Titanium alloy

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Titanium alloys are alloys that contain a mixture of titanium and other chemical elements. Such alloys have very high tensile strength and toughness (even at extreme temperatures). They are light in weight, have extraordinary corrosion resistance and the ability to withstand extreme temperatures. However, the high cost of both raw materials and processing limit their use to military applications, aircraft, spacecraft, bicycles, medical devices, jewelry, highly stressed components such as connecting rods on expensive sports cars and some premium sports equipment and consumer electronics.

Contents

Although "commercially pure" titanium has acceptable mechanical properties and has been used for orthopedic and dental implants, for most applications titanium is alloyed with small amounts of aluminium and vanadium, typically 6% and 4% respectively, by weight. This mixture has a solid solubility which varies dramatically with temperature, allowing it to undergo precipitation strengthening. This heat treatment process is carried out after the alloy has been worked into its final shape but before it is put to use, allowing much easier fabrication of a high-strength product.

Categories

Titanium alloys are generally classified into four main categories: [1]

Beta-titanium

Beta titanium alloys exhibit the BCC allotropic form of titanium (called beta). Elements used in this alloy are one or more of the following other than titanium in varying amounts. These are molybdenum, vanadium, niobium, tantalum, zirconium, manganese, iron, chromium, cobalt, nickel, and copper.

The titanium alloys have excellent formability and can be easily welded. [4]

Beta titanium is nowadays largely utilized in the orthodontic field and was adopted for orthodontics use in the 1980s. This type of alloy replaced stainless steel for certain uses, as stainless steel had dominated orthodontics since the 1960s. It has strength/modulus of elasticity ratios almost twice those of 18-8 austenitic stainless steel, larger elastic deflections in springs, and reduced force per unit displacement 2.2 times below those of stainless steel appliances.

Some of the beta titanium alloys can convert to hard and brittle hexagonal omega-titanium at cryogenic temperatures [5] or under influence of ionizing radiation. [6]

Transition temperature

The crystal structure of titanium at ambient temperature and pressure is close-packed hexagonal α phase with a c/a ratio of 1.587. At about 890 °C, the titanium undergoes an allotropic transformation to a body-centred cubic β phase which remains stable to the melting temperature.

Some alloying elements, called alpha stabilizers, raise the alpha-to-beta transition temperature, [lower-roman 1] while others (beta stabilizers) lower the transition temperature. Aluminium, gallium, germanium, carbon, oxygen and nitrogen are alpha stabilizers. Molybdenum, vanadium, tantalum, niobium, manganese, iron, chromium, cobalt, nickel, copper and silicon are beta stabilizers. [7]

Properties

Generally, beta-phase titanium is the more ductile phase and alpha-phase is stronger yet less ductile, due to the larger number of slip planes in the bcc structure of the beta-phase in comparison to the hcp alpha-phase. Alpha-beta-phase titanium has a mechanical property which is in between both.

Titanium dioxide dissolves in the metal at high temperatures, and its formation is very energetic. These two factors mean that all titanium except the most carefully purified has a significant amount of dissolved oxygen, and so may be considered a Ti–O alloy. Oxide precipitates offer some strength (as discussed above), but are not very responsive to heat treatment and can substantially decrease the alloy's toughness.

Many alloys also contain titanium as a minor additive, but since alloys are usually categorized according to which element forms the majority of the material, these are not usually considered to be "titanium alloys" as such. See the sub-article on titanium applications. Commercial (99.2% purity) grades of titanium have an ultimate tensile strength of about 434 MPa, equal to that of common, low-grade steel alloys, but are less dense. Titanium is 60% denser than aluminium, but more than twice as strong as the most commonly used 6061-T6 aluminium alloy. The titanium used for surface alloying of AISI304 stainless steel was CP-Ti, grade2, 300µm thick sheet. [8]

Titanium alone is a strong, light metal. It is stronger than common, low-carbon steels, but 45% lighter. It is also twice as strong as weak aluminium alloys but only 60% heavier. Titanium has outstanding corrosion resistance to seawater, and thus is used in propeller shafts, rigging and other parts of boats that are exposed to seawater. Titanium and its alloys are used in airplanes, missiles, and rockets where strength, low weight, and resistance to high temperatures are important. Further, since titanium does not react within the human body, it and its alloys are used in artificial joints, screws, and plates for fractures, and for other biological implants. See Titanium#Orthopedic implants.

