Chinese name: titanium carbonitride
English name: Titanium carbonitride
CAS: 12654-86-3
MDL: MFCD01868685
Molecular formula: TiCN
Molecular weight: 121.75
Melting point: 2900℃
Density: 5.08 g/mL at 25 °C(lit.)
Hardness (HV) : 34GPaI density 4.52

Properties: Gray or gray black powder, with hexagonal crystal structure, with low internal stress, high toughness, good lubricity, high hardness, wear resistance and other characteristics, suitable for occasions requiring lower friction coefficient and high hardness.
Technical performance:
1. The ceramic made of titanium carbonitride has the following characteristics: the hardness (HRA) is as high as 91-95, which can reach the hardness level of non-metallic ceramic tools; It has good wear resistance and ideal anti-crescent wear ability, and the wear rate is very low when cutting steel at high speed, and its wear resistance is 3-4 times higher than that of WC-based cemented carbide. It has high heat resistance, high temperature hardness, high temperature strength and high temperature wear resistance are better, and it can still be cut at high temperature of 1100-1300℃, and the general cutting speed is 2-3 times higher than that of WC-based carbide. It has good chemical stability and high antioxidant capacity. Compared with cemented carbide, titanium carbonitride cermet has high wear resistance, lower oxidation degree, better thermal shock resistance, suitable for high-speed cutting tool materials, can well control the geometric accuracy and tolerance of the workpiece, high finish, high feed speed; Good results can be obtained when processing carbon steel, stainless steel, microalloyed steel, and ductile iron.
2. Titanium carbonitride is a glossy black powder, a zero-dimensional ternary solid solution, TiC and TiN are the basis of titanium carbonitride, both of which have a face-centered cubic lattice nacL-type structure, and can also form solid solutions with TaC, NbC and other transition metal carbides. Titanium carbonitride is a complex compound formed by nitrogen atom (N) occupying the position of original carbon atom (C) in the lattice in a single TiC lattice. There are two ideal modes for the ratio of carbon and nitrogen atoms in TiCxNy, namely TiC0.5N0.5 and TiC0.3N0.7. Because TiCN has the combined properties of TiC and TiN, its hardness is higher than TiC and TiN, so it is an ideal tool coating material. Titanium carbonitride can not only improve the bonding strength of the coating with the substrate, but also have the comprehensive properties of various materials.
Uses: 1) Wear resistance, acid and alkali resistance, strong electrical and thermal conductivity, small coefficient of thermal expansion, excellent chemical stability and thermal resistance. Widely used in cutting tools, powder metallurgy and cermet products.
2) Coating: TiCN has a lower friction coefficient and higher hardness than TiN, and the tool plated with titanium nitride carbide is more suitable for cutting hard materials such as stainless steel, titanium alloy and nickel alloy, with more wear resistance and high temperature stability, which can significantly improve the life of the tool. Titanium nitride coating (TiN) is a universal PVD coating with a coating thickness of 2300HV, which is a mature and widely used hard coating material. Features: High hardness, high wear resistance and oxidation resistance. Application: Suitable for most cutting tools and high-speed steel cutting tools or forming tools to improve their processing performance. It is also suitable for most forming molds and anti-wear parts. Titanium nitride carbide coating (TiCN), in which the addition of carbon to increase tool hardness and obtain better surface lubricity to reduce the coefficient of friction, is the ideal coating for high-speed steel tools. The thickness of the coating is 2800HV, which prevents crack propagation and reduces blade breakage.
3) It has the advantages of TiC and TiN, in addition to being very suitable for high-end precision machining and near-net molding processing, it maintains TiC characteristics on the basis of the introduction of N, TiC brittle characteristics have been significantly improved. With the increase of N content, the hardness decreases and the toughness increases. It is precisely because of its excellent comprehensive performance that titanium carbonitride based ceramics have been widely used in the cutting field, high temperature resistant materials, measuring tools, petroleum and chemical industry, watch appearance and other fields.
4) Refractory, non-oxide added to the refractory, will bring some excellent performance. Studies have shown that the presence of titanium carbonitride can significantly improve the performance of refractory materials.
Preparation method:
1, high temperature solution method
High temperature solid solution method is the traditional method to prepare Ti(C, N) powder, usually by a certain amount of TiN and TiC powder uniformly mixed at 1700 ~ 1800℃ hot pressing solid solution formation, or in Ar or N2 atmosphere at a higher temperature through solid solution to obtain. In order to inhibit grain growth and improve powder activity and sintering properties, the solution temperature can also be appropriately reduced. Even if the solution temperature is reduced, the high temperature solution method has some shortcomings, such as high reaction temperature, high energy consumption, difficult to obtain high purity powder, and difficult to accurately control N/C ratio.
2, TiN and C powder high temperature nitriding method
High temperature nitriding method is usually TiN powder and C powder as raw materials, mixed in high temperature and N2 or Ar atmosphere for a long time carbonitriding treatment, so as to obtain Ti(C, N) powder. Frederic et al. used nano-sized TiN powder +10wt% carbon black to hold heat at 1430℃ in Ar air stream for 3h, solid phase to form Ti(C, N) powder, showing regular shape of submicron particles. Similarly, high temperature nitriding method has the disadvantages of high reaction temperature, low production efficiency, large energy consumption and high production cost.
3, high temperature self-spreading reaction method
The high temperature self-propagating reaction method is to evenly mix Ti powder and C powder, prepress forming to obtain compact, and then "ignite" the reaction at high temperature in the device containing N2, so as to obtain the bulk product, and Ti(C, N) powder can be obtained by crushing and refining.
4, high-energy ball mill induced self-propagating synthesis method
As a powder processing method, high-energy ball milling can not only uniformly mix and activate powder to reduce sintering reaction temperature and promote alloying, but also induce self-propagating reaction to synthesize nano Ti(C, N) powder at room temperature. High energy ball mill induced self-propagating Ti(C, N) synthesis technology integrates powder mixing and reaction, overcomes the traditional high temperature conditions, and can directly obtain Ti(C, N) powder.
5. TiO2 carbonothermal reduction nitriding method
Carbothermic reduction nitriding method is a process of synthesizing Ti(C, N) powder by reducing TiO2 and C powder as raw materials in N2 at high temperature. The size and morphology of the products of carbothermic reduction method can be controlled by process parameters, and it is widely used in industrial large-scale production.
6. Ammoniolysis
Ammoniolysis method is usually at room temperature, TiCl4 is dissolved in the appropriate solvent and added with additives, mixed evenly and NH3 reaction, to produce a uniform mixture of Ti amine compound and additive intermediate, and then the intermediate and NH4Cl solution mixed precipitation and remove the amine in the intermediate. The Ti(C, N) powder was then pyrolyzed at 1200 ~ 1600℃ under vacuum or Ar atmosphere. The characteristics of the ammoniolysis method are that the preparation temperature is lower than that of the traditional preparation method (high temperature solid solution method, 1800℃), and the Ti(C, N) powder obtained has the advantages of high specific surface area, small particle size, concentrated particle size distribution and high purity, but the cost is high and the process is complex.
Storage conditions:
Storage precautions Store in a cool, dry, well-ventilated special warehouse, packing sealed.

