Multistage sintering process for Ni3Al powder metallurgical products

A multistage sintering process for powder metallurgical products of nickel aluminide intermetallic compound has been investigated. It comprises at least two stages of sintering and interstage cold deformation to collapse and eliminate the sintering pores. Most of all, a thermally absorbing material has to keep in contact with the powder compacts during the preliminary heating stage (650 °C, the first stage of reactive sintering). It depresses the maximum temperature of specimens to develop the useful transient phase Ni₂Al₃. This transient phase is a brittle and especially crispy material with a relatively low melting point (1135 °C). It plays an important role in preventing the development of any significantly large cracks during the pore-eliminating process. The purpose of the second stage of sintering material at an elevated temperature (1200 °C) is to develop a transient liquid phase from the Ni₂Al₃ to heal or eliminate any microcracks, crazes, and collapsed pores from previous steps, as well as to transfer the material to the final Ni₃Al structure. It is beneficial to produce a sound product having a large dimension and excellent mechanical properties. Consequently, the specimens will be further densified by a repeated cycle of thermal mechanical treatment (TMT).     

A study on the improvement of the sintered density of W-Ni-Mn heavy alloy

Liquid phase sintering behavior of 90W-6Ni-4Mn heavy alloy has been studied. The present work takes into account the thermodynamic oxidation/reduction reactions of the constituent elements W, Ni, and Mn. The sintering cycle consists of heating under high purity nitrogen gas, holding at reduction temperatures after the atmosphere is changed to dry hydrogen, and sintering at 1260 °C for 1 hour. As the reduction temperature increases from 1050 °C to 1200 °C, the relative sintered density increases from 92 pct, reaching 100 pct at temperatures above 1150 °C. The relative density increases with increasing holding time at the reduction temperature and remains unchanged with heating rate. The sintered microstructure has been analyzed by a scanning electron microscope and energy dispersive X-ray spectroscopy. The relative density was compared with those obtained from other investigators. It is found that the formation of manganese oxide due to reducing reactions of W and Ni powders should be avoided in order to obtain a W-Ni-Mn heavy alloy without pores.     

Structural characteristics of Nb3Sn produced by three P/M techniques

Powder metallurgical techniques have been applied to the problem of preparing monolithic samples of Nb₃Sn of a homogeneity, density and stability suitable for unambiguous plastic deformation studies. Cold pressing and reaction sintering, infiltration, and hot isostatic pressing (HIP) of Nb and Sn powders have been evaluated, with HIP processing producing a decidedly superior structure. The most homogeneous structure was produced by HIP processing at 1630°C for one h at a pressure of 160 MPa. A continuous matrix of Nb₃Sn was produced with a porosity of 2.6 pct and a secondary phase content of 3.3 pct. The principal secondary phase was NbO and no unreacted Nb remained. The Nb₃Sn matrix was quite homogeneous with microprobe analysis revealing an off-stoichiometric composition of 72.2 to 73.2 pct Nb. An equiaxed grain size of about 60 μm was developed and X-ray diffraction analysis revealed a high degree of long range order. HIP processing at 1200°C produced a finer grain size, increased porosity, and an incompletely reacted structure involving 3.5 pct unreacted Nb. The composition of the Nb₃Sn phase was nearly the same, regardless of processing technique. Considerable evidence of dislocations arrayed in low angle, sub-grain boundaries was observed in the 1630°C HIP processed material. Simple, isolated dislocations were predominant in the 1200°C HIP processed material.     

Effect of liquid phase on the densification of tungsten-copper and molybdenum-copper pseudoalloys in sintering

The paper examines how the amount of the liquid phase influences the densification of loose W-Cu and Mo-Cu powder mixtures in liquid-phase sintering at 1200°C, with the content of the low-melting component ranging from 20 to 90 wt.%. It is observed that the density grows continuously with increasing amount of the liquid phase in both W-Cu and Mo-Cu systems. It is shown that samples sintered with a great amount of the liquid phase in the W-Cu and Mo-Cu systems retain their shape.     