Titanium grades

The ASTM International standard on titanium and titanium alloy seamless pipe references the following alloys, requiring the following treatment:

"Alloys may be supplied in the following conditions: Grades 5, 23, 24, 25, 29, 35, or 36 annealed or aged; Grades 9, 18, 28, or 38 cold-worked and stress-relieved or annealed; Grades 9, 18, 23, 28, or 29 transformed-beta condition; and Grades 19, 20, or 21 solution-treated or solution-treated and aged." [9]

"Note 1—H grade material is identical to the corresponding numeric grade (that is, Grade 2H = Grade 2) except for the higher guaranteed minimum UTS, and may always be certified as meeting the requirements of its corresponding numeric grade. Grades 2H, 7H, 16H, and 26H are intended primarily for pressure vessel use." [9]

"The H grades were added in response to a user association request based on its study of over 5200 commercial Grade 2, 7, 16, and 26 test reports, where over 99% met the 58 ksi minimum UTS." [9]

Grade 1
is the most ductile and softest titanium alloy. It is a good solution for cold forming and corrosive environments. ASTM/ASME SB-265 provides the standards for commercially pure titanium sheet and plate. [10]
Grade 2
Unalloyed titanium, standard oxygen.
Grade 2H
Unalloyed titanium (Grade 2 with 58 ksi minimum UTS).
Grade 3
Unalloyed titanium, medium oxygen.
Grades 1-4 are unalloyed and considered commercially pure or "CP". Generally the tensile and yield strength goes up with grade number for these "pure" grades. The difference in their physical properties is primarily due to the quantity of interstitial elements. They are used for corrosion resistance applications where cost, ease of fabrication, and welding are important.
Grade 5 also known as Ti6Al4V, Ti-6Al-4V or Ti 6-4
not to be confused with Ti-6Al-4V-ELI (Grade 23), is the most commonly used alloy. It has a chemical composition of 6% aluminum, 4% vanadium, 0.25% (maximum) iron, 0.2% (maximum) oxygen, and the remainder titanium. [11] It is significantly stronger than commercially pure titanium (grades 1-4) while having the same stiffness and thermal properties (excluding thermal conductivity, which is about 60% lower in Grade 5 Ti than in CP Ti). [12] Among its many advantages, it is heat treatable. This grade is an excellent combination of strength, corrosion resistance, weld and fabricability.

"This alpha-beta alloy is the workhorse alloy of the titanium industry. The alloy is fully heat treatable in section sizes up to 15 mm and is used up to approximately 400 °C (750 °F). Since it is the most commonly used alloy – over 70% of all alloy grades melted are a sub-grade of Ti6Al4V, its uses span many aerospace airframe and engine component uses and also major non-aerospace applications in the marine, offshore and power generation industries in particular." [13]

"Applications: Blades, discs, rings, airframes, fasteners, components. Vessels, cases, hubs, forgings. Biomedical implants." [11]

