Titanium nitride

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Titanium nitride
Titanium nitride TiN.jpg
Titanium-nitride-crystal-3D-vdW.png
Names
IUPAC name
Titanium nitride
Other names
Titanium(III) nitride
Identifiers
3D model (JSmol)
ECHA InfoCard 100.042.819 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 247-117-5
PubChem CID
UNII
  • InChI=1S/N.Ti
  • N#[Ti]
Properties
TiN
Molar mass 61.874 g/mol
AppearanceBrown as a pure solid, coating of golden color
Odor Odorless
Density 5.21 g/cm3 [1]
Melting point 2,947 °C (5,337 °F; 3,220 K) [1]
insoluble
+38×10−6 emu/mol
Thermal conductivity 29 W/(m·K) (323 K) [2]
Structure [3]
Face-centered cubic (FCC), cF8
Fm3m, No. 225
a = 0.4241 nm
4
Octahedral
Thermochemistry
24 J/(K·mol) (500 K) [2]
Std molar
entropy
(S298)
−95.7 J/(K·mol) [4]
−336 kJ/mol [4]
Related compounds
Related coating
Titanium aluminum nitride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Titanium nitride (TiN; sometimes known as tinite) is an extremely hard ceramic material, often used as a physical vapor deposition (PVD) coating on titanium alloys, steel, carbide, and aluminium components to improve the substrate's surface properties.

Contents

Applied as a thin coating, TiN is used to harden and protect cutting and sliding surfaces, for decorative purposes (for its golden appearance), and as a non-toxic exterior for medical implants. In most applications a coating of less than 5 micrometres (0.00020 in) is applied.

Characteristics

TiN has a Vickers hardness of 1800–2100, hardness of 31 ± 4 GPa, [5] a modulus of elasticity of 550 ± 50 GPa, [5] a thermal expansion coefficient of 9.35×10−6 K−1, and a superconducting transition temperature of 5.6 K. [6] [5]

TiN will oxidize at 800 °C in a normal atmosphere. TiN has a brown color, and appears gold when applied as a coating. It is chemically stable at 20 °C, according to laboratory tests, but can be slowly attacked by concentrated acid solutions with rising temperatures. [6] Depending on the substrate material and surface finish, TiN will have a coefficient of friction ranging from 0.4 to 0.9 against another TiN surface (non-lubricated). The typical TiN formation has a crystal structure of NaCl-type with a roughly 1:1 stoichiometry; TiNx compounds with x ranging from 0.6 to 1.2 are, however, thermodynamically stable. [7]

TiN becomes superconducting at cryogenic temperatures, with critical temperature up to 6.0 K for single crystals. [8] Superconductivity in thin-film TiN has been studied extensively, with the superconducting properties strongly varying depending on sample preparation, up to complete suppression of superconductivity at a superconductor-insulator transition. [9] A thin film of TiN was chilled to near absolute zero, converting it into the first known superinsulator, with resistance suddenly increasing by a factor of 100,000. [10]

Natural occurrence

Osbornite is a very rare natural form of titanium nitride, found almost exclusively in meteorites. [11] [12]

Uses

Titanium nitride coating.jpg
TiN-coated drill bit
Paraframe.jpg
Dark gray TiCN coating on a Gerber pocketknife

A well-known use for TiN coating is for edge retention and corrosion resistance on machine tooling, such as drill bits and milling cutters, often improving their lifetime by a factor of three or more. [13]

Because of the metallic gold color of TiN, this material is used to coat costume jewelry and automotive trim for decorative purposes. TiN is also widely used as a top-layer coating, usually with nickel (Ni) or chromium (Cr) plated substrates, on consumer plumbing fixtures and door hardware. As a coating it is used in aerospace and military applications and to protect the sliding surfaces of suspension forks of bicycles and motorcycles as well as the shock shafts of radio controlled cars. TiN is also used as a protective coating on the moving parts of many rifles and semi automatic firearms, as it is extremely durable. As well as being durable, it is also extremely smooth, making removing the carbon build up extremely easy. TiN is non-toxic, meets FDA guidelines, and has seen use in medical devices such as scalpel blades and orthopedic bone saw blades, where sharpness and edge retention are important. [14] TiN coatings have also been used in implanted prostheses (especially hip replacement implants) and other medical implants.

