Combustion characteristics of the Ni3Ti-TiB2 intermetallic matrix composites

Combustion synthesis (SHS) of Ni₃Ti-TiB₂ metal matrix composites (MMCs) was selected to investigate the effect of gravity in a reaction system that produced a light, solid ceramic particle (TiB₂) synthesized in situ in a large volume (>50 pct) of the liquid metallic matrix (Ni₃Ti). The effects of composition, green density of pellets, and nickel particle size on the combustion characteristics are presented. Combustion reaction temperature, wave velocity, and combustion behavior changed drastically with change in reaction parameters. Two types of density effects were observed when different nickel particle sizes were used. The structures of the combustion zones were characterized using temperature profile analysis. The combustion zone can be divided into preflame, reaction, and after-burning zones. The combustion mechanism was studied by quenching the combustion front. It was found that the combustion reactions proceeded in the following sequence: formation of liquid Ni-Ti eutectic at 940 °C → Ni₃Ti+NiTi phases → reduction of NiTi with B→TiB₂+Ni₃Ti.     

Combustion synthesis of HfB2-Al composites

Combustion synthesis (SHS) of HfB₂-Al composite materials with a wide range of HfB₂-to-Al ratios corresponding to either metal (Al) or ceramic (HfB₂) matrix was carried out with the emphasis on 60 and 70 vol pct Al. The effects of composition and green density of pellets on the combustion characteristics were studied. Combustion temperature, wave velocity, and reaction mode all changed drastically with composition and green density. The combustion mechanisms were also studied using temperature profile analysis. The combustion zone can be divided into preflame and main reaction zones, and the width of the latter was much larger than that of the former. It was also found that the combustion reaction was initiated at the melting of the aluminum and consisted of a two-step reaction sequence corresponding to the initial formation of Al₃Hf and, subsequently, HfB₂ compounds. The formation of Al₃Hf triggered the HfB₂ formation according to the following reaction mechanism:

Production of Ni3Ti-TiC x intermetallic-ceramic composites employing combustion synthesis reactions

Combustion synthesis (CS) of nickel, titanium, and carbon (graphite) reactant particles can result in NiTi-TiC (stoichiometric) or Ni₃Ti-TiC _x (nonstoichiometric) composites. Since NiTi exhibits both superelasticity and shape memory properties while Ni₃Ti does not, it is important to understand the SHS reaction conditions under which each of these composite systems may be synthesized. The stoichiometry of TiC _x , for which 0.3 ≤ x ≤ 0.5, has an important controlling effect on the formation of either Ni₃Ti or NiTi; i.e., formation of TiC_0.7 results in a depletion of titanium and formation of Ni₃Ti. This deficiency should be considered when developing the SHS reaction. This article examines the SHS conditions under which Ni₃Ti-TiC _x composites are produced. Ignition, combustion, and microstructure characteristics of nickel, titanium, and carbon (graphite) particles were investigated as a function of initial relative density and thermophysical properties of the reactant mixture. Combination of the thermophysical properties and burning velocities controlled TiC _x particle size, yielding a dependence of particle size on cooling rate. Theoretical calculations were performed and are in good agreement with the experimental data presented.     

Fabrication of metal matrix composites of

Fine fibrous titanium carbide (TiC) was processed through the self-propagating high-temperature synthesis (SHS) method and employed to fabricate aluminum matrix composites. Two consol-idation methods were investigated: (1) combustion synthesis of TiC fiber/Al composites directly using titanium powders and carbon fibers ignited simultaneously with varying amounts of the matrix metal powder and (2) combustion synthesis of TiC using titanium powders and carbon fibers followed by consolidation into different amounts of the metal matrix powder, Al,via hot isostatic pressing (HIP). In the former method, when the amount of the Al in the matrix was increased, the maximum temperature obtained by the combustion reaction decreased and the propagation of the synthesis reactions became difficult to maintain. Preheating was required for the mixture of reactants with more than approximately 5 mole pct aluminum matrix powders in order to ignite and maintain the propagation rate. Microstructural analysis of the products from the Al/C/Ti reaction without preheating shows that small amounts of an aluminum carbide phase (AI4C3) are present. In the second method, following separation of the individual fibers in the TiC product, dense composites containing the SHS products were obtained by HIP of a mixture of the TiC fibers and Al powders. No ternary phase was formed during this procedure. Formerly Graduate Research Assistant, Department of Chemical Engineering, Michigan Technological University, is with Particle Technology, Inc., Hanover, MD 21076. This paper is based on a presentation made in the symposium “Reaction Synthesis of Materials” presented during the TMS Annual Meeting, New Orleans, LA, February 17–21, 1991, under the auspices of the TMS Powder Metallurgy Committee.     

