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Production of TiC

Production of TiC

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Published by: ozgelke on Oct 31, 2011
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This work consists of five main stages including  Historical development of titanium carbide,  General properties of titanium carbide,  The production of titanium carbide,  Application of titanium carbide,  Prices. In this investigation, I would like to mostly emphasize the three production methods of titanium carbide among the other production methods. And we will discuss them in detail as much as I can.

1. Historical Development of Titanium Carbide Titanium carbide powder has been the subject of research for over 100 years. Beginning as early as 1887, TiC was separated from titanium-bearing cast iron. Shimer accomplished this with treatment by hydrochloric acid. In order to isolate titanium metal, Moissan attempted the reduction of TiO2 in the presence of carbon in an electric arc furnace, resulting in the production of TiC. This TiC was of very low purity, but the method used seems to be the basis for the carbothermal reduction process in use today. Miyamoto et al. proposed high-pressure self-combustion sintering (HPCS) as a combined process of SHS and high-pressure sintering in 1984 and demonstrated the simultaneous synthesis and densification of TiB2.

93 Density (g/cm3) Mohs Hardness (kg/mm2. Figure 2.89 Melting Point (ºC) 3140 Boiling Point (ºC) 4820 4. @ 20 ºC) Coefficient of Thermal Expansion (µm/m ºK) Electrical Resistivity (Microhm-cm) 3200 451 0. The generally accepted bonding scheme for TiC is a combination of metallic. covalent. TiC has very high hardness. @ 20 ºC) Modulus of Elasticity (GPa) Thermal Conductivity (cal/cm sec.. extremely high melting point. similar to ceramics.7 180-250 Table 1. TITANIUM CARBIDE TiC 59.2. in which the interstitial sites are occupied by the Y (C) atoms. . The unique properties of TiC are derived from its complex bonding nature.041 – 0. Crystal structure of TiC The NaCl-structured transition metal carbides and nitrides are often referred to as interstitial compounds. but still maintains very good electrical and thermal conductivity associated with the parent metal. General Properties of TiC TiC holds an B1 NaCl crystal structure. General Properties of Titanium Carbide Titanium carbide has a wide range of properties similar to both metallic and ceramic materials. X. ºK. The structure can be viewed as an fcc lattice of Me (Ti) atoms.074 7. For example. and ionic bonding. Each titanium atom is surrounded by six carbon atoms and each carbon atom is surrounded by six titanium atoms in a perfect lattice. as we can see from the Fig.1.

the parent metal. Variations in all these factors give rise to the wide range of material properties for TiC. According to the Ti-C phase diagram in Figure. Titanium carbide has long been recognized as a defect structure. the ideally stoichiometric TiC phase would prefer to split into substoichiometric TiCx. valance. i. it contains vacancies.e.2. must change its structure to an fcc or hcp structure which creates octahedral sites that are large enough to accommodate carbon atoms.96 – 0. atomic size and bond length which are still not fully understood. where x <1:0. the high temperature form of β-titanium has the bcc structure. This change from the bcc to the fcc structure also causes the Ti-Ti distance between the host metal atoms to change. many of the cubic carbides and nitrides tend to be substoichiometric (a phase with a smaller concentration of Y atoms than of Me ones. TiC is stable over a wide range of composition. Under realistic experimental conditions. Figure 2. Phase diagram for Ti-C system Correlation of structure and properties for TiC is difficult because of the effects of bond strength. is called substoichiometric or hypostoichiometric). MeYx. TiC most often contains at least a few percent of C vacancies.TiC is often discussed as an interstitial carbide where titanium occupies a close-packed structure and the carbon is located on a specific interstitial sites. and concequently is not a true interstitial structure as the initial metal framework is altered. As a result. In this case. These vacancies generally occur on the carbon site and to a lesser degree on the Ti site.97 and a pure C phase. titanium. vacancies. stoichiometry. . For example. For example. However. x ~ 0. this classical description of titanium carbide is not scientifically correct.

The binary Ti-C phase diagram .Figure 2.3.