Generally, Ti-6Al-4V is used in applications up to 400 degrees Celsius. It has a density of roughly 4420 kg/m3, Young's modulus of 120 GPa, and tensile strength of 1000 MPa. [14] By comparison, annealed type 316 stainless steel has a density of 8000 kg/m3, modulus of 193 GPa, and tensile strength of 570 MPa. [15] Tempered 6061 aluminium alloy has a density of 2700 kg/m3, modulus of 69 GPa, and tensile strength of 310 MPa, respectively. [16]
Ti-6Al-4V standard specifications include: [17]
  • AMS: 4911, 4928, 4965, 4967, 6930, 6931, T-9046, T9047
  • ASTM: B265, B348, F1472
  • MIL: T9046 T9047
  • DMS: 1592, 1570
Grade 6
contains 5% aluminium and 2.5% tin. It is also known as Ti-5Al-2.5Sn. This alloy is used in airframes and jet engines due to its good weldability, stability and strength at elevated temperatures. [18]
Grade 7
contains 0.12 to 0.25% palladium. This grade is similar to Grade 2. The small quantity of palladium added gives it enhanced crevice corrosion resistance at low temperatures and high pH. [19]
Grade 7H
is identical to Grade 7 with enhanced corrosion resistance. [19]
Grade 9
contains 3.0% aluminium and 2.5% vanadium. This grade is a compromise between the ease of welding and manufacturing of the "pure" grades and the high strength of Grade 5. It is commonly used in aircraft tubing for hydraulics and in athletic equipment.
Grade 11
contains 0.12 to 0.25% palladium. This grade has enhanced corrosion resistance. [20]
Grade 12
contains 0.3% molybdenum and 0.8% nickel. [20]
Grades 13, 14, and 15
all contain 0.5% nickel and 0.05% ruthenium.
Grade 16
contains 0.04 to 0.08% palladium. This grade has enhanced corrosion resistance.
Grade 16H
contains 0.04 to 0.08% palladium.
Grade 17
contains 0.04 to 0.08% palladium. This grade has enhanced corrosion resistance.[ citation needed ]
Grade 18
contains 3% aluminium, 2.5% vanadium and 0.04 to 0.08% palladium. This grade is identical to Grade 9 in terms of mechanical characteristics. The added palladium gives it increased corrosion resistance.[ citation needed ]
Grade 19
contains 3% aluminium, 8% vanadium, 6% chromium, 4% zirconium, and 4% molybdenum.
Grade 20
contains 3% aluminium, 8% vanadium, 6% chromium, 4% zirconium, 4% molybdenum and 0.04% to 0.08% palladium.
Grade 21
contains 15% molybdenum, 3% aluminium, 2.7% niobium, and 0.25% silicon.
Grade 23 also known as Ti-6Al-4V-ELI or TAV-ELI
contains 6% aluminium, 4% vanadium, 0.13% (maximum) Oxygen. ELI stands for Extra Low Interstitial. Reduced interstitial elements oxygen and iron improve ductility and fracture toughness with some reduction in strength. [20] TAV-ELI is the most commonly used medical implant-grade titanium alloy. [20] [21]
Ti-6Al-4V-ELI standard specifications include: [21]
  • AMS: 4907, 4930, 6932, T9046, T9047
  • ASTM: B265, B348, F136
  • MIL: T9046 T9047
Grade 24
contains 6% aluminium, 4% vanadium and 0.04% to 0.08% palladium.
Grade 25
contains 6% aluminium, 4% vanadium and 0.3% to 0.8% nickel and 0.04% to 0.08% palladium.
Grades 26, 26H, and 27
all contain 0.08 to 0.14% ruthenium.
Grade 28
contains 3% aluminium, 2.5% vanadium and 0.08 to 0.14% ruthenium.
Grade 29
contains 6% aluminium, 4% vanadium and 0.08 to 0.14% ruthenium.
Grades 30 and 31
contain 0.3% cobalt and 0.05% palladium.
Grade 32
contains 5% aluminium, 1% tin, 1% zirconium, 1% vanadium, and 0.8% molybdenum.
Grades 33 and 34
contain 0.4% nickel, 0.015% palladium, 0.025% ruthenium, and 0.15% chromium .[ citation needed ]
Grade 35
contains 4.5% aluminium, 2% molybdenum, 1.6% vanadium, 0.5% iron, and 0.3% silicon.
Grade 36
contains 45% niobium.
Grade 37
contains 1.5% aluminium.
Grade 38
contains 4% aluminium, 2.5% vanadium, and 1.5% iron. This grade was developed in the 1990s for use as an armor plating. The iron reduces the amount of Vanadium needed as a beta stabilizer. Its mechanical properties are very similar to Grade 5, but has good cold workability similar to grade 9. [22]

Heat treatment

Titanium alloys are heat treated for a number of reasons, the main ones being to increase strength by solution treatment and aging as well as to optimize special properties, such as fracture toughness, fatigue strength and high temperature creep strength.

Alpha and near-alpha alloys cannot be dramatically changed by heat treatment. Stress relief and annealing are the processes that can be employed for this class of titanium alloys. The heat treatment cycles for beta alloys differ significantly from those for the alpha and alpha-beta alloys. Beta alloys can not only be stress relieved or annealed, but also can be solution treated and aged. The alpha-beta alloys are two-phase alloys, comprising both alpha and beta phases at room temperature. Phase compositions, sizes, and distributions of phases in alpha-beta alloys can be manipulated within certain limits by heat treatment, thus permitting tailoring of properties.