Structure and phase formation of combustion products during the synthesis of γ-AlON in self-propagating high-temperature synthesis

Synthesis of aluminum oxynitride (γ-AlON) in conditions of self-propagating high-temperature synthesis (SHS) gas-statting under high pressures (10–100 MPa) of gaseous nitrogen, including the mode of so-called coupled combustion reactions (chemical furnaces) is investigated. It is shown that chemical and phase compositions of combustion products, as well as their structure and morphology of powder particles, depend on the reagent ratio in Al–Al₂O₃ initial mixture, as well as on nitrogen pressure, combustion temperature of highly exothermic components of chemical furnaces, and grade of initial reagents. The structure of γ-AlON powder particles are determind and its relation with operation conditions of SHS. Optimal SHS parameters for Al₅O₆N (γ-AlON) formation are established.     

Production of Ni3Ti?TiC x intermetallic-ceramic composites employing combustion synthesis reactions

Combustion synthesis (CS) of nickel, titanium, and carbon (graphite) reactant particles can result in NiTi−TiC (stoichiometric) or Ni₃Ti−TiC _x (nonstoichiometric) composites. Since NiTi exhibits both superelasticity and shape memory properties while Ni₃Ti does not, it is important to understand the SHS reaction conditions under which each of these composite systems may be synthesized. The stoichiometry of TiC _x , for which 0.3≤x≤0.5, has an important controlling effect on the formation of either Ni₃Ti or NiTi; i.e., formation of TiC_0.7 results in a depletion of titanium and formation of Ni₃Ti. This deficiency should be considered when developing the SHS reaction. This article examines the SHS conditions under which Ni₃Ti−TiC _x composites are produced. Ignition, combustion and microstructure characteristics of nickel, titanium, and carbon (graphite) particles were investigated as a function of initial relative density and thermophysical properties of the reactant mixture. Combination of the thermophysical properties and burning velocities controlled TiC _x particle size, yielding a dependence of particle size on cooling rate. Theoretical calculations were performed and are in good agreement with the experimental data presented. Guglielmo Gottoli, formerly Graduate Research Assistant, Metallurgical and Materials Engineering Department, Institute for Space Resources, Colorado School of Mines     

Production of Ni3Ti?TiC x intermetallic-ceramic composites employing combustion synthesis reactions

Combustion synthesis (CS) of nickel, titanium, and carbon (graphite) reactant particles can result in NiTi−TiC (stoichiometric) or Ni₃Ti−TiC _x (nonstoichiometric) composites. Since NiTi exhibits both superelasticity and shape memory properties while Ni₃Ti does not, it is important to understand the SHS reaction conditions under which each of these composite systems may be synthesized. The stoichiometry of TiC _x , for which 0.3≤x≤0.5, has an important controlling effect on the formation of either Ni₃Ti or NiTi;i.e., formation of TiC_0.7 results in a depletion of titanium and formation of Ni₃Ti. This deficiency should be considered when developing the SHS reaction. This article examines the SHS conditions under which Ni₃Ti−TiC _x composites are produced. Ignition, combustion and microstructure characteristics of nickel, titanium, and carbon (graphite) particles were investigated as a function of initial relative density and thermophysical properties of the reactant mixture. Combination of the thermophysical properties and burning velocities controlled TiC _x particle size, yielding a dependence of particle size on cooling rate. Theoretical calculations were performed and are in good agreement with the experimental data presented. Guglielmo Gottoli, formerly Graduate Research Assistant, Metallurgical and Materials Engineering Department, Institute for Space Resources, Colorado School of Mines     

Combustion synthesis of Ni3Al and Ni3Al-matrix composites

The self-propagating mode of combustion synthesis (SHS) of Ni₃Al starting from compacts of stoichiometrically mixed Ni and Al powders readily forms fully reacted structures with about 3 to 5 pct porosity, if green density of the compacts is greater than about 75 pct of theoretical. SHS-produced Ni₃Al matrix composites with up to 2 wt pct A1₂O₃ whiskers also have relatively low porosity levels. Porosity increases rapidly with lower green densities, higher Al₂O₃, or SiC whisker contents, and the degree of reaction completeness diminishes. The SiC whiskers undergo reaction with the matrix, while Al₂O₃ whiskers are nonreactive. All of these observations correlate well with temperature measurements made during the course of the reaction. The SHS mode can be achieved with agglomerated particle size ratioD _Al/D _Ni ≥ 1, larger than the limit established from studies of the thermal explosion mode of combustion synthesisD _Al/D _Ni ≃ 0.3. This paper is based on a presentation made in the symposium “Reaction Synthesis of Materials” presented during the TMS Annual Meeting, New Orleans, LA, February 17–21, 1991, under the auspices of the TMS Powder Metallurgy Committee.     