The reaction proceeds as: Ti + C → TiC Ti and C powders is used as beginning material and processed at 2500 – 3000 ºC. this process allows excessive grain growth to occur as well as producing strong agglomerates. this process makes use of carbon black mixed with titania. Using reaction temperatures between 1700°C and 2100°C. necessitating milling to produce fine TiC powders. Unfortunately. This reaction suffers several severe limitations. With reaction time being from 5-20 hours.1. TiC can be produced according to the following reaction : TiO2 + 3C = TiC + 2CO(g) The theoretical thermodynamic reaction temperature (when the Gibbs energy becomes negative) for this reaction is 1289°C. the cost of elemental titanium is high. Direct Carburization Tthe most basic TiC production method is the direct carburization of titanium.3. and attaining submicron particles from the titanium is a difficult prospect. 3. First. Carbothermal Reduction The most widely applied method for producing TiC on a commercial scale is carbothermal reduction. The basis of the process usage of the gases that occurs in the process. as the smaller particles are pyrophoric. making them difficult to handle. The high pressure which is made by these gases increases the reaction between Ti and C.2. physical mixing allows only limited contact . Production Techniques of Titanium Carbide • Direct Carburization • Carbothermal Reduction • Self-propagating High Temperature Synthesis (SHS) • Mechanical Alloying • High Pressure Self Combustion Sintering • Chemical Vapor Deposition 3. Commercially.

Figure 3.between the reactants. a wide size distribution. and particle agglomeration. The Gibbs Free Energy vs.1. Temperature for TiC Formation Reaction . This has the effect of increasing reaction time (as long as 10 hours) to produce powders having unreacted carbon and TiO2.

high exothermic reaction can be initiated by high energy ball milling. nanocrystalline materials and so on. High-energy ball milling can induce structural and microstructural modifications and produce various nonequilibrium materials: supersaturated solid solution.3. Furthermore.2. Figure 3. During the ball milling. large particles may be plastic deformed and fragmented.3. and is commonly referred to high energy ball milling. Mechanical alloying is a potential method for producing commercial nanocrystalline powders. small particles may coalesce by cold-welding. It is easy to obtain TiC with nanocrsytalline size by using ball milling at room temperature. amorphous alloy. Ball milling and grinding media for laboratory investigations . Mechanical Alloying Mechanical alloying is a kind of milling process.

5. finer grain size.Figure 3. Figure 3. Wider peaks. Milling Time When the milling time reached 115 min. X-ray diffraction patterns of TiC (mol)=1:1 at different milling time a) 120 min b) 240 min c) 600 min TiC with 20 nm crsytallites is fabricated by ball milling of Ti and C powders just after reaction 120 min.3. the temperature of the vial increased abruptly and . longer time.4. High efficiency ball mills in industry TiC is able to be synthesized for a short time at room temperature. Nanocrsytalline Size vs. Figure 3.

. XRD analysis supports this.reached its climax. The large particles appear to be agglomerates of finer particles with about 1 mm in diameter. Xb. X. 120 min b) 240 min c) 600 min Briefly. the crystalline size decreased gradually. SEM micrographs of milled powder at different times a) just after an exothermic raction. This is associated with the exothermic reaction of Ti and C. the exothermic reaction of Ti and C can be carried out by the mechanical alloying technique.. The self propagating reaction induced by mechancial alloying takes place in a short time. The average crystalline size reached about 7 nm when ball milled for 10 h. Figure 3. Fig. During the subsequent milling. Milling Time We can conclude that TiC powders are able to be manufactured by mechanical alloying after 120 minutes milling time. Fig. Figure 3. Fig.6. shows the scanning electron microscopy (SEM) images of product powder particles. Temperature vs. Xa. shows the micrograph of a TiC powder particle just after an exothermic reaction. Xa.7. shows the magnified micrograph in a typical region of a larger particle of Fig.

This method has received considerable attention as an alternative to conventional furnace technology. High Pressure Self Combustion Sintering (HPCS) Firstly. The temperature of the combustion can be very high (as 5000 K) and the rate of wave propagation can be very rapid (as 25 cm/s). In the typical combustion synthesis the reactants are usually fine powders. like TiC. The products of the reaction are extremely porous. The SHS is based on systems able to react exothermally when ignited and to sustain them to form a combustion wave.4. composites and intermetallic compounds. and energy efficient. SHS process enables the synthesis of powder materails. mixed and pressed into a pellet to increase an intimate contact between these. relatively low energy . hence this process offers the opportunity to investigate reactions in conditions of extreme thermal gradients (as 105 K/cm). it is simple. Reactions between particulate materials are an alternative way to produce various types of materials considering the extreme simplicity of the process. The reactant mixture is placed in a refractory container and ignited in vacuum or inert atmosphere. since HPCS is a combined process of SHS. Moreover. we should introduce self-propagating high temperature synthesis (SHS). in a very short time by utilizing an exothermic reaction.3. Self-propagating High-temperature Synthesis (SHS) is a relatively novel and simple method for making certain advanced ceramic. typically 50% of theoretical density.