Alpha and near-alpha alloys
The micro-structure of alpha alloys cannot be strongly manipulated by heat treatment since alpha alloys undergo no significant phase change. As a result, high strength can not be acquired for the alpha alloys by heat treatment. Yet, alpha and near-alpha titanium alloys can be stress relieved and annealed.
Alpha-beta alloys
By working as well as heat treatment of alpha-beta alloys below or above the alpha-beta transition temperature, large micro-structural changes can be achieved. This may give a substantial hardening of the material. Solution treatment plus aging is used to produce maximum strengths in alpha-beta alloys. Also, other heat treatments, including stress-relief heat treatments, are practiced for this group of titanium alloys as well.
Beta alloys
In commercial beta alloys, stress-relieving and aging treatments can be combined.

Titanium alloys by application or use

Aerospace structures

Architectural cladding

Titanium alloys used biomedically

Titanium plate for wrist Titanium plaatje voor pols.jpg
Titanium plate for wrist

Titanium alloys have been extensively used for the manufacturing of metal orthopedic joint replacements and bone plate surgeries. They are normally produced from wrought or cast bar stock by CNC, CAD-driven machining, or powder metallurgy production. Each of these techniques comes with inherent advantages and disadvantages. Wrought products come with an extensive material loss during machining into the final shape of the product and for cast samples the acquirement of a product in its final shape somewhat limits further processing and treatment (e.g. precipitation hardening), yet casting is more material effective. Traditional powder metallurgy methods are also more material efficient, yet acquiring fully dense products can be a common issue. [23]

With the emergence of solid freeform fabrication (3D printing) the possibility to produce custom-designed biomedical implants (e.g. hip joints) has been realized. While it is not applied currently on a larger scale, freeform fabrication methods offers the ability to recycle waste powder (from the manufacturing process) and makes for selectivity tailoring desirable properties and thus the performance of the implant. Electron Beam Melting (EBM) and Selective Laser Melting (SLM) are two methods applicable for freeform fabrication of Ti-alloys. Manufacturing parameters greatly influence the microstructure of the product, where e.g. a fast cooling rate in combination with low degree of melting in SLM leads to the predominant formation of martensitic alpha-prime phase, giving a very hard product. [23]

Ti-6Al-4V / Ti-6Al-4V-ELI
This alloy has good biocompatibility, and is neither cytotoxic nor genotoxic. [24] Ti-6Al-4V suffers from poor shear strength and poor surface wear properties in certain loading conditions: [11]

Bio compatibility: Excellent, especially when direct contact with tissue or bone is required. Ti-6Al-4V's poor shear strength makes it undesirable for bone screws or plates. It also has poor surface wear properties and tends to seize when in sliding contact with itself and other metals. Surface treatments such as nitriding and oxidizing can improve the surface wear properties. [11]

Ti-6Al-7Nb
This alloy was developed as a biomedical replacement for Ti-6Al-4V, because Ti-6Al-4V contains vanadium, an element that has demonstrated cytotoxic outcomes when isolated. [25] :1 Ti-6Al-7Nb contains 6% aluminium and 7% niobium. [25] :18

Ti6Al7Nb is a dedicated high strength titanium alloy with excellent biocompatibility for surgical implants. Used for replacement hip joints, it has been in clinical use since early 1986. [26]

Related Research Articles

Metal Type of material

A metal is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typically malleable or ductile. A metal may be a chemical element such as iron; an alloy such as stainless steel; or a molecular compound such as polymeric sulfur nitride.

Stainless steel steel alloy resistant to corrosion

Stainless steel is a family of iron-based alloys that contain a minimum of approximately 11% chromium, a composition that prevents the iron from rusting, as well as providing heat-resistant properties. Different types of stainless steel include the elements carbon, nitrogen, aluminium, silicon, sulfur, titanium, nickel, copper, selenium, niobium, and molybdenum. Specific types of stainless steel are often designated by a three-digit number, e.g., 304 stainless.

Titanium Chemical element with atomic number 22

Titanium is a chemical element with the symbol Ti and atomic number 22. It is a lustrous transition metal with a silver color, low density, and high strength. Titanium is resistant to corrosion in sea water, aqua regia, and chlorine.

