Investigation of the influence of Ni powder size on microstructural evolution and the thermal explosion combustion synthesis of NiTi

A key microstructural feature that controls the sintering behavior of Ni + Ti powders was determined to be the transformation of alpha-Ti to beta-Ti during heating. The use of very fine Ni powders causes this transformation to occur at the eutectoid temperature (i.e., 765 °C). The use of coarse Ni powders causes a gradual beta-Ti transformation from 765 to 882 °C. At 950 °C a large volume fraction of beta-Ti remains in coarse Ni/Ti mixtures whereas in fine Ni/Ti mixtures this phase is almost eliminated. Further heating above 950 °C causes the beta-Ti to melt, initiating a large exothermic reaction in the coarse Ni/Ti mixtures (i.e., 158 J/g) at 980 °C. The use of fine Ni significantly reduces this reaction (i.e., 3 J/g). Consequently, Ni powder size, and its influence over beta-Ti content can be used to control the reactive sintering behavior of Ni + Ti mixtures.     

Self-ignition combustion synthesis of TiFe in hydrogen atmosphere

This paper describes the self-ignition combustion synthesis (SICS) of highly active titanium iron (TiFe) in a high-pressure hydrogen atmosphere without employing an activation process. In the experiments, well-mixed powders of Ti and Fe in the molar ratio of 1:1 were uniformly heated up to 1085 °C, the eutectic temperature of Ti–Fe binary system, in pressurized hydrogen at 0.9 MPa. The electric source was disconnected immediately after the ignition between Ti and Fe, and the mixture was cooled naturally. In this study, the exothermic reaction Ti + Fe = TiFe + 40 kJ occurred at around 1085 °C after the hydrogenation and decomposition of Ti. X-ray diffraction analysis showed that the final product had only one phase—TiFeH_0.06—which can store hydrogen of 1.55 mass% under hydrogen pressure of 4 MPa. The product obtained by SICS contained considerably more hydrogen quickly as compared to the commercially available product; this fact can be explained by the porous structure of the obtained product, which was observed using a scanning electron microscope. In conclusion, the SICS of TiFe saved time and energy, yields products with high porosity and small crystals, enabled easy hydrogenation, and did not require activation processes.     

Effects of C particle size on the ignition and combustion characteristics of the SHS reaction in the 20 wt.% Ni–Ti–C system

C particle size plays an important role in the ignition and combustion characteristics of the SHS reaction in the 20 wt.% Ni–Ti–C system. When coarse C particles (38 and 75 μm) are used, the SHS reactions consist of two different combustion stages with different brightness intensity of the combustion wave; XRD results indicate that the first and second combustion stages mainly correspond to the formation of Ni–Ti compounds and TiC ceramics, respectively. However, the final reaction is incomplete with a few Ni–Ti compounds and unreacted C. In contrast, when the fine C particle (1 μm) is used, the SHS reaction consists of only one combustion stage with high brightness intensity of the combustion wave; XRD result indicates that final products consist of TiC and Ni, without any intermediate phase. With the decrease of C particle size, the wave velocities increase, and the ignition time becomes shorter. In addition, the morphology of TiC particulate changes to near-spherical, as C particle size decreases.     

Synthesis of nanocrystalline Gd doped ceria by combustion technique

High ionic conductivity of doped ceria at comparatively lower operating temperatures (650 °C) makes it suitable solid oxide fuel cell (SOFC) electrolyte. In the present investigation, successful attempt has been made to synthesize Ce_0.9Gd_0.1O_1.95 (GDC10) solid solution by cost effective and simple chemical method of combustion where in the combustion of precursors results in the formation of nanoparticles relatively at lower processing temperature. The thermogravimetric study was carried out to understand the ignition temperature and optimize the fuel-to-oxidant ratio. The successful synthesis of single phase nanocrystalline GDC10 was confirmed by XRD, TEM and particle size analysis. Further SEM and surface measurements were carried out to confirm higher sample densities.     