A sintering study on the β-spodumene-based glass ceramics prepared from gel-derived precursor powders with LiF additive

Beta-spodumene (Li₂O·Al₂O₃·4SiO₂, LAS) powders were prepared by a sol-gel process using Si(OC₂H₅)₄, Al(OC₄H₉)₃, and LiNO₃ as precursors and LiF as a sintering aid agent. Dilatometry, X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), and electron diffraction (ED) were utilized to study the sintering, phase transformation, microstructure, and properties of the β-spodumene glass-ceramics prepared from the gel-derived precursor powders with and without LiF additives. For the LAS precursor powders containing no LiF, the only crystalline phase obtained was β-spodumene. For the pellets containing less than 4 wt pct LiF and sintered at 1050 °C for 5 hours the crystalline phases were β-spodumene and β-eucryptite (Li₂O·Al₂O₃·2SiO₂). When the LiF content was 5 wt pct and the sintering process was carried out at 1050 °C for 5 hours, the crystalline phases were β-spodumene, β-eucryptite (triclinic), and eucryptite (rhombohedral (hex.)) phases. With the LiF additive increased from 0.5 to 4 wt pct and sintering at 1050 °C for 5 hours, the open porosity of the sintered bodies decrease from 30 to 2.1 pct. The grains size is about to 4 to 5 μm when pellect LAS compact contains LiF 3 wt pct as sintered at 1050 °C for 5 hours. The grains size grew to 8 to 25 μm with a remarkable discontinuous grain growth for pellet LAS compact contain LiF 5 wt pct sintered at 1050 °C for 5 hours. Relative densities greater than 90 pct could be obtained for the LAS precursor powders with LiF > 2 wt pct when sintered at 1050 °C for 5 hours. The coefficient of thermal expansion of the sintered bodies decreased from 8.3 × 10⁻⁷ to 5.2 × 10⁻⁷/°C (25 °C to 900 °C) as the LiF addition increased from 0 to 5 wt pct.     

Sulfation of a nickeliferous laterite

The sulfur trioxide roasting of a ferruginous, nickeliferous laterite was investigated at temperatures from 500° to 800°C. The kinetics of the fixed bed sulfation appeared to be logarithmic and this was interpreted to indicate a transport controlled process. Reaction rate constants were evaluated and it was found that the time for equivalent sulfation of nickel was more than 5 orders of magnitude greater at 800°C than at 600°C. The composition of the products appeared to dominate the reaction kinetics through changes in their physical nature. Nickel and cobalt sulfated quite rapidly at temperatures from 600° to 700°C but favorable selectivity over iron could be obtained only at temperatures >750°C where the nickel sulfation rate falls off rapidly. A two-step sulfation process was investigated that takes advantage of the rate characteristics of the low temperature process and attains selectivity by reversing the iron reaction at a higher temperature. Approximately 87 pct of the nickel, 97 pct of the cobalt, and 2 pct of the iron were extracted in a two-step process without additives.     

Multistage sintering approach to prepare Ni3Al/α-Al2O3 composites

The nickel aluminide intermetallic matrix composites (IMC), Ni₇₆Al₂₄B_0.1 with either 5 or 10 vol pct α-Al₂O₃, were synthesized through a multistage sintering approach from the elemental powders of Ni, Al, and oxide of α-Al₂O₃. An electroless nickel-boron (Ni-B) plating process was adopted to improve the contacted interface between the reinforced oxide ceramics and the metal matrix, as well as to supply the atomic scale boron in the metallic matrix of the IMCs. The entire process comprises steps involving preparing a powdery starting material, sealing it within a metal sheath or can, compacting or cold deforming it, preliminarily heating the compacted material at a relatively low temperature, executing a pore-eliminating (mechanical deforming) process to eliminate the pores resulting from the preceding heating step, and sintering the material at a relatively high temperature to develop a transient liquid phase to heal or to eliminate any microcracks, crazes, or collapsed pores from the previous steps. Most of all, it is important that contact with a heat absorbent material, such as a metal sheath, produces the Ni₂Al₃ phase during preliminary heating. This new phase is a brittle and crispy material with a low melting point (1135 °C). It has been found to play an important role in preventing any significant cracks during the pore-eliminating process and in developing a transient liquid phase in the following 1200 °C sintering step. This multistage sintering with a heat absorbent process is beneficial for producing a product that has large dimensions, a desirable shape, good density, and excellent mechanical properties. The resulting elongation of tensile tests in air reaches 14.6 and 8.9 pct for the present 5 and 10 vol pct powder metallurgy IMCs, respectively.     

