include: AMS 2801, AMS 4901, AMS 4904, AMS 4905, AMS 4911, AMS 4928, AMS 4931, AMS 4935, AMS 4943, AMS 4945, AMS 4965, AMS 4967, AMS 4975, AMS 4979, AMS 4984, AMS-H-81200 and AMS-T-9046 to name a few. IH

References 1. Wood, J. R., and P. A. Russo, Heat Treatment of Titanium Alloys, Industrial Heating, December 2004. 2. Kirk-Othmer, Encyclopedia of Chemical Technology, Titanium and Titanium Alloys, 3rd Edition, John Wiley & Sons. 3. Molchanova, M., Phase Diagrams of Titanium Alloys, Israel Program for Scientic Translations, Jerusalem, Israel,1965. 4. Titanium Technology: Present Status and Future Trends, F. H. Froes, D. Eylon, and H. B. Bomberger (Eds.), International Titanium Association, 1985. 5. Materials Property Handbook: Titanium Alloys, R. Boyer, G. Welsch, and E. Collings, (Eds.), ASM International, 1994. 6. Donachie, M. J., Titanium, A Technical Guide, ASM International, 1988. 7. Polmear, I. J., Light Alloys, Metallurgy of the Light Metals, 3rd ed., Edward Arnold, 1996. 8. Margolin, H. and H. Neilson, Titanium Metallurgy,Modern Materials, Advances in Development and Applications, H. H. Hauser (Ed.), Academic Press, New York, vol. 2, 1960, pp. 225325. 9. Joseph, S. S. and F. H. Froes, Light Metal Age, 4-6 (11-12), 5-12, 1988. 10. Herring, D. H., Practical Aspects Related to the Heat Treatment of Titanium and Titanium Alloys, Industrial Heating, February 2007. 11. Mr. Robert Hill, Solar Atmospheres of Western Pennsylvania, private correspondence