Ethanol-assistant solution combustion method to prepare La2O2S:Yb,Pr nanometer phosphor

La₂O₂S:Yb,Pr nanometer phosphor have been prepared by a novel ethanol-assistant solution combustion (EASC) method in ethanol–water solution medium via a relatively mild and slow combustion process, using ethanol as preigniting fuel and inexpensive thioacetamide as sulfur-containing organic fuel. Investigation results show: ethanol preigniting serves the role of ignition combustion decomposition reaction between rare earth nitrate and organic fuel and promotes the formation of uniform and less agglomerative rare earth oxysulfide nanocrystals. Single phase Ln₂O₂S:Yb,Pr nanocrystals are obtained with appropriate ethanol/water ratio and further annealing at 1000 °C for 2 h in reduced atmosphere. The La₂O₂S:Yb,Pr nanocrystals exhibit an intense green emission assigned to the Pr³⁺ ions ³P₀ → ³H₄ transition and a broad near infrared (NIR) emission under 980 nm pump. The defects residing in La₂O₂S:Yb,Pr nanocrystals is the probable origins for the NIR emission. The annealing process makes the green emission improve and the NIR emission weaken. After annealing treatment at 1000 °C, the upconversion luminescence intensity is close to that of the bulk sample prepared by a solid-state reaction method.     

On the four-phase reactions in the Ti–Ni–Al system

Two four-phase reactions of transition type in the Ti–Ni–Al system were studied on several alloys, which were annealed at carefully set temperatures and quenched. The phase constitution was established by XRD and EPMA analyses. Due to sluggish reaction kinetics, the transition temperatures were defined by annealing and quenching techniques as no DTA signals could be received. For the reaction NiAl + TiNiAl  TiNiAl₂ + TiNi₂Al, the transition temperature was found to be 925 °C ± 15 °C and for the reaction TiNiAl + Ti₃NiAl₈  TiAl₂ + TiNiAl₂, the transition temperature was found to be 990 °C ± 15 °C. Furthermore we confirmed the three-phase field TiNi₂Al + Ti₃Al + Laves phase (TiNiAl), as reported at 900 °C by Huneau et al. in 1999.     

Preparation of platinum-iridium nanoparticles on titania nanotubes by MOCVD and their catalytic evaluation

Pt based catalysts are commonly used in several industrial processes involving hydrogenation and dehydrogenation reactions. New deposition methods as well as support materials are being investigated to generate new catalysts with superior catalytic activity. In this work, platinum-iridium (Pt-Ir) nanoparticles of about 5 nm in size were supported on titania (TiO₂) nanotubes by metal organic chemical vapor deposition (MOCVD). The TiO₂ nanotubes were prepared by an alkali hydrothermal method using sodium hydroxide solution at 100 °C, during 64.8 ks. Pt-Ir nanoparticles were obtained by controlling the MOCVD conditions at 400 °C and 66.6 kPa.Textural properties and particle size were investigated by nitrogen physisorption (BET method), X-ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy. Catalytic activity was measured in cyclohexene disproportion as the test molecule for hydrogenation/dehydrogenation reactions. The TiO₂ nanotubes exhibit a considerable high surface area of about 425,000 m²/kg, however, after calcination at 400 °C their nanotubular morphology was partially transformed. In spite of this change, the 5 nm Pt-Ir nanoparticles supported on TiO₂ nanotubes were more active in the cyclohexene disproportion reaction than conventional Pt-Ir/alumina catalysts in the whole range of temperatures investigated (50–250 °C). Hydrogenation reactions (high selectivity to cyclohexane) predominate at temperatures below 150 °C.     

Combustion synthesis of TiC–TiB2 composites

An experimental study on formation of TiC–TiB₂ in situ composites with a broad range of compositions was conducted by self-propagating high-temperature synthesis (SHS) using the reactant compacts from different combinations of Ti, B₄C, C, and B powders. Direct reaction of Ti with B₄C at stoichiometry of Ti:B₄C = 3:1 yields a TiB₂-rich composite with TiC:TiB₂ = 1:2. Formation of the products containing 20, 33.3, and 50 mol% of TiB₂ was achieved by the Ti–B₄C–C reactants. In addition, the test specimen composed of Ti, B₄C, and B was employed for the synthesis of a composite with 80 mol% TiB₂. Among three different types of the powder compacts, the boron-containing sample was characterized by the fastest combustion wave and the highest reaction temperature. The lowest combustion temperature and wave velocity were observed in the Ti–B₄C compact. When fine Ni particles were added to the Ti–B₄C reactant, it was found that the propagation rate of the reaction front was increased and the densification of the end product was enhanced significantly. This was attributed to formation of the Ti–Ni eutectic liquid during the reaction. As a result, the relative density of a TiC + 2TiB₂ composite increases from 30 to 86% with the Ni content from 0 to 20 mol%. Based upon the XRD analysis, small amounts of TiNi₃ and TiB were detected in the Ni-reinforced TiC–TiB₂ composites.     