Sintering kinetics and alumina yield in lime-soda sinter process for alumina from coal wastes

An investigation of the application of the lime-soda sinter process to alumina extraction from coal wastes has been carried out. In the sintering stage, the optimal operating conditions have been obtained for the highest yield of alumina. The kinetics of sodium aluminate formation have also been studied in the sintering stage. The sinter mixes have been fired isothermally in air in the temperature range 1100 to 1350 °C. Alumina recovery of about 80 pct has been obtained by sintering coal-waste mixes having molar ratios of Na₂O/Al₂O₃ = 1.3 and CaO/SiO₂ = 1.8 at 1200 to 1250 °C for 20 to 30 minutes. Insoluble alumina compounds are responsible for the incomplete recovery. The major sinter components are identified as sodium aluminate and β-dicalcium silicate. The nucleation and growth kinetics equation is used to correlate the experimental data of sodium aluminate formation obtained under atmospheric pressure in the temperature range 1000 to 1200 °C. An activation energy of 286 kJ/mol has been calculated for fine coal-waste powder mixtures. Formerly Graduate Student in Metallurgy.     

Rapid synthesis of ternary carbide Ti3SiC2 through pulse-discharge sintering technique from Ti/Si/TiC powders

Ti/Si/TiC powders with molar ratios of 1:1:2 (M1) and 2:2:3 (M2) were prepared for the synthesis of a ternary carbide Ti₃SiC₂ by using the mixture method for 24 hours in an Ar atmosphere. The synthesis process was conducted at 1200 °C to 1400 °C under a pressure of 50 MPa, using the pulse-discharge sintering (PDS) technique. After sintering, the phase constituents and microstructures of the samples were analyzed by X-ray diffraction (XRD) technique and observed by optical microscopy and scanning electron microscopy. The results showed that the phases in all the samples consisted of Ti₃SiC₂ and small amounts of TiC, and the optimum sintering temperature was found to be in the relatively low range of 1250 °C to 1300 °C. By the standard additive method, the relative content of Ti₃SiC₂ was calculated. For the M1 samples, the lowest TiC content can be only decreased to about 3 to 4 wt pct, whereas the content of Ti₃SiC₂ in the M2 samples is always lower than that in the M1 samples. When the M2 powder was sintered at 1300 °C for 8 to 240 minutes, the TiC peaks were found to show a very low intensity, and the corresponding content of Ti₃SiC₂ was calculated to be higher than 99 wt pct. The grain size of Ti₃SiC₂ increased from 5 to 10 μm to 80 to 100 μm in the entire applied sintering temperature range. The relative density of the M2 samples was measured to be higher than 99 pct at sintering temperatures above 1275 °C. It indicates that the PDS technique can rapidly synthesize high-content Ti₃SiC₂ from the Ti/Si/TiC powders in a relatively low temperature range.     

Fabrication of a multi-phase porous high-temperature Mo–Si–B alloy by in situ reaction synthesis

ABSTRACT

The pore formation process has been studied for a high-temperature porous Mo–Si–B alloy produced by in situ reaction synthesis from elemental starting powders. The expansions, phase transformations, microstructure and pore parameters were investigated systematically as a function of the sintering temperature. For sintering temperatures of 1200°C and above, a multiphase mixture of the oxidation-resistant intermetallic compounds Mo₃Si, Mo₅Si₃ and Mo₅SiB₂ was obtained. It was found that the porous alloys exhibit uniform skeletons with fine grains, high porosities and centred pore size distributions. Characterisation data obtained from samples sintered at temperatures from 1200 to 1600°C are used to deduce the processes which occur at each stage in the reaction synthesis. This helps to explain the formation mechanism for the pores and skeletons in this novel material.     