Preparation of titanium carbonitride powder

1 High temperature solution method

High temperature solid solution method is the traditional method to prepare Ti(C, N) powder, usually by a certain amount of TiN and TiC powder uniformly mixed at 1700 ~ 1800℃ hot pressing solid solution formation, or in Ar or N2 atmosphere at a higher temperature through solid solution to obtain. In order to inhibit grain growth and improve powder activity and sintering properties, the solution temperature can also be appropriately reduced. Even if the solution temperature is reduced, the high temperature solution method has some shortcomings, such as high reaction temperature, high energy consumption, difficult to obtain high purity powder, and difficult to accurately control N/C ratio.

High temperature nitriding of 2TiN and C powder

High temperature nitriding method is usually TiN powder and C powder as raw materials, mixed in high temperature and N2 or Ar atmosphere for a long time carbonitriding treatment, so as to obtain Ti(C, N) powder. Frederic et al. used nano-sized TiN powder +10wt% carbon black to hold heat at 1430℃ in Ar air stream for 3h, solid phase to form Ti(C, N) powder, showing regular shape of submicron particles. Similarly, high temperature nitriding method has the disadvantages of high reaction temperature, low production efficiency, large energy consumption and high production cost.

3TiO2 carbonothermal reduction nitriding method

Carbothermic reduction nitriding method is a process of synthesizing Ti(C, N) powder by reducing TiO2 and C powder as raw materials in N2 at high temperature. The size and morphology of the products of carbothermic reduction method can be controlled by process parameters, and it is widely used in industrial large-scale production.

4 Sol-gel method

In the sol-gel method, TiO(OH)2 sol is used as Ti source, carbon black is mixed and dispersed in the liquid phase, and Ti(C, N) powder is obtained by heat treatment at high temperature under N2 after a series of reactions. Some researchers formed a gel formed by mixing TiO(OH)2 sol with nanoscale carbon black. After drying, Ti(Cx, N1-x) was obtained by high temperature reaction at 1400 ~ 1600℃ in N2 atmosphere, where 1-x=0.2 ~ 0.7, the average particle size of Ti(Cx, N1-x) ultrafine powder was less than 100nm. The x value can be improved by increasing the C/Ti ratio of raw material, increasing the reaction temperature, extending the holding time and reducing the nitrogen flow rate.