Though less visible, thin films of TiN are also used in microelectronics, where they serve as a conductive connection between the active device and the metal contacts used to operate the circuit, while acting as a diffusion barrier to block the diffusion of the metal into the silicon. In this context, TiN is classified as a "barrier metal" (electrical resistivity ~ 25 µΩ·cm [2] ), even though it is clearly a ceramic from the perspective of chemistry or mechanical behavior. Recent chip design in the 45 nm technology and beyond also makes use of TiN as a "metal" for improved transistor performance. In combination with gate dielectrics (e.g. HfSiO) that have a higher permittivity compared to standard SiO2 the gate length can be scaled down with low leakage, higher drive current and the same or better threshold voltage. [15] Additionally, TiN thin films are currently under consideration for coating zirconium alloys for accident-tolerant nuclear fuels. [16] [17] It is also used as a coating on some compression driver diaphragms to improve performance.

Owing to their high biostability, TiN layers may also be used as electrodes in bioelectronic applications [18] like in intelligent implants or in-vivo biosensors that have to withstand the severe corrosion caused by body fluids. TiN electrodes have already been applied in the subretinal prosthesis project [19] as well as in biomedical microelectromechanical systems (BioMEMS). [20]

Fabrication

Titanium nitride (TiN) coated punches using cathodic arc deposition technique TiNCoatedPunches NanoShieldPVD Thailand.JPG
Titanium nitride (TiN) coated punches using cathodic arc deposition technique

The most common methods of TiN thin film creation are physical vapor deposition (PVD, usually sputter deposition, cathodic arc deposition or electron beam heating) and chemical vapor deposition (CVD). [21] In both methods, pure titanium is sublimed and reacted with nitrogen in a high-energy, vacuum environment. TiN film may also be produced on Ti workpieces by reactive growth (for example, annealing) in a nitrogen atmosphere. PVD is preferred for steel parts because the deposition temperatures exceeds the austenitizing temperature of steel. TiN layers are also sputtered on a variety of higher melting point materials such as stainless steels, titanium and titanium alloys. [22] Its high Young's modulus (values between 450 and 590 GPa have been reported in the literature [23] ) means that thick coatings tend to flake away, making them much less durable than thin ones. Titanium nitride coatings can also be deposited by thermal spraying whereas TiN powders are produced by nitridation of titanium with nitrogen or ammonia at 1200 °C. [6]

Bulk ceramic objects can be fabricated by packing powdered metallic titanium into the desired shape, compressing it to the proper density, then igniting it in an atmosphere of pure nitrogen. The heat released by the chemical reaction between the metal and gas is sufficient to sinter the nitride reaction product into a hard, finished item. See powder metallurgy.

Other commercial variants

A knife with a titanium oxynitride coating Smith&Wesson CKLPR.jpg
A knife with a titanium oxynitride coating

There are several commercially used variants of TiN that have been developed since 2010, such as titanium carbon nitride (TiCN), titanium aluminium nitride (TiAlN or AlTiN), and titanium aluminum carbon nitride, which may be used individually or in alternating layers with TiN. These coatings offer similar or superior enhancements in corrosion resistance and hardness, and additional colors ranging from light gray to nearly black, to a dark, iridescent, bluish-purple, depending on the exact process of application. These coatings are becoming common on sporting goods, particularly knives and handguns, where they are used for both aesthetic and functional reasons.

As a constituent in steel

Titanium nitride is also produced intentionally, within some steels, by judicious addition of titanium to the alloy. TiN forms at very high temperatures because of its very low enthalpy of formation, and even nucleates directly from the melt in secondary steel-making. It forms discrete, micrometre-sized cubic particles at grain boundaries and triple points, and prevents grain growth by Ostwald ripening up to very high homologous temperatures. Titanium nitride has the lowest solubility product of any metal nitride or carbide in austenite, a useful attribute in microalloyed steel formulas.

Related Research Articles

<span class="mw-page-title-main">Boron nitride</span> Refractory compound of boron and nitrogen with formula BN

Boron nitride is a thermally and chemically resistant refractory compound of boron and nitrogen with the chemical formula BN. It exists in various crystalline forms that are isoelectronic to a similarly structured carbon lattice. The hexagonal form corresponding to graphite is the most stable and soft among BN polymorphs, and is therefore used as a lubricant and an additive to cosmetic products. The cubic variety analogous to diamond is called c-BN; it is softer than diamond, but its thermal and chemical stability is superior. The rare wurtzite BN modification is similar to lonsdaleite but slightly softer than the cubic form.

