TITANIUM CARBIDE

CONTENT Synthesis of Nano-structured TiC by Mg Thermal Reduction Self Propagating High-temperature Synthesis (SHS) TiC Reinforced Aluminum Composites Production of TiC Reinforced Aluminum Composites with Addition of Elemental Carbon TiC Reinforced Magnesium Matrix Composites Production of TiC Reinforced AZ91 Magnesium Alloy Matrix Composite Synthesis of Nano-structured TiC by Mg Thermal Reduction Titanium carbide has been widely used in the fields of wear resistance tools and aerospace materials due to its high melting point of 3338 K, the production of bulk materials containing the TiC component has been made possible by TiC powder consolidation only. The finer the stoichiometric titanium carbide powder particles, the higher the mechanical strength of the consolidated materials obtained.Also, the lower the quantity of free carbon and the higher the purity, the higher becomes the mechanical strength of consolidated materials. Although several methods have been employed to produce TiC powder such as carbothermal, selfheated reactive sintering and solgel processes.They have all shown drawbacks such as: -formation of a coarse sintered structure, -nonstoichiometric composition -TiCxOy formation -need for initial titanium powder of high purity -need for post-milling

(Reaction steps) A solution of liquid metal chlorides (TiCl4 and CCl4) was reacted with liquid magnesium for the formation of released Ti and C atoms by magnesium reduction of metal chlorides. The TiCl4 +CCl4 solution is fed into liquid magnesium with the feeding rate below 0.3334 g/s, the reaction temperature is above 1273 K, and a CCl4 concentration of 105% per chemical equivalent in solution is used.The corresponding reaction equation is : TiCl4 (g) + CCl4 (g) + 4Mg (l) = TiC (s) + 4MgCl2 (l) The thermodynamics of free energy for reduction of each component at a temperature of around 1273 K: TiCl4 (g) + 2Mg (l) = Ti (s) + 2MgCl2 (l) , G1300 K = - 296 kj/mol CCl4 (g) + 2Mg (l) = C (s) + 2MgCl2 (l) , G1300 K = - 960 kj/mol Ti (s) + C (s) = TiC (s) , G1300 K = - 184 kj/mol TiCl4 (g) + CCl4 (g) + 4Mg (l) = TiC (s) + 4MgCl2 (l) , G1300 K = - 1140 kj/mol A solution composed of TiCl4 and CCl4 is fed vertically to an insulated cylindrical chamber made of steel, where the liquid magnesium is molten protected with argon gas at 111.46 kPa.A sufficient quantity of magnesium is prepared in the chamber to provide the complete reduction without formation of intermediate phases such as TiCl3, TiCl2, C6Cl6. The reaction temperatures is changed within the range of 11731373 K. The residual products of Mg and MgCl2 after reduction is removed by vacuum separation at conditions of 1.333103 kPa for 3 h.By this process, a high quality crystalline form of TiC0:96 with about 1.0 wt.% of free carbon is produced.The lattice parameter of the product is 0.43267 nm, near the standard value, and the crystal size is approximately 50 nm.

Main process parameters are : -the composition of liquid solution -its feeding rate into liquid magnesium -reaction temperature.

Self Propagating High-temperature Synthesis (SHS)

SHS is also known as combustion synthesis, has many attractive advantages such as: -high purity of product -low processing cost -efficiency in energy and time

TiC Reinforced Composites

TiC Reinforced Aluminium Composites

Aluminium based composite materials have been taking great attention especially in the industries such as aviation, space and automotive.The superior properties of aluminium matrix composite materials over conventional ones are : -high strength -high elastic modules -excellent friction and wear resistance -low heat expansion coefficients TiC is used as reinforcement phase because of its: -high hardness -high elastic module -low density -good wettability with molten aluminium -low chemical reactivity Production Methods Exothermic dispersion (XD) Reaction gas injection Self propagating high-temperature synthesis (SHS) Liquidsolid reactions Liquidliquid reactions

Production of TiC Reinforced Aluminum Composites with Addition of Elemental Carbon At elevated temperatures carbon reacts with AlTi melt and produces TiC which acts as reinforcement phase.The stability of Al4C3 and TiC phases in aluminum melt depends on their free energies. transformation free energy for one mole TiC is lower than that of Al4C3 , therefore it can be concluded that thermodynamically TiC is more stable than Al4C3 . Ti + C = TiC 4/3 Al + C = 1/3 Al4C3 G = - 186606 + 13.22 T j/mol G = - 88840 + 32.1 T j/mol

Process : AlTi alloys having different chemical compositions were melted in a pure alumina coated graphite crucible utilizing induction furnaceMelt temperature was raised to 1200 -C and held for 30 min to dissolve Al3Ti phase completely.Pre heated (850 C) 1 g carbon (an average particle size of 1020 microns) particles were packed in aluminium foils and added into crucible, then temperature was raised to the reaction temperature and kept there until the full reaction takes place.After the completion of casting process, Al based TiC reinforced composites were subjected to rolling operation at 400C by applying three passes.