Effects of iron catalyst on the formation of crystalline domain during carbonization of electrospun acrylic nanofiber

To investigate the effects of introducing the iron compound on the carbonization behavior polyacrylonitile (PAN)-based electrospun nanofibers were carbonized with or without iron(III) acetylacetonate (AAI) over the temperature range of 900–1500 °C in nitrogen atmosphere. The morphological characteristics of the carbon nanofibers were investigated using X-ray diffractometer (XRD), Raman spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy. The electrical conductivity of the carbon nanofiber web was measured by four-point probe method. The iron catalyst had a profound effect on the crystal structure of the carbonized nanofiber. In the presence of AAI the nanofibers carbonized at 1300 °C developed graphite structure, which could be obtained at the temperature higher than 2000 °C in the absence of the catalyst. The in-plane size of the graphite crystals (L_a) was measured to be about 6.5 nm by Raman spectroscopy and the (0 0 2) spacing by XRD was 0.341 nm.     

Effect of pressure on combustion synthesis of TiC/Fe-Cu composites under the action of electric current

Using electric-current-assisted combustion synthesis (ECACS) in a Gleeble thermal simulation instrument, composites of TiC/Fe-Cu have been in-situ synthesized directly from elemental powders of iron, copper, titanium and graphite. This study was focused on the effect of pressure on the combustion synthesis of TiC/Fe-Cu composites and the properties of TiC/Fe-Cu composites. With the aid of a high electric current, a relatively low onset temperature for the combustion reaction, between 747 °C and 768 °C, could be achieved. The ignition temperature decreased with the increase of the pressure in the heating process. The final products of samples were composed of Fe, Cu, TiC and the pressure had little influence on the phase composition. All the titanium carbide particles were fine and in a range of about 0.2 μm–0.35 μm. When the pressure increased, the density and microhardness of sample increased, so the wear resistance improved.     

The effect of dopant Cu, Fe, Ni or La on the structures and properties of mesoporous Co-Ce-O compound catalysts

A series of Co-Ce-O mesoporous catalysts doped with Cu, Fe, Ni or La and the undoped one were synthesized by using tri-block copolymer P-123 as the template. These catalysts show wormhole-like structures, high surface areas (144–167 m²/g) and uniform meso-pore size distributions (4.0–4.8 nm) after calcination at 500 °C. The activity for low-temperature CO oxidation and the thermal stability of the mesoporous Co-Ce-O catalyst are largely modified by the dopant Cu, Fe, Ni or La in different ways. It is revealed by in situ diffuse reflectance infrared spectroscopy that CO oxidation over all the samples except the Ni-doped one undergoes carbonates pathway. In this case, the oxidation activities of the catalysts are mainly determined by the mobility of surface lattice oxygen species, which is indicated by the temperature-programmed reduction and desorption results. Doping with Cu greatly enhances the oxidation activity of Co-Ce-O catalyst at the calcination temperatures of 500 °C and 650 °C, and doping with La significantly improves its activity at the calcination temperature of 800 °C. However, doping with Fe always decreases the activity of Co-Ce-O catalyst regardless of the calcination temperature. Largely different from other dopants, the addition of Ni induces a change of the mechanism for CO oxidation and results in a remarkable decrease in the activity.     

Bimetallic nanoalloys: Preparation, characterization and their catalytic activity

Bimetallic nanoalloys (BMNAs) of 3d-series (Ni–Cu, Ni–Co and Ni–Zn) were prepared by hydrazine reduction of respective metal chloride in ethylene glycol at 60 °C. These were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM) and particle size was found to be in the order of 34, 43 and 30 nm, respectively. The thermolysis of ammonium perchlorate (AP) and AP-HTPB composite solid propellants was found to be catalyzed with BMNAs and burning rate was found to be enhanced considerably. TG and ignition delay studies demonstrated that higher temperature decomposition (HTD) of AP is enhanced enormously by these additives and Ni–Co nanoalloy is the best catalyst.     

An experimental technique for the measurement of temperature on CBN tool face in end milling

An infrared radiation pyrometer with two optical fibers connected by a fiber coupler was developed and applied to the measurement of tool–chip interface temperature in end milling with a binderless CBN tool. The infrared rays radiated from the tool–chip interface and transmitted through the binderless CBN are accepted by the optical fiber inserted in the tool and are then sent to the pyrometer. A combination of the two fibers and the fiber coupler makes it possible to transmit the accepted rays to the pyrometer, which is set up outside of the machine tool. This method is very practical in end milling for measuring the temperature history at tool–chip interface during chip formation. The maximum tool–chip interface temperature in up milling of a 0.55% carbon steel is 480 °C when the cutting speed is 2.2 m/s and 560 °C at 4.4 m/s, and in the down milling, 500 °C at 2.2 m/s and 600 °C at 4.4 m/s.     

