Possibilities and prospects for producing silumins with different silicon contents using amorphous microsilica

The main objective of this work is to research complex physical−chemical processes of Al(l)−SiO₂ interface and develop a new technology for producing foundry silumins based on amorphous microsilica obtained from silicon production waste. Effective methods for producing hypoeutectic, eutectic, and hypereutectic silumins using amorphous microsilica were developed. Alloys with a silicon content of 7 wt.% were obtained by blowing preheated amorphous microsilica into the aluminum melt (t=900 °C) along with the stream of argon followed by intense mixing. Alloys with a silicon content of 21 wt.% were manufactured by induction melting of a silicon-containing mixture (60% SiO₂, 40%Al + 20%3NaF·2AlF₃) subjected to the presintering when the amorphous microsilica was reduced to crystalline silicon. It is found that crystalline silicon, which is formed during the roasting of the tableted burden, is smoothly absorbed by the aluminum melt. Aluminum oxide, obtained during the redox reaction, dissolves in cryolite, after which aluminum and silicon are fused together and transferred to the melt. The calculation of the economic efficiency of producing silumins using amorphous microsilica demonstrates a quick project payback period, as well as a high level of its profitability.     

Changes in the transport properties of silicon dioxide due to doping by foreign ions

Based on the model that in the intrinsic disorder of SiO₂ oxygen-ion vacancies dominate at low oxygen pressure and oxygen-ion interstitials at high oxygen pressure, a model is presented which explains the formation of mobile interstitial silicon ions preferentially at high oxygen pressure by doping of SiO₂ with Ti³⁺ and/or Ti²⁺ ions. Analogously an attempt has been made to understand an increase in the solubility of MoO₃ in SiO₂ by Al₂O₃ dissolved in SiO₂. Doping and co-dissolution are in particular to be expected in the oxidation of SiO₂ forming ceramics because SiO₂ has very probable dissolved impurities of the ceramic or/and sinter additives.     

Synthesis of Al2O3/SiC composites by the SHS microwave heating process

Alumina/silicon carbide composites were synthesized by the microwave induced SHS (Self-propagating High-temperature Synthesis) process. SiO₂/Al/C powders were used as starting materials and samples were ignited by using a 2.45 GHz multimode home microwave oven (700W). Effects of the mixing ratio of SiO₂/Al/C powders, reaction environments, and weight percent of KNO₃ as a reaction promoter on the formation of the final product were studied.     

Effects of oxide precursors on fabrication of Mo5Si3–Al2O3 composites via thermite-based combustion synthesis

Fabrication of the Mo₅Si₃–Al₂O₃ composite with a broad composition range was studied by thermite-based combustion synthesis. The addition of two thermite mixtures composed of 0.6MoO₃ + 0.6SiO₂ + 2Al and MoO₃ + 2Al into the Mo–Si reaction system was thermally beneficial for the self-sustaining combustion process. The former thermite reagent is less exothermic than the latter. Moreover, experimental results showed that the combustion temperature and flame-front velocity decreased with increasing molar ratio of Mo₅Si₃ to Al₂O₃ formed in the composite. As a consequence, the MoO₃/SiO₂/Al-based reaction scheme was adopted to synthesize composites with Mo₅Si₃/Al₂O₃ from 0.4 to 0.7, and MoO₃/Al-based system was for the products with Mo₅Si₃/Al₂O₃ from 0.8 to 1.6. The XRD pattern indicated Mo₅Si₃ as the dominant silicide. Mo₃Si was formed as the minor phase, because a small amount of Si dissolved in Al₂O₃. This was confirmed by the presence of both Al₂O₃ and aluminum silicate, a solid solution of Al₂O₃ and SiO₂, in the final products.     

Thermally Formed Oxide Films on Al–XSi Alloys Heated in Different Gases

Thermogravimetric analysis (TGA) testing was used to measure the change in weight of polished samples of Al–XSi (X = 0 and 1.2 mass%) alloys. The samples were heated at 843 K for 6 h in dry air or nitrogen gas. X-ray diffraction was used to monitor the formation of the oxide films on the surface of the samples. The surface oxide films were more compact after the Al alloy samples were heated in air, and the oxide films showed some cracks after being heated in nitrogen gas. The thermally formed surface oxide films on the Al–1.2 mass% Si alloy samples heated in air and in nitrogen gas possessed loose structures, which comprised mainly γ-alumina, diaspore, and gibbsite, along with metallic silicon and/or aluminum. The weight variation curve of the films appeared serrated; this can be attributed to chain reactions (3Si + 3O₂ → 3SiO₂ + 4Al → 3Si + 2Al₂O₃) that occurred within the film.     