Design of strong tough Fe/Mo/C martensitic steels and the effects of cobalt

The microstructures and mechanical properties of a series of vacuum melted Fe/(2 to 4) Mo/(0.2 to 0.4) C steels with and without cobalt have been investigated in the as-quenched fully martensitic condition and after quenching and tempering for 1 h at 673 K (400°C) and 873 K (600°C); austenitizing was done at 1473 K (1200°C) in argon. Very good strength and toughness properties were obtained with the Fe/2 Mo/0.4 C alloy in the as-quenched martensitic condition and this is attributed mainly to the absence of internal twinning. The slightly inferior toughness properties compared to Fe/Cr/C steels is attributed to the absence of interlath retained austenite. The two 0.4 pct carbon steels having low Mo contents had approximately one-half the amount of transformation twinning associated with the two 0.4 pct carbon steels having high Mo contents. The plane strain fracture toughness of the steels with less twinning was markedly superior to the toughness of those steels with similar alloy chemistry which had more heavily twinned microstructures. Experiments showed that additions of Co to a given Fe/Mo/C steel raised M_s but did not decrease twinning nor improve toughness. Molybdenum carbide particles were found in all specimens tempered at 673 K (400°C). The Fe/Mo/C system exhibits secondary hardening after tempering at 873 K (600°C). The precipitate is probably Mo₂C. This secondary hardening is associated with a reduction in toughness. Additions of Co to Fe/Mo/C steels inhibited or eliminated the secondary hardening effect normally observed. Toughness, however, did not improve and in fact decreased with Co additions.     

Effect of conventional and microwave sintering on the properties of yttria alumina garnet-dispersed austenitic stainless steel

The current study examines the effect of heating mode, temperature, and varying yttria alumina garnet (YAG) addition (5 and 10 wt pct) on the densification and properties of austenitic (316L) stainless steel. The straight 316L stainless steel and 316L-YAG composites were heated in a radiatively heated (conventional) and 2.45 GHz microwave sintering furnace. The compacts were consolidated through solid state as well as supersolidus sintering at 1200 °C and 1400 °C, respectively. Both 316L and 316L-YAG compacts couple with microwaves and heat to the sintering temperature rapidly (∼45 °C/min). The overall processing time was reduced by about 90 pct through microwave sintering. As compared to conventional sintering, compacts sintered in microwaves exhibit higher densification and finer microstructure but no corresponding improvement in mechanical properties and wear resistance. This has been correlated to elongated, irregular pore structure in microwave-sintered compacts.     

Effect of interaction between the structural components of W-Co-Sn pseudo-alloys on the kinetics of their compaction during liquid-phase sintering

Compaction kinetics during liquid-phase sintering of W-Co-Sn powder composites containing 90 mass% refractory component and 10 mass% readily-melting component is studied. It is established that compaction kinetics depends markedly on cobalt content in the melt. Specimens with a cobalt content up to 3 mass% at 1200 °C (in the nonisothermal heating stage) undergo an increase in volume, and then they are compacted at a rate typical for liquid-phase sintering. The nonuniform nature of compaction is observed with an increase in cobalt in the test composites. Specimens with a cobalt mass fraction of more than 2% (cobalt content with three-phase equilibrium) experience considerable additional growth due to formation of the intermetallic compound W₆Co₇ whose decomposition temperature exceeds the liquid-phase sintering temperature.     