<span class="mw-page-title-main">Titanium</span> Chemical element, symbol Ti and atomic number 22

Titanium is a chemical element with the symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in sea water, aqua regia, and chlorine.

A cermet is a composite material composed of ceramic and metal materials.

<span class="mw-page-title-main">Titanium diboride</span> Chemical compound

Titanium diboride (TiB2) is an extremely hard ceramic which has excellent heat conductivity, oxidation stability and wear resistance. TiB2 is also a reasonable electrical conductor, so it can be used as a cathode material in aluminium smelting and can be shaped by electrical discharge machining.

<span class="mw-page-title-main">Titanium carbide</span> Chemical compound

Titanium carbide, TiC, is an extremely hard refractory ceramic material, similar to tungsten carbide. It has the appearance of black powder with the sodium chloride crystal structure.

<span class="mw-page-title-main">Superalloy</span> 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. Key characteristics of a superalloy include mechanical strength, thermal creep deformation resistance, surface stability, and corrosion and oxidation resistance.

<span class="mw-page-title-main">Zirconium nitride</span> Chemical compound

Zirconium nitride is an inorganic compound used in a variety of ways due to its properties.

<span class="mw-page-title-main">Silicon nitride</span> Compound of silicon and nitrogen

Silicon nitride is a chemical compound of the elements silicon and nitrogen. Si
3
N
4
is the most thermodynamically stable and commercially important of the silicon nitrides, and the term ″Silicon nitride″ commonly refers to this specific composition. It is a white, high-melting-point solid that is relatively chemically inert, being attacked by dilute HF and hot H
3
PO
4
. It is very hard. It has a high thermal stability with strong optical nonlinearities for all-optical applications.

<span class="mw-page-title-main">Nitriding</span> Nitrogen diffusion case-hardening process

Nitriding is a heat treating process that diffuses nitrogen into the surface of a metal to create a case-hardened surface. These processes are most commonly used on low-alloy steels. They are also used on titanium, aluminium and molybdenum.

<span class="mw-page-title-main">Physical vapor deposition</span> Method of coating solid surfaces with thin films

Physical vapor deposition (PVD), sometimes called physical vapor transport (PVT), describes a variety of vacuum deposition methods which can be used to produce thin films and coatings on substrates including metals, ceramics, glass, and polymers. PVD is characterized by a process in which the material transitions from a condensed phase to a vapor phase and then back to a thin film condensed phase. The most common PVD processes are sputtering and evaporation. PVD is used in the manufacturing of items which require thin films for optical, mechanical, electrical, acoustic or chemical functions. Examples include semiconductor devices such as thin-film solar cells, microelectromechanical devices such as thin film bulk acoustic resonator, aluminized PET film for food packaging and balloons, and titanium nitride coated cutting tools for metalworking. Besides PVD tools for fabrication, special smaller tools used mainly for scientific purposes have been developed.

<span class="mw-page-title-main">Sputter deposition</span> Method of thin film application

Sputter deposition is a physical vapor deposition (PVD) method of thin film deposition by the phenomenon of sputtering. This involves ejecting material from a "target" that is a source onto a "substrate" such as a silicon wafer. Resputtering is re-emission of the deposited material during the deposition process by ion or atom bombardment. Sputtered atoms ejected from the target have a wide energy distribution, typically up to tens of eV. The sputtered ions can ballistically fly from the target in straight lines and impact energetically on the substrates or vacuum chamber. Alternatively, at higher gas pressures, the ions collide with the gas atoms that act as a moderator and move diffusively, reaching the substrates or vacuum chamber wall and condensing after undergoing a random walk. The entire range from high-energy ballistic impact to low-energy thermalized motion is accessible by changing the background gas pressure. The sputtering gas is often an inert gas such as argon. For efficient momentum transfer, the atomic weight of the sputtering gas should be close to the atomic weight of the target, so for sputtering light elements neon is preferable, while for heavy elements krypton or xenon are used. Reactive gases can also be used to sputter compounds. The compound can be formed on the target surface, in-flight or on the substrate depending on the process parameters. The availability of many parameters that control sputter deposition make it a complex process, but also allow experts a large degree of control over the growth and microstructure of the film.