5 Ammoniolysis

Ammoniolysis method is usually at room temperature, TiCl4 is dissolved in the appropriate solvent and added with additives, mixed evenly and NH3 reaction, to produce a uniform mixture of Ti amine compound and additive intermediate, and then the intermediate and NH4Cl solution mixed precipitation and remove the amine in the intermediate. The Ti(C, N) powder was then pyrolyzed at 1200 ~ 1600℃ under vacuum or Ar atmosphere. The characteristics of the ammoniolysis method are that the preparation temperature is lower than that of the traditional preparation method (high temperature solid solution method, 1800℃), and the Ti(C, N) powder obtained has the advantages of high specific surface area, small particle size, concentrated particle size distribution and high purity, but the cost is high and the process is complex.

6 High temperature self-propagating reaction method

The high temperature self-propagating reaction method is to evenly mix Ti powder and C powder, prepress forming to obtain compact, and then "ignite" the reaction at high temperature in the device containing N2, so as to obtain the bulk product, and Ti(C, N) powder can be obtained by crushing and refining.

7 Plasma chemical vapor deposition method

Ti(C, N) plasma chemical vapor deposition (CVD) is usually a technology that activates TiCl4 reaction gas with plasma to promote its chemical reaction on the surface of the matrix or near the surface space to generate Ti(C, N) solid film. Later, in order to avoid the corrosion of TiCl4 on the reaction vessel and pollution to the environment, chlorine-free Ti-containing organic matter is often used to replace TiCl4. This kind of Ti containing organic matter mainly includes tetramethylgrease titanate, tetraethyl titanate, tetraisopropyl titanium, tetrabutylgrease titanate and titanium amino.

8 High energy ball mill induced self-propagating synthesis

As a powder processing method, high-energy ball milling can not only uniformly mix and activate powder to reduce sintering reaction temperature and promote alloying, but also induce self-propagating reaction to synthesize nano Ti(C, N) powder at room temperature. High energy ball mill induced self-propagating Ti(C, N) synthesis technology integrates powder mixing and reaction, overcomes the traditional high temperature conditions, and can directly obtain Ti(C, N) powder.

The application of titanium carbonitride

1Ti(C, N) fund is a ceramic tool

Ti(C, N) foundation ceramic is a very important structural material, with the preparation of the tool and WC-based cemented carbide compared to the processing shows a higher red hardness, similar strength, low corrosion, thermal conductivity and friction coefficient, with a higher life or in the same life can be used in the case of higher cutting speed, The workpiece to be machined has a good surface finish. It is understood that Japan's Ti(C, N) fund ceramic tool materials have accounted for more than 30% of all its tool materials market share.

2Ti(C, N) is a ceramic coating

Ti(C, N) foundation ceramics can be made into wear-resistant coatings and mold materials. Ti(C, N) coating has excellent mechanical and tribological properties. As a hard wear-resistant coating, it has been widely used in cutting tools, drills and molds, etc., and has broad application prospects. The preparation process mainly includes plasma chemical vapor deposition, medium temperature chemical vapor deposition and traditional CVD method. Ti(C, N)

Compared with die steel, it has the characteristics of no phase change, high temperature resistance, low friction coefficient and good adhesion resistance, and has certain strength and toughness, which is a mold material with great potential for development.

3 Multiphase ceramic materials

Ti(C, N) can be combined with other ceramics to form composite materials, such as Ti(C, N)/Al2O3, Ti(C, N)/SiC, Ti(C, N)/Si3N4, Ti(C, N)/TiB2 and other composite ceramic materials, Ti(C, N) as a reinforcement can improve the strength and fracture toughness of the material. It can also improve electrical conductivity.

4 Refractory materials

The addition of non-oxides to refractory materials will bring some excellent properties. Studies have shown that the presence of titanium carbonitride can significantly improve the performance of refractory materials.

5 Synthesis of Ti(C, N) whisker

As early as 2011, Drexel University first prepared titanium carbide 2D materials and found that this material has many special properties, including high strength, high electrical conductivity and molecular filtration ability. The property of titanium carbide was that it blocked and absorbed electromagnetic interference more effectively than any known material at the time, including the metal foil used in most electronic devices today. When Drexel University continued to examine other members of the family, they found that titanium carbonitride had superior properties, making it a more promising candidate for shielding against electromagnetic interference. This also means that titanium carbonitride could be used to individually coat components inside a device to contain their electromagnetic radiation, even if they are placed close together. Companies like Apple have been trying this containment strategy for several years, but the success rate is limited by the thickness of the copper foil. As device designers strive to make devices ubiquitous by making them smaller, less visible, and more integrated, this strategy is likely to become the new standard.