high purity of the products obtained. The possibility of the formation of metastable phases is based on high thermal gradients and rapid cooling rate associated with the reaction. Some materials produced by SHS . Schematic diagram of SHS Table 2. volatile impurities are expelled as the wave propagates through the sample. Higher purity of products is the consequence of high temperature associated to the combustion.requirement. the possibility to obtain metastable phases.8. and the possibility of simultaneous synthesis and densification. Figure 3.

• Pressure is applied by means of a hydraulic uniaxial press • Boron nitride die • Argon atmosphere • Ignition agent.A high pressure self combustion sintering (HPCS) process is applied to synthesis and simultaneous sintering in a very short time by use of exothermic reaction under high pressure.9. Schematic diagram of the experimental system for HPCS .5 to 2. mixture of titanium and boron • The electrical current at 1.0 kV · A for 2 s for ignition agent is passed through a tungsten heater Figure 3. Dense TiC (>95% of theoretical) can be fabricated by this HPCS method.

80. This situation leads to existence of unreacted carbon elements in the structure. Lattice constant as a function of molar ratio.80 must yield a product which consists of only single-phase TiC.Figure 3. The phase diagram of the Ti. the residual carbon is available due to excessively initial carbon amount. vickers microhardness is directly proportional to the density. as shown in Fig. The microhardness increases with increasing density. As we can see from the related figures.TiC system suggests that the achievement of complete reaction for a reactant mixture with C/Ti = 0. The lattice constant decreases with increasing pressure. X.11. Moreover. X-ray powder diffraction patterns of the products by HPCS under 65 MPa Small peaks due to titanium and carbon appeared in the X-ray diffraction pattern for the product from the reactant mixture with C/Ti = 0. C/Ti . Figure 3. This results in producing a denser and a harder product.10.

(Generally.Figure 3.12. Both elements impinge upon each other in the gas phase and the compound condenses. instead of C fibers. in this investigation C fibers were employed to highligt the possibilities mentioned above). 1. However. Structuralization When the reaction to form TiC occurs. the most commonly encountered possibilities are second and third ones. 3. 1. and then compound formation occurs. Compund formation occurs at the boundry of the two elements in the condensed phase. Relationship between Vickers microhardness and Density Combustion synthesis seems to be completed through three steps. C powders can be used in HPCS. Transport elements to encounter the reaction 2. Either element is transported to the surface of the other element through gas phase. An exothermic synthesis reaction 3. without transport of the elements through the gas phase. It is obvious that carbon fiber remains in the product and the combustion reaction is incomplete. seen from the figures X.However. the following three mechanism are possible. 2. .

while the initial was smooth These micrographs. Therefore. A certain carrier for the transport of titanium and/or carbon should be taken into consideration. . SEM photograph of the carbon fiber before the production. oxygen plays an important role as a carrier for carbon. also.  There is a gap between the unreacted carbon fiber and the surrounding product TiC  The diameter of the residual carbon fiber is 5µm.Figure 3. a very fast combustion process such as in fabrication of TiC cannot be explained.13. since it can exist in the starting elements and BN dies.14. while the initial was 7 µm  The surface of the residual carbon fiber is very rough. because even under vapor pressure in equilibrium at the adiabatic temperature (3210 ºK for TiC). support to second and third possibilities.80 by HPCS under 65 MPa Figure 3. SEM photographs of the fractured surface of the product from the reactant mixture with C/Ti = 0.