Studies on hot deformation of sintered cobalt

The hot deformation behavior of sintered cobalt powder was studied. The Co powder prepared by thermal decomposition of cobalt oxalate was subsequently compacted by cold isostatic pressing (CIP) and sintered at 1300 °C under H₂ atmosphere. Cobalt rods of 95 pct theoretical density were obtained. Strain rate change tests in compression were conducted in the temperature range of 900 °C to 1300 °C by changing strain rates from 0.001 to 3.2 s⁻¹. Uninterrupted hot compression tests at constant strain rates and selective temperatures were also conducted. Microcracks as well as surface cracks were observed in the samples tested below 1200 °C. It was observed that the strain rate sensitivity (SRS) increased with increasing temperature and decreasing strain rate, with the maximum SRS of 0.3 being obtained at 1285 °C and strain rate of 10⁻³ s⁻¹. Despite the higher SRS at low strain rates, the hot workability of sintered cobalt was found to be poor. Extensive grain boundary microcracking was observed, with the density being lowered after deformation. However, the samples tested at higher strain rates showed less microcracking and an increase in density. On the basis of the results, it was concluded that ease of grain boundary sliding at lower strain rates and higher temperatures was responsible for the poor workability at these conditions.     

Effect of LiF as Sintering Agent on the Densification and Phase Formation in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-4 Wt Pct Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> Ceramic Compound

Different amounts of LiF were added to an Al₂O₃-4 pct Nb₂O₅ basic ceramic, as sintering agent. Improved new ceramics were obtained with LiF concentrations varying from 0.25 to 1.50 wt pct and three sintering temperatures of 1573 K, 1623 K, and 1673 K (1300 °C, 1350 °C, and 1400 °C). The addition of 0.5 wt pct LiF yielded the highest densification, 94 pct of the theoretical density, in association with a sintering temperature of 1673 K (1400 °C). Based on X-ray diffraction (XRD), this improvement was due not only to the presence of transformed phases, more precisely Nb₃O₇F, but also to the absence of LiAl₅O₈. The preferential interaction of LiF with Nb₂O₅, instead of Al₂O₃, contributed to increase the alumina sintering ability by liquid phase formation. Scanning electron microscopy (SEM) results revealed well-connected grains and isolated pores, whereas the chemical composition analysis by energy dispersive energy (EDX) indicated a preferential interaction of fluorine with niobium, in agreement with the results of XRD. It was also observed from thermal analysis that the polyethylene glycol binder burnout temperature increased for all LiF concentrations. This may be related to the formation of hydrogen bridge bonds.     

Dilatometry study of the sintering behavior of boron-alloyed Fe-1.5 pct Mo powder

The effect of different boron concentrations on the sintering behavior of an Fe-1.5 pct Mo (wt pct) prealloyed powder was investigated. Sintering was carried out in a dilatometer so that all dimensional changes involved with the densification process could be followed. Several transformations were found to occur by heating powder compacts to 1200 °C and then cooling them to room temperature. At high temperatures, boron promoted the formation of liquid phases that, through a more-efficient sintering kinetics, promoted a satisfactory densification. Faster heating rates also had beneficial effects on the density of the final products. From a microstructural point of view, boron tended to destabilize the ferritic phase and to form iron and molybdenum borides. These borides can be found both in the intergranular regions, with a typical eutectic morphology, and dispersed in the ferritic matrix, in the form of nanometer-sized precipitates. This feature, having a significant effect on the hardness of the bulk material, has been ascribed to a bainite-like precipitation of borides from an undercooled austenitic phase.     

Development of austenitic nanostructures in high-nitrogen steel powders processed by mechanical alloying

In this work, mechanical alloying was employed in producing high-nitrogen Fe18Cr11Mn stainles-steel powders. It was found that the nitrogen solubility in the powder mixtures increases exponentially with milling time at room temperature. Maximum nitrogen levels of 2.47 wt pct N were achieved after milling for 170 hours. In addition, the grain size structure continually decreased and reached a plateau at nanometric grain sizes of the order of 3 nm. In addition, measured, interplanar lattice spacing, d₍₁₁₀₎, did not follow a linear trend. Apparently, initially the nitrogen tendency was to be preferentially dissolved at dislocations and grain boundaries. However, after long milling times, the crystal lattice tended to be saturated with N. Annealing at 900 °C to 1200 °C for 2 hours led to various microstructures, where the matrix was almost always γ-iron, but Cr₂N, CrN, and α-iron were also present depending on the annealing temperatures. In particular, it was found that a fully austenitic, nanometric grain structure can be achieved by annealing at 1000 °C and 1100 °C Fe18Cr11Mn alloys with 1.02 and 0.7 wt pct N, respectively.     