The effect of sintering temperature on densification of nanoscale dispersed W–20–40%wt Cu composite powders

Nanoscale dispersed particles of W–20–40%wt Cu were synthesized using a chemical procedure including initial precipitating, calcining the precipitates and reducing the calcined powders. The powders were characterized using X-ray diffraction and map analyses. The effect of sintering temperature was investigated on densification and hardness of the powder compacts. Relative densities more than 98% were achieved for the compacts which sintered at 1200 °C. The results showed that in the case of W–20%wt Cu composite powders, the hardness of the sintered compacts increased by elevating the sintering temperature up to 1200 °C while for the compacts with 30 and 40%wt Cu, the sintered specimens at 1150 °C had the maximum hardness value. The microstructural evaluation of the sintered compacts by scanning electron microscopy showed homogenous dispersion of copper and tungsten and a nearly dense structure. A new proposal for the variation of the mean size and morphologies of W-particles with volume percent of copper melt within the composites has been suggested.     

Influence of nanocrystalline Ni–Ti reaction agent on self-propagating high-temperature synthesized porous NiTi

Nanocrystalline Ni–Ti was used in self-propagating high-temperature synthesis (SHS) to fabricate porous NiTi. The SHS of porous NiTi using elemental powders was also prepared for comparison. Results showed that the main phase was NiTi with unreacted Ni when using elemental powders, which is detrimental to medical use. A large amount of Ti₂Ni secondary phase was also detected. By employing mechanically alloyed nanocrystalline Ni–Ti as a reaction agent, the secondary intermetallic phase (i.e. Ti₂Ni) was significantly reduced and the unreacted Ni was eliminated. The addition of 25 wt% nanocrystalline Ni–Ti reaction agent produced porous NiTi with an average porosity of 52–55 vol% and a general pore size of 100–600 μm under preheating temperatures of 200 and 300 °C. This general pore size in the range of 100–600 μm is beneficial to biomedical application for osseointegration. By further increase of the reaction agent to 50 wt% in the reactant, a porous NiTi part was produced at ambient temperature (i.e. no preheating was necessary) and a dense part was formed at preheated temperature of 200 °C due to the large amount of energies in the nanocrystalline reaction agent. This revealed that the use of nanocrystalline reaction agent effectively lowered the activation barriers for combustion synthesis reaction.     

Hot isostatic pressing (HIP) of α-Al2O3 submicron ceramics pressureless sintered at different temperatures: Improvement in mechanical properties for use in total hip arthroplasty (THA)

The effect of hot isostatic pressing (HIPing) on as-sintered α-Al₂O₃ ceramics for total hip arthroplasty (THA) was investigated. The sinterability of these powders and the minimum temperature required to obtain closed porosity have been determined by pressureless sintering in air at temperatures between 1280 and 1460 °C for 2 h. Temperatures of 1300 and 1325 °C and applied pressures of 150 MPa for 30 min were utilised in the HIP cycles. Densities >98% of the theoretical density (TD) have been obtained after HIPing, and the grain sizes previously obtained during pressureless sintering increased slightly during the HIP treatment. The microstructures before and after HIP treatments were observed by means of scanning electron microscopy (SEM). The fracture toughness was obtained by the indentation fracture technique using a Vickers hardness tester at a load of 10 N with a dwell time of 15 s for all cases. The ceramics obtained at the lowest HIP temperature (1300 °C) presented a grain size of 0.62 ± 0.04 μm, hardness of 20.5 ± 0.6 GPa, and fracture toughness of 4.8 ± 0.3 MPa m^1/2. The reported values were higher than those obtained by other authors and were in concordance with international standards that could make these ceramics available as a replacement for metal-on-polyethylene in orthopaedic surgery.     

Synthesis of a NiFe2O4 catalyst for the preferential oxidation of carbon monoxide (PROX)

The aim of this work was to study the NiFe₂O₄ spinel catalyst obtained by combustion reaction in the preferential oxidation of carbon monoxide reaction to conversion reactants H₂, CO and O₂ and to conversion products CH₄, H₂O and CO₂. The powders were prepared according to propellants chemical concept and characterized by XRD, TEM and catalytic tests. The XRD pattern shows the characteristic peaks of the spinel phase. The particle size calculated by TEM was 10.7 nm. The catalyst proved to be more selective to reagents for conversion into O₂ (89.5%) at 350 °C.     