The advantage of this new sintering process is that the synthesis and sintering of Tic can be accomplished by a simple and extremely short-time process and with low electric power.5% and 31 GN/m2. the HPCS process is useful to fabricate the dense titanium carbide ceramics directly from the constituent elements without additives. CVD may be defined as a technique in which a mixture of gases interacts with the surface of substrate at a relatively high temperature. 3.95. respectively. In formal terms. The maximum values of the relative density and the Vickers microhardness is 96. if there is sufficient oxygen available. resulting in the decomposition of some of the constituents of the gas mixture and the formation of a solid film of coating of a metal or a compound on the substrate. The mixtures of Ti and C converted entirely to the nonstoichiometric TiC. at room temperature. Chemical Vapor Deposition (CVD) Chemical vapor deposition (CVD) is a technique of modifiying properties of surface of engineering componenets by depositing a layer or layers of another metal or compound through chemical reactions in a gaseous medium surrounding the componenet at elevated temperature.5.Carbon transport by CO is considered in the combustion reaction of titanium and carbon. . compounds in the mixing range of C/Ti≤O. The reaction most likely proceeds by 2C +O2 → CO 2 2C +Ti → O TiC +C 2 O CO 2 +C → CO 2 Briefly.

Reaction chamber 4. Gas scrubber 14. Gas tank regulators 17. Temperature sensor and controller 8. Flow control valves 16. Metal halide (liquid) vaporizer 12. Substrate support 18.Figure 3. Flow meter 15.10. Power controller 6. Water-cooled end flanges 5. Particulate trap 13. Heating elements 3. Precursor gas sources 9. Reactor 2. Pressure gauge 7. Substrate .15. Schematic diagram showing various components of a typcial chemical vapor deposition system 1.11.

Process parameters Type of precursors Gas ratio Substrate T/ DepositionT Pressure Flow rate Deposition time Reactor geometry Coating properties Nucleation and growth Deposition rate Microstructure Composition/Stoichiometry Coating thickness Uniformity and adhesion Physical/chemical/electrical/ optical/magnetical/ mechanical properties CVD phenomena Thermodynamics Chemical kinetics (gas phase/surface) Mass transport Figure 3. The gas mixture (which typically consists of hydrogen.16. and a system for the treatment and disposal of exhaust gases. or argon. and reactive gases such as metal halides and hydrocarbons) is carried into a reaction chamber that is heated to desired temperature by suitable means. Process/Microstructure/Property Relationship in CVD A modern CVD system includes a system of metering a mixture of reactive and carrier gases. a heated reaction chamber. nitrogen. Typical parameters in CVD . Table 3.

corrosive gases. powders. The CVD technique is applicable for the deposition of a wide variety of materials. These products contain various reactive and potentially hazardous constituents. TiN.All CVD systems require a mechanism by which the products of the chemical reaction are treated. ceramics. This is usually done by using nonreactive materials for pump components. In addition. as well as particulate matter. the pumping equipment must be protected from relatively hot. and whiskers. Applications of the CVD Technique Table 5. and their combinations. Typical Materials Deposited by CVD One of the most widely known and practiced applications of CVD is in the manufacture of coated cemented carbide cutting tools. Table 4. compunds. . such as metals. and Al2O3. which must be trapped and neutralized before the gases are exhausted to the atmosphere. as most CVD process are carried out at subatmospheric pressures. The commonly used coatings include TiC.

nitrides.  Because of the wide range properties for TiC. an extremely high melting point and desirable properties of corrosion resistance. . and borides due to their extreme hardness. especially fusion reactors and superhard cutting devices.Another application in tribological coating includes refractory compounds such as carbides. Moreover. it can be added to WC-Co as a secondary carbide. fracture toughness etc. high elastic modulus. to avoid diffusion of WC into the steel surface during machining operation. it lowers density of the carbide.%. up to 15wt. 4. One of the elegant applications of CVD tribological coatings is for ball bearings. extrusion and similar metalworking operations. Applications of TiC  TiC is an important ceramic because it has a specific strength at a high temperature. used in molding.  TiC is an attractive compound for a wide range of engineering applications. Other applications of tribological coatings include various steel components such as coating on dies.

Advantages of Titanium Carbide Coated balls: • • • • • • • • • Extended bearing life Minimized adhesion and fretting wear Reduced race wear Reduced cage (retainer) wear Extends life of lburicant and also has high tolerance towards all types of lubes: chemical inertia of coating Low coefficient of friction (3 x’s lower than steel) Works in low lubrication conditions Excellent wettability characteristics In contrast to ceramic balls. TiC balls exhibit the bulk properties of the steel substrate (identical Young’s modulus. thermal expansion and hardness of steel balls and races) • Complete traceability . dies.  TiC + Al2O3 ceramic inserts. Because of its hardness and wear resistance it is mainly used for cutting tool tips. saws.  Titanium carbide coated 440C stainless steel balls. and wear resistant coatings.