Brazing High-temperature soldering; metal-joining technique by high-temperature molten metal filling

Brazing is a metal-joining process in which two or more metal items are joined together by melting and flowing a filler metal into the joint, the filler metal having a lower melting point than the adjoining metal.

High-strength low-alloy steel

High-strength low-alloy steel (HSLA) is a type of alloy steel that provides better mechanical properties or greater resistance to corrosion than carbon steel. HSLA steels vary from other steels in that they are not made to meet a specific chemical composition but rather specific mechanical properties. They have a carbon content between 0.05–0.25% to retain formability and weldability. Other alloying elements include up to 2.0% manganese and small quantities of copper, nickel, niobium, nitrogen, vanadium, chromium, molybdenum, titanium, calcium, rare earth elements, or zirconium. Copper, titanium, vanadium, and niobium are added for strengthening purposes. These elements are intended to alter the microstructure of carbon steels, which is usually a ferrite-pearlite aggregate, to produce a very fine dispersion of alloy carbides in an almost pure ferrite matrix. This eliminates the toughness-reducing effect of a pearlitic volume fraction yet maintains and increases the material's strength by refining the grain size, which in the case of ferrite increases yield strength by 50% for every halving of the mean grain diameter. Precipitation strengthening plays a minor role, too. Their yield strengths can be anywhere between 250–590 megapascals (36,000–86,000 psi). Because of their higher strength and toughness HSLA steels usually require 25 to 30% more power to form, as compared to carbon steels.

Refractory metals are a class of metals that are extraordinarily resistant to heat and wear. The expression is mostly used in the context of materials science, metallurgy and engineering. The definition of which elements belong to this group differs. The most common definition includes five elements: two of the fifth period and three of the sixth period. They all share some properties, including a melting point above 2000 °C and high hardness at room temperature. They are chemically inert and have a relatively high density. Their high melting points make powder metallurgy the method of choice for fabricating components from these metals. Some of their applications include tools to work metals at high temperatures, wire filaments, casting molds, and chemical reaction vessels in corrosive environments. Partly due to the high melting point, refractory metals are stable against creep deformation to very high temperatures.

In modern Western body piercing, a wide variety of materials are used. Some cannot be autoclaved, and others may induce allergic reactions, or harbour bacteria. Certain countries, such as those belonging to the EU, have legal regulations specifying which materials can be used in new piercings.

Maraging steel steel

Maraging steels are steels that are known for possessing superior strength and toughness without losing ductility. Aging refers to the extended heat-treatment process. These steels are a special class of low-carbon ultra-high-strength steels that derive their strength not from carbon, but from precipitation of intermetallic compounds. The principal alloying element is 15 to 25 wt% nickel. Secondary alloying elements, which include cobalt, molybdenum and titanium, are added to produce intermetallic precipitates. Original development was carried out on 20 and 25 wt% Ni steels to which small additions of aluminium, titanium, and niobium were made; a rise in the price of cobalt in the late 1970s led to the development of cobalt-free maraging steels.

Ferroalloy refers to various alloys of iron with a high proportion of one or more other elements such as manganese (Mn), aluminium (Al), or silicon (Si). They are used in the production of steels and alloys. The alloys impart distinctive qualities to steel and cast iron or serve important functions during production and are, therefore, closely associated with the iron and steel industry, the leading consumer of ferroalloys. The leading producers of ferroalloys in 2014 were China, South Africa, India, Russia and Kazakhstan, which accounted for 84% of the world production. World production of ferroalloys was estimated as 52.8 million tonnes in 2015.

Superalloy alloy with higher durability than normal metals

A superalloy, or high-performance alloy, is an alloy with the ability to operate at a high fraction of its melting point. Several key characteristics of a superalloy are excellent mechanical strength, resistance to thermal creep deformation, good surface stability, and resistance to corrosion or oxidation.

Orthodontic archwire

An archwire in orthodontics is a wire conforming to the alveolar or dental arch that can be used with dental braces as a source of force in correcting irregularities in the position of the teeth. An archwire can also be used to maintain existing dental positions; in this case it has a retentive purpose.