A comparative study on combustion synthesis of Ta–Si compounds

A comparative study on the preparation of tantalum silicides (including TaSi₂, Ta₅Si₃, Ta₂Si, and Ta₃Si) in the Ta–Si system was conducted by self-propagating high-temperature synthesis (SHS) from elemental powder compacts of corresponding stoichiometries. For the powder compacts of Ta:Si = 5:3 and 2:1, upon ignition a planar combustion front traversing the entire sample was easily achieved even without prior heating. In contrast, a preheating temperature of 300 °C was required for the samples of Ta:Si = 3:1 and 1:2 to establish the propagation of a planar reaction front in a self-sustaining manner. It was found that the flame-front propagation velocity and combustion temperature were increased by increasing the preheating temperature and sample compaction density. Among the test samples of different compositions, the reactant compact of Ta:Si = 5:3 exhibited the highest flame speed, followed sequentially by the powder compacts of Ta:Si = 2:1, 3:1, and 1:2. The variation of combustion temperature with starting stoichiometry of the reactant compact was in a manner consistent with that of the flame-front velocity. According to the XRD analysis, a complete conversion yielding single-phase disilicide TaSi₂ was achieved from the sample compact of Ta:Si = 1:2. The silicides phases Ta₅Si₃ and Ta₂Si were obtained in relatively pure form through combustion reactions of the powder compacts with Ta:Si = 5:3 and 2:1, respectively. However, a poor degree of phase transformation was observed in the case of Ta:Si = 3:1, which produced a multiphase product composed mostly of Ta₂Si and Ta₅Si₃, along with small amounts of Ta₃Si and elemental Ta. In addition, based upon the temperature dependence of combustion wave velocity established in this study, the activation energies associated with combustion synthesis of Ta₅Si₃, Ta₂Si, and TaSi₂ were determined to be 105.2, 65.5, and 153.8 kJ/mol, respectively.     

Combustion synthesis of CaSc2O4:Ce nano-phosphors in a closed system

The CaSc₂O₄:Ce³⁺ nano-phosphors were successfully prepared by a single-step combustion method at an ignition temperature as low as 200 °C in a closed autoclave using glycine as a fuel and PEG4000 as a dispersant. The samples were characterized by X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscope (TEM). The results revealed that CaSc₂O₄:Ce³⁺ nano-phosphors can be conveniently prepared at an ignition temperature as low as 200 °C, which was much lower than that in the ordinary combustion methods. The optimized ignition temperature was 220 °C. The CaSc₂O₄:Ce³⁺ nano-phosphors give a uniform particle size in the range of 15-20 nm. The low ignition temperature and the addition of PEG4000 dispersant play important roles in the formation of small sized nanoparticles. The as-prepared nano-phosphors were incompact aggregates, but highly dispersed nano-phosphors can be obtained after further ultrasonic treatment. The CaSc₂O₄:Ce³⁺ nano-phosphors give satisfactory luminescence characteristic benefiting from the closed circumstance, in which cerium atoms can be isolated from the oxidizing atmosphere and non-fluorescent Ce⁴⁺ ions can be ruled out. The present highly dispersed CaSc₂O₄:Ce³⁺ nano-phosphors with efficient fluorescence are promising in the field of biological labeling, and the present low temperature combustion method is facile and convenient and can be applied as a universal process for preparing non-aggregate oxide nano-phosphors, especially those being sensitive to air at high temperature.     

Combustion synthesis of Ti(C, N)–TiB2 from a Ti–C–BN system

In this paper, a simple way of fabricating TiC_xN_y–TiB₂ ceramics through the combustion reaction of Ti, C and BN powder mixtures in an argon atmosphere is reported with an emphasis on the effects of the C/(C + N) ratio on the SHS reaction behaviors and mechanism. With the increase in the C/(C + N) ratio, the combustion temperature shows a zigzag variation behavior; the combustion wave velocity displays a similar variation tendency as did in the combustion temperature while the ignition delay time increases progressively. XRD results confirmed that TiC_xN_y–TiB₂ could form in all the samples. Microstructural observations revealed that both TiC_xN_y and TiB₂ grains had fine sizes of less than 1 μm in the products when the C/(C + N) ratio was lower than 0.5. Based on the characterization of quenched samples, the formation mechanism of the titanium carbonitride is proposed. Namely, the formations of TiN_0.3 and TiN are followed by the incorporation of C in TiN_x to form the titanium carbonitride solid solution.