High-power impulse magnetron sputtering is a method for physical vapor deposition of thin films which is based on magnetron sputter deposition. HIPIMS utilises extremely high power densities of the order of kW⋅cm−2 in short pulses (impulses) of tens of microseconds at low duty cycle of < 10%. Distinguishing features of HIPIMS are a high degree of ionisation of the sputtered metal and a high rate of molecular gas dissociation which result in high density of deposited films. The ionization and dissociation degree increase according to the peak cathode power. The limit is determined by the transition of the discharge from glow to arc phase. The peak power and the duty cycle are selected so as to maintain an average cathode power similar to conventional sputtering (1–10 W⋅cm−2).

Aluminium magnesium boride or Al3Mg3B56, colloquially known as BAM, is a chemical compound of aluminium, magnesium and boron. Whereas its nominal formula is AlMgB14, the chemical composition is closer to Al0.75Mg0.75B14. It is a ceramic alloy that is highly resistive to wear and has an extremely low coefficient of sliding friction, reaching a record value of 0.04 in unlubricated and 0.02 in lubricated AlMgB14−TiB2 composites. First reported in 1970, BAM has an orthorhombic structure with four icosahedral B12 units per unit cell. This ultrahard material has a coefficient of thermal expansion comparable to that of other widely used materials such as steel and concrete.

<span class="mw-page-title-main">Cemented carbide</span> Type of composite material

Cemented carbides are a class of hard materials used extensively for cutting tools, as well as in other industrial applications. It consists of fine particles of carbide cemented into a composite by a binder metal. Cemented carbides commonly use tungsten carbide (WC), titanium carbide (TiC), or tantalum carbide (TaC) as the aggregate. Mentions of "carbide" or "tungsten carbide" in industrial contexts usually refer to these cemented composites.

<span class="mw-page-title-main">Superconducting wire</span> Wires exhibiting zero resistance

Superconducting wires are electrical wires made of superconductive material. When cooled below their transition temperatures, they have zero electrical resistance. Most commonly, conventional superconductors such as niobium–titanium are used, but high-temperature superconductors such as YBCO are entering the market.

<span class="mw-page-title-main">Titanium aluminium nitride</span> Group of metastable hard coatings

Titanium aluminium nitride (TiAlN) or aluminium titanium nitride is a group of metastable hard coatings consisting of nitrogen and the metallic elements aluminium and titanium. This compound as well as similar compounds(such as TiN and TiCN) are most notably used for coating machine tools such and endmills and drills to change their properties, such as increased thermal stability and/or wear resistance. Four important compositions are deposited in industrial scale by physical vapor deposition methods:

Ultra-high-temperature ceramics (UHTCs) are a type of refractory ceramics that that can withstand extremely high temperatures without degrading, often above 2,000 °C. They also often have high thermal conductivities and are highly resistant to thermal shock, meaning they can withstand sudden and extreme changes in temperature without cracking or breaking. Chemically, they are usually borides, carbides, nitrides, and oxides of early transition metals.

<span class="mw-page-title-main">High-entropy alloy</span> Alloys with high proportions of several metals

High-entropy alloys (HEAs) are alloys that are formed by mixing equal or relatively large proportions of (usually) five or more elements. Prior to the synthesis of these substances, typical metal alloys comprised one or two major components with smaller amounts of other elements. For example, additional elements can be added to iron to improve its properties, thereby creating an iron-based alloy, but typically in fairly low proportions, such as the proportions of carbon, manganese, and others in various steels. Hence, high-entropy alloys are a novel class of materials. The term "high-entropy alloys" was coined by Taiwanese scientist Jien-Wei Yeh because the entropy increase of mixing is substantially higher when there is a larger number of elements in the mix, and their proportions are more nearly equal. Some alternative names, such as multi-component alloys, compositionally complex alloys and multi-principal-element alloys are also suggested by other researchers.

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.

In chemistry, a hydridonitride is a chemical compound that contains hydride and nitride ions in a single phase. These inorganic compounds are distinct from inorganic amides and imides as the hydrogen does not share a bond with nitrogen, and contain a larger proportion of metals.

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