Alloy steel steel that is alloyed with a variety of elements

Alloy steel is steel that is alloyed with a variety of elements in total amounts between 1.0% and 50% by weight to improve its mechanical properties. Alloy steels are broken down into two groups: low alloy steels and high alloy steels. The difference between the two is disputed. Smith and Hashemi define the difference at 4.0%, while Degarmo, et al., define it at 8.0%. Most commonly, the phrase "alloy steel" refers to low-alloy steels.

Aluminium alloy Alloy in which aluminium is the predominant metal

Aluminium alloys are alloys in which aluminium (Al) is the predominant metal. The typical alloying elements are copper, magnesium, manganese, silicon, tin and zinc. There are two principal classifications, namely casting alloys and wrought alloys, both of which are further subdivided into the categories heat-treatable and non-heat-treatable. About 85% of aluminium is used for wrought products, for example rolled plate, foils and extrusions. Cast aluminium alloys yield cost-effective products due to the low melting point, although they generally have lower tensile strengths than wrought alloys. The most important cast aluminium alloy system is Al–Si, where the high levels of silicon (4.0–13%) contribute to give good casting characteristics. Aluminium alloys are widely used in engineering structures and components where light weight or corrosion resistance is required.

Titanium Beta C refers to Ti Beta-C, a trademark for an alloy of titanium originally filed by RTI International. It is a metastable "beta alloy" which was originally developed in the 1960s; Ti-3Al-8V-6Cr-4Mo-4Zr, nominally 3% aluminum, 8% vanadium, 6% chromium, 4% molybdenum, 4% zirconium and balance (75%): titanium.

Titanium ring

Titanium rings are jewelry rings or bands which have been primarily constructed from titanium. The actual compositions of titanium can vary, such as "commercial pure" or "aircraft grade", and titanium rings are often crafted in combination with other materials, such as gemstones and traditional jewelry metals. Even with these variations in composition and materials, titanium rings are commonly referred to as such if they contain any amount of titanium.

Ti-6Al-4V, also sometimes called TC4 or Ti64, is an alpha-beta titanium alloy with a high strength-to-weight ratio and excellent corrosion resistance. It is one of the most commonly used titanium alloys and is applied in a wide range of applications where low density and excellent corrosion resistance are necessary such as e.g. aerospace industry and biomechanical applications.

Ti-6Al-7Nb is an alpha-beta titanium alloy first synthesized in 1977 containing 6% aluminum and 7% niobium. It features high strength and has similar properties as the cytotoxic vanadium containing alloy Ti-6Al-4V. Ti-6Al-7Nb is used as a material for hip protheses. Ti―6Al―7Nb is one of the titanium alloys that built of hexagonal α phase and regular body-centred phase β. The alloy is characterized by added advantageous mechanical properties, it has higher corrosion resistance and biotolerance in relation to Ti-6Al-4V alloys.

Titanium adhesive bonding is an engineering process used in the aerospace industry, medical-device manufacture and elsewhere. Titanium alloy is often used in medical and military applications because of its strength, weight, and corrosion resistance characteristics. In implantable medical devices, titanium is used because of its biocompatibility and its passive, stable oxide layer. Also, titanium allergies are rare and in those cases mitigations like Parylene coating are used. In the aerospace industry titanium is often bonded to save cost, touch times, and the need for mechanical fasteners. In the past, Russian submarines' hulls were completely made of titanium because the non-magnetic nature of the material went undetected by the defense technology at that time. Bonding adhesive to titanium requires preparing the surface beforehand, and there is not a single solution for all applications. For example, etchant and chemical methods are not biocompatible and cannot be employed when the device will come into contact with blood and tissue. Mechanical surface roughness techniques like sanding and laser roughening may make the surface brittle and create micro-hardness regions that would not be suitable for cyclic loading found in military applications. Air oxidation at high temperatures will produce a crystalline oxide layer at a lower investment cost, but the increased temperatures can deform precision parts. The type of adhesive, thermosetting or thermoplastic, and curing methods are also factors in titanium bonding because of the adhesive's interaction with the treated oxide layer. Surface treatments can also be combined. For example, a grit blast process can be followed by a chemical etch and a primer application.

References

Notes
  1. In a titanium or titanium alloy, alpha-to-beta transition temperature is the temperature above which the beta phase becomes thermodynamically favorable.
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