Microsegregation in high Nb containing TiAl alloy ingots beyond laboratory scale

Microsegregation in big ingots of Ti–45Al–(8–9)Nb–(W, B, Y) alloy had been studied. The composition and microstructural morphology of the large ingot exhibited significant microinhomogeneity. Three types of microsegregation were observed in as-cast microstructure of the large ingot. First is the solidification segregation (S-segregation) at interdendritic area, in which the composition is characterized by higher Al, B (boride), and Y (oxide) contents and lower Nb and W contents. Second is the β-segregation at the boundary and triple junctions among α grain due to the phase transformation of β → α. The composition at the segregation area is characterized by higher Nb and W additions that lead to the formation of β particles and γ phase. Third is the α-segregation that forms local lamellar structure composed of β, γ and α plates due to phase transformation of α → α₂ + β + γ. The microsegregation for the PAM ingot is lower than that for SM ingot in terms of the volume fraction of β phase. The reason is that the PAM melting can offer better control of pouring temperature and rather fast cooling rate by water-cooled copper crucible.     

Laser cladding of SiC/Si composite coating on Si-SiC ceramic substrates

Pieces of silicon infiltrated silicon carbide (Si-SiC) were coated with a SiC particles reinforced Si matrix composite (SiC/Si) obtained from mixtures of SiC + SiO₂ and SiC + Si by laser cladding. A Nd:YAG pulsed laser delivering an average power of 920 W was used to apply such coatings using the powder blowing technique. The results demonstrate that the use of the SiC + SiO₂ powder mixture produces a severe damage on the base material, whereas the use of the SiC + Si mixture leads to the formation of sound coatings without substrate damage. XRD and nanoindentation measurements corroborate the production of silicon carbides surrounded by a metallic silicon matrix. This method could be used for repairing surface defects of silicon infiltrated silicon carbide ceramics (Si-SiC).     

FASHS技术制备TiB2+Ni/Ni3Al/405不锈钢梯度材料

采用电场激活自蔓延高温合成(FASHS)技术制备了TiB2 Ni/Ni3Al/405不锈钢梯度材料.试验中首先将镍粉和铝粉球磨处理以促进燃烧反应发生,然后采用FASHS技术利用自蔓延燃烧反应热连接制备了TiB2 Ni/Ni3Al/405不锈钢梯度材料.用SEM和XRD分析了梯度材料各层的界面微观组织及相组成,用洛氏硬度计、显微硬度计及磨料磨损试验机分析了材料的力学性能、硬度及表面抗磨性.结果表明,金属陶瓷复合层、Ni3Al层和405不锈钢金属片间形成了可靠的冶金结合,金属陶瓷复合材料表面硬度为90HRA,材料的化学成分和显微硬度呈梯度分布,耐磨性优于20Cr渗碳钢.     

Preparation of Al2O3–ZrO2–SiO2 ceramic composites by high-gravity combustion synthesis

By a furnace-free technique of high-gravity combustion synthesis, Al₂O₃–ZrO₂–SiO₂ ceramic composites were prepared via melt solidification instead of conventional powder sintering. The solidification kinetics and microstructure evolution of the ceramic composites in high-gravity combustion synthesis were discussed. The phase assemblage of the ceramic composites depended on the chemical composition, where both (Al₂O₃ + ZrO₂) and (mullite + ZrO₂) composites were obtained. The ceramic composites consisted of ultrafine eutectics and sometimes also large primary crystals. In the (mullite + ZrO₂) composites, two different morphologies and orientations were observed for the primary mullite crystals, and the volume fraction of mullite increased with increasing SiO₂ content. The ceramic composites exhibited a hardness of 11.2–14.8 GPa, depending on the chemical composition and phase assemblage.     

VAlSiN 硬质涂层的结构与机械性能

目的研究Si的掺入对VAlN硬质涂层机械性能的影响行为。方法利用双靶(V50Al50靶与Si靶)磁控溅射沉积技术,保持V50Al50靶的功率为一定值,通过控制Si靶的功率,获得Si含量不同的VAlSiN硬质涂层,分析涂层的成分、相组成、硬度及耐磨损性能。结果 Si在涂层中以Si3N4非晶相存在,Si3N4起到细化晶粒的作用,少量Si的掺入可使涂层的硬度与耐磨性能得到提升。但当Si大量掺入后,Si3N4非晶相成为涂层中的主相,导致涂层的硬度与耐磨性能出现下降。结论少量Si的掺入有益于VAlN涂层机械性能的提升。     

Oxidation of Ti3SiC2 between 900 and 1200 °C in Air

Ti₃SiC₂ materials were synthesized by hot pressing using a new starting-material system consisting of a TiC_x(x=0.6)/Si powder mixture. The oxidation of Ti₃SiC₂ at temperatures between 900 and 