Interdiffusional effects between tungsten fibers and an iron-nickel-base alloy

Tungsten fibers in the INCOLOY* 903 alloy were annealed for over 100 hours at 1038 °C and 1200 °C. It was found that interdiffusion results in the formation of a reaction zone. SEM-EDS probe analysis showed that the chemistries across this zone were constant, suggesting the zone was a compound phase. The composition of the compound was estimated to be that of a μ-type phase. The local chemistry (in atomic percent) at the reaction zone/alloy matrix interface was found to be approximately 8 pct W, 1.2 pct Nb, 40 pct Fe, 14 pct Co, and 36 pct Ni. In addition, recrystallization was observed in both the remaining tungsten fiber and the nearby INCOLOY 903 matrix after annealing at 1200 °C, but not at 1038 °C. The results of this study suggest that reaction zone growth kinetics can be minimized by the reduction of Co and Fe and the increase of W in the matrix alloy.     

Design of strong tough Fe/Mo/C martensitic steels and the effects of cobalt

The microstructures and mechanical properties of a series of vacuum melted Fe/(2 to 4) Mo/(0.2 to 0.4) C steels with and without cobalt have been investigated in the as-quenched fully martensitic condition and after quenching and tempering for 1 h at 673 K (400°C) and 873 K (600°C); austenitizing was done at 1473 K (1200°C) in argon. Very good strength and toughness properties were obtained with the Fe/2 Mo/0.4 C alloy in the as-quenched martensitic condition and this is attributed mainly to the absence of internal twinning. The slightly inferior toughness properties compared to Fe/Cr/C steels is attributed to the absence of interlath retained austenite. The two 0.4 pct carbon steels having low Mo contents had approximately one-half the amount of transformation twinning associated with the two 0.4 pct carbon steels having high Mo contents. The plane strain fracture toughness of the steels with less twinning was markedly superior to the toughness of those steels with similar alloy chemistry which had more heavily twinned microstructures. Experiments showed that additions of Co to a given Fe/Mo/C steel raisedM _S but did not decrease twinning nor improve toughness. Molybdenum carbide particles were found in all specimens tempered at 673 K (400°C). The Fe/Mo/C system exhibits secondary hardening after tempering at 873 K (600°C). The precipitate is probably Mo₂C. This secondary hardening is associated with a reduction in toughness. Additions of Co to Fe/Mo/C steels inhibited or eliminated the secondary hardening effect normally observed. Toughness, however, did not improve and in fact decreased with Co additions.     

Mechanical properties of Ir-Nb alloys containing Ni and Al

Two alloys made by adding 5 or 10 at. pct, respectively, of Ni-18.9 at. pct Al to an Ir-15 at. pct Nb alloy were investigated. The microstructure and compressive strength at temperatures between room temperature and 1800 °C were investigated to evaluate the potential of these alloys for ultra-high-temperature use. Their microstructural evolution indicated that the two alloys formed fcc and L1₂-Ir₃Nb two-phase structures. The fcc and L1₂ two-phase structures were examined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The 0.2 pct flow stresses were above 1000 MPa at temperatures up to 1200 °C, about 150 MPa at 1500 °C, and over 100 MPa at 1800 °C. The strength of the quaternary Ir-base alloys at 1200 °C was even higher than that of Ir-base binary and ternary alloys. And the strength of quaternary Ir-Nb-Ni-Al was equivalent to that of the Ir-15 at. pct Nb binary alloy at 1800 °C. The compressive ductility of quaternary (around 20 pct) was improved drastically compared with that of the Ir-base binary alloy (lower than 10 pct) and the ternary Ir-base alloys (about 11 pct). An excellent balance of high-temperature strength and ductility was obtained in the alloy with 10 at. pct Ni-18.9 at. pct Al. The effect of Ni and Al on the strength of the Ir-Nb binary alloy is discussed.