Thermodynamic effect of alloying addition on <Emphasis Type="Italic">in-situ</Emphasis> reinforced TiB<Subscript>2</Subscript>/Al composites

From the viewpoint of thermodynamics, using the Wilson equation and an extended Miedema model, the effect of the alloying element on the stability of the precipitated phases during the fabrication of in-situ reinforced TiB₂/Al composites was evaluated. The result shows that additions of alloying elements, such as Mg, Cu, Zr, Ni, Fe, V, and La, can promote the formation of Al₃Ti and TiB₂ phases. Particularly, Zr has the most pronounced effect among these alloying elements. In addition, alloying elements can hinder the formation of AlB₂ to a small extent. The calculation results also show that it is easier for magnesium to react with the salts to form TiB₂ than aluminum during the fabrication of in-situ reinforced TiB₂/Al using the flux-assisted synthesis (FAS) technology.     

Development of TiB<Subscript>2</Subscript> reinforced in-situ Ti aluminide matrix composite through reaction synthesis

TiB₂ reinforced in-situ titanium aluminide matrix composite was made through reaction synthesis process using high purity elemental powders of Ti, Al, Cr, Nb and B. XRD of the synthesized block showed presence of mainly Al₃Ti and TiB₂ phases. To obtain γ Ti aluminide based matrix, the material was homogenized in two phase region (α₂+γ). Presence of γ phase matrix alongwith α₂ was confirmed through XRD, SEM and TEM. Uniform distribution of TiB₂ phase was confirmed through elemental mapping and by analyzing specimens of different locations. Differential scanning calorimetry of powder mixture showed presence of endothermic peak for Al melting and exothermic peak of Ti aluminide and TiB₂ formation.     

Thermal analysis of self-propagating high-temperature reactions in titanium, boron, and aluminum powder compacts

This article focuses on the characterization of self-propagating high-temperature synthesis (SHS) reactions that occur in powder compacts containing titanium, boron, and aluminum. Interest in this powder system is based on the critical need to develop new joining techniques for bonding ceramics to metals. The exothermic reactions of particular interest in this study include those that generate TiB₂, TiB, Ti₃Al, and TiAl from their elemental powders. Data from differential thermal analysis (DTA), thermogravimetric analysis (TGA), and X-ray diffractometry are presented. These results demonstrate that the gas phase surrounding the SHS powders plays an important role in initiating the SHS reaction and in determining which reaction products will form in the final bond.     

Effects of TiB2/TiCx ratios on compression properties and abrasive wear resistance of in situ 50 vol.-% (TiB2–TiCx)/Al–Cu composites

Effects of TiB₂/TiC_x ratios on compression properties and abrasive wear resistance of 50?vol.-% (TiB₂–TiC_x)/Al–Cu composites fabricated via the combustion synthesis (CS) method assisted with hot press from the Al–Ti–B₄C system were studied. With decrease in the TiB₂/TiC_x ratio from 3:1 to 1:3, the shape of TiB₂ changed from platelike to clubbed while the size of TiC_x particles increased, which directly led to different mechanical properties. The 50?vol.-% (TiB₂–TiC_x)/Al–Cu composite with the TiB₂/TiC_x ratio of 2:1 exhibited good compression strength without sacrificing the fracture strain, while the composite possessed the highest abrasive wear resistance when the TiB₂/TiC_x ratio was 3:1. The appropriate TiB₂/TiC_x ratio was recommended to be 2:1 in this research.     

Unlubricated fretting wear of TiB2-containing composites against bearing steel

Fretting tests under dry unlubricated conditions (22 °C to 25 °C, 50 to 55 pct RH) were performed on monolithic TiB₂, TiB₂-based cermet with a Ni₃(Al,Ti) binder, sialon-TiB₂, and ZrO₂-TiB₂ composites to assess their relative wear performance against bearing-grade steel. Based on the measured friction and wear data, the relative ranking of the investigated fretting couples is established. The fretting wear of all investigated tribocouples was found to fall in the tribochemical wear regime. The extent of the tribochemical reaction was observed to be strongly dependent on the chemical solubility of TiB₂ and the binder phases in steel at the tribocontacts and was accompanied by tribo-oxidation. For the monolithic TiB₂ and TiB₂-based cermet materials, however, abrasion and adhesive wear, in addition to the tribochemical reactions, are found to be the cause for the high volumetric wear loss of these tribosystems. On the other hand, mild abrasion coupled with reduced tribochemical reactions is observed to play a major role in the low wear loss of the ZrO₂-TiB₂/steel fretting couple. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis of the tribochemical layer formed in the monolithic TiB₂/steel tribocouple revealed the formation of mixed oxides containing predominantly TiO₂ (anatase), B₂O₃, and Fe₂O₃. Based on the thermodynamic calculations and the experimental observations, a tribochemical wear model is proposed to explain the observed tribological behavior of the investigated tribosystems.     