Figure 4.1.2. Al2O3 ceramic inserts in white and TiC + Al2O3 ceramic inserts in black . TiC cutting tools Figure 4.

Figure 4. total C ≥19.60 . O <0. TiC saws 5.7%. Ball coated with TiC and ball bearing Figure 4. average particle size (APS) <3 µ m.25%. Prices for TiC Prices can be higher depending on the quantities of the TiC powders.4%.270 $ 10 TiC inserts can be bought by 40 $ Material Titanium Carbide powder.4. 70 $ . free C <0. APS <3 µ m Name Formula TiC Specification 99.7% (metal basis). 99.2% Quantity & 250 g $ 48.3.

3140 oC.60/kg $ 39. Matsushita Electric Industrial Co.50 $ 86. Japan).7%. 4820 500 g 1 kg 2 kg 5 kg 10 kg 20 kg 50 kg 100-500 kg 1 metric ton (1000 kg) 2-10 tons $ 73.. Osaka Industrial University. Daito. Ibaraki. Japan). Osaka 567. Osaka 570. Journal of the American Ceramic Society. APS <3 µ m m. “Fabrication of Titanium Carbide Ceramics by High Pressure Self Combustion Sintering of Titanium Powder and Carbon Fiber”.50/kg $ 26. and Toshihiro Mihara (Central Research Laboratory. Moriguchi.90/kg $ 46.80/kg $ 42. 99.p. Osaka 574.70/kg $ 54.p. . Osamu Yamada (College of General Education. Yoshinari Miyamoto and Mitsue Koizumi (Institute of Scientific and Industrial Research.Price Product # 22R-0601 TiC Powder. b.. Japan). Osaka University. Ltd. 1989.70/kg - References  Seiji Adachi. Takahiro Wada.20 $ 112.

Lin Qiushi. Daito. A.  Zhu Xinkun.hooverprecision. The Pennsylvania State University.uni pv.com/html/hoover_-_titanium_carbide__tic. Department of Materials. Kunming UniÕersity of Science and Technology.com. “Hardmetals and other hard materials”.tr/imgres? imgurl=http://www. Su Yunsheng. TiBCN. Chen Tieli.  Kenneth J.unica. “COATINGS TECHNOLOGY HANDBOOK”. 1998. ASM Handbook Volume 02.org/  http://www. electron beamphysical vapor deposition (EB-PVD)”. 2006. Japan). Kunming 650093. Osamu Yamada (College of General Education. Brookes.html  http://images.com.google. People’s Republic of China.  http://en.it/materials/HighLights/SHS. “Synthesis of nanocrystalline TiC powder by mechanical alloying”.it/materials/images/cs1. TiB2/TiC and TiC/CrC multilayer coatings by reactive and ion beam assisted.j .“High-pressure Self-Combustion Sintering of Titanium Carbide”.dicm. Osaka Industrial University.htm&h=262&w=586&sz=8&hl=tr&start=80&um= 1&tbnid=nOzxBbK4wYQd1M:&tbnh=60&tbnw=135&prev=/images%3Fq%3D %2522self-propagating%2Bhigh-temperature%2Bsynthesis%2522%26start %3D60%26ndsp%3D20%26svnum%3D10%26um%3D1%26hl%3Dtr%26sa %3DN  http://images.  Douglas E.gif&imgrefurl=http://chifis1.google. 2001. 1987.  “Properties and Selection Nonferrous Alloys”.unipv.wikipedia. Communications of the American Ceramic Society.it/~cincotti/gruppo/instrumentation_file/image008.  Arthur A. Tracton. Cheng Baochang. Zhang Xiuqin. Zhao Kunyu. “Synthesis and characterization of TiC. 2001. Wolfe. Osaka 574.tr/imgres? imgurl=http://chifis1.

dicm.unica.html&h= 481&w=642&sz=45&hl=tr&start=16&um=1&tbnid=jACMSlZCFT5AFM:&tbnh= 103&tbnw=137&prev=/images%3Fq%3D%2522self-propagating%2Bhightemperature%2Bsynthesis%2522%26svnum%3D10%26um%3D1%26hl%3Dtr %26sa%3DN .pg&imgrefurl=http://www.it/~cincotti/gruppo/instrumentation.

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