Parameters : temperature, amount of excess carbon and duration

Phase diagram of TiAl system

Advantages of this method : Easy of production Nucleation of a reinforcement phase in Al matrix No need for sophisticated production technology Low production cost No wettability problem (which is seen in other production methods)

No contamination in between matrix-reinforced phase which lowers mechanical properties

SEM pictures of samples (a) and (b) showing the presence of both TiC and Al3Ti and (c) showing only TiC phase within the structure at 1300 C for 15 min. Conclusions : TiC reinforced Al matrix composites were produced by the additions of elemental carbon to both Al+4%Ti and Al+5%Ti alloy. In elemental carbon addition method, TiC forms between the reaction of carbon and Ti in solution. In both Al+4%Ti (sample no:3) and Al+5%Ti (sample no:6), with the addition of 30% excess carbon at 1300 -C for a duration time of 15 min Al3Ti phase disappears and completely transforms to TiC particles having less than 1 micron size. Both Al3Ti and TiC particles were determined within the microstructure subjected to 1200 -C for 30 min indicating uncompleted transformation of Al3Ti under these conditions.

TiC Reinforced Magnesium Matrix Composites Particle reinforced magnesium matrix composites have a great potential to be applied in automobile and aerospace industries because of their high specific tensile strength and modulus, as well as their high wear resistance.In general, particle reinforced magnesium matrix composites are produced by: -stir casting, -powder metallurgy -squeeze casting -spray forming. In all these methods, the reinforcing particle size is coarse, rarely below 5 microns. Other main drawbacks that have to be overcome are the interfacial reaction and poor wettability between the reinforcements and the matrices due to surface contamination of the reinforcements.Properties of particle reinforced magnesium matrix composites are controlled by the size and volume fraction of the reinforcement as well as the bonding characteristics of the matrix-reinforcement interfaces.The high mechanical properties can be obtained when fine and thermodynamically stable ceramic particles are dispersed homogeneously in the matrix. Production of TiC Reinforced AZ91 Magnesium Alloy Matrix Composite In this study TiC particle reinforced magnesium matrix composite is fabricated by adding a TiCAl master alloy processed by using self-propagating high-temperature synthesis (SHS) reaction into molten magnesium and using the semi-solid slurry stirring technique. The TiCAl master alloy was processed by the SHS reaction of TiCAl system. TiC particles in the master alloy are fine, spherical, and the surface of TiC particles is coated with aluminum and is thus uncontaminated, and this has significantly improved the wetting of the TiC particles inthe magnesium alloy.TiC particles can be easily incorporated into the magnesium alloy matrix by the TiCAl master alloy, and dispersed uniformly in the matrix. Processing steps: 1-Adding the TiCAl master alloy to molten magnesium 2-Semi-solid slurry stirring 3-Casting Chemical compositions of Mg-9 pct Al-1 pct Zn alloy AZ91were selected to prepare the matrix.About 1 kg of pure magnesium melt was prepared at 1023 K in a steel crucible in an electric resistance furnace of 5 kW under a SF6/CO2 protective atmosphere.TiCAl master alloy which was preheated to 200 OC was subsequently charged into the magnesium melt, held at that temperature until the alloy dissolved.Stirring was carried out in the semi-solid temperature range for 3040 min, and then the composite slurry was poured into a preheated steel mould with 55 mm diameter and 180 mm height.

SEM micrograph on the left shows that the uniform dispersion of TiC particles throughout the magnesium alloy matrix, and the agglomeration of TiC particles is not obvious.Micrograph on the right shows the good and clean interface between TiC particles and matrix.

Conclusions : Magnesium matrix composites reinforced with TiC particles can be fabricated by adding a TiCAl master alloy processed by using SHS reaction into molten magnesium and using the semi-solid slurry stirring technique. TiC particles in the master alloy are fine, spherical,and since TiC particles are surrounded by aluminum, the particle surfaces are uncontaminated, which makes the wetting of TiC particles in the magnesium alloy significantly improved. By stirring, a particle reinforced magnesium matrix composite with dispersed homogenously clean fine TiC particles embedded in a magnesium alloy matrix can be obtained. Porosity is obviously reduced by inhibiting gas bubble formation, and limiting gas bubble size when stirring in the semi-solid temperature range. The properties of the composite prepared such as tensile strength , hardness, and wear resistance are higher than those of the unreinforced magnesium alloy