Boron removal by titanium addition in solidification refining of silicon with Si-Al melt

In order to effectively remove B from Si for its use in solar cells, a process involving B removal by solidification refining of Si using a Si-Al melt with Ti addition was investigated. For clarifying the effect of Ti addition on B removal from the Si-Al melt, TiB₂ solubilities in Si-64.6 at. pct Al melt at 1173 K and Si-60.0 at. pct Al melt at 1273 K were determined by measuring the equilibrium concentrations of B and Ti in the presence of TiB₂ precipitates. The small solubilities of TiB₂ in the Si-Al melt indicate the effective removal of B from the Si-Al melt by Ti addition. Further, solidification experiments of Si-Al alloys containing B by Ti addition were performed, and the effect of Ti addition on the solidification refining of Si with the Si-Al melt was successfully confirmed.     

Grain refinement in aluminum alloyed with titanium and boron

The aluminum corner of the ternary Al-B-Ti diagram was explored. A eutectic: Liq — Al + TiAl₃ + (Al, Ti)B₂ was found at approximately 0.05 wt pct Ti, 0.01 wt pct B; 659.5‡C. TiB₂ and A1B₂ form a continuous series of solid solutions, but no distinct ternary phase was found. The addition of boron to aluminum-titanium alloys expands the field of primary crystallization of TiAl₃ toward lower titanium contents and steepens the liquidus. In equilibrium conditions, pronounced grain refinement is found only in alloys in which TiAl₃ is primary and nucleates the aluminum solid solution before any other impurity can act. The peritectic reaction facilitates this priority but it is not necessary for grain refinement. Because of the low diffusivity of titanium and boron in aluminum, equilibrium is seldom attained and in commercial practice grain refinement by TiAl₃ is found also outside its equilibrium field of primary crystallization.     

Fabrication of aluminum–ceramic skeleton composites based on the Ti<Subscript>2</Subscript>AlC MAX phase by SHS compaction

A one-stage manufacturing technology of aluminum–ceramic skeleton composites by combining the processes of self-propagating high-temperature synthesis (SHS) of a porous skeleton formed by the MAX phase of the Ti₂AlC composition and its impregnation by the aluminum melt under pressure (SHS compaction) is considered. A composition of the exothermic charge 2Ti + C + 22.5 wt % Al + 10 wt % TiH₂, which provides the formation of a porous skeleton of the Ti₂AlC phase without impurity phases by the SHS technology, is selected. It is shown that, when impregnating the hot SHS skeleton with aluminum, new phases are formed such as the MAX phase (Ti₃AlC₂), titanium carbide (TiC), and titanium aluminide (Al₃Ti). However, the content of the basic MAX phase remains high, and the ceramic component of the material consists of Ti₂AlC by 76%. When analyzing the microstructure, it is revealed that the composite has certain residual porosity after impregnation and cooling. The influence of the impregnation pressure (q = 22, 28, and 35 MPa) on the distribution of the aluminum content over the height and radius of the diametral sample section is investigated experimentally. It is shown that the nonuniform Al distribution over the sample bulk is caused by the nonuniform pressure and temperature fields, as well as the different compactibility of hot inner and colder outer sample parts. The degree of compaction of characteristic zones is leveled as the impregnation pressure increases, and the composition inhomogeneity over the sample bulk decreases. The difference in aluminum concentration over the sample bulk at q = 35 MPa does not exceed 5%. The SHS-compacted aluminum–ceramic skeleton composite based on the Ti₂AlC MAX phase corresponds to high-strength Al-Zn–Mg–Cu aluminum alloys by the hardness level (HB ≈ 150 kg/mm²).     

Effects of powder processing on densification of titanium diboride based cermets

Abstract

The sinterability of TiB₂-Ni₃(Al,Ti) based cermets has been significantly improved by aggressive milling of the starting TiB₂-Ni-TiAl₃ powder mixtures. This technique improves not only liquid spreading by reducing TiAl₃ particle size but also eliminates alumina agglomerates and the associated porosity found after vacuum sintering. Liquid phase sintering of TiB₂-Ni-TiAl₃ powder mixtures involves the presence of Ni based secondary borides at low temperatures (1200°C), which react afterwards with TiAl₃ particles leading to the formation of the final TiB₂-Ni₃(Al,Ti) eutectic liquid. Apart from improving liquid spreading around TiB₂ grains, aggressive milling is also found to disperse alumina agglomerates, which reduces the porosity associated to these particles. By this refined procedure, the amount of binder phase required for full densification of TiB₂ cermets by sinter hipping has been reduced from a previous limit of 16 vol.-% to 10 vol.-%. The hardness of these TiB₂-10 vol.-%Ni₃(Al,Ti) cermets is in the range of ultrafine WC-Co hardmetals in spite of their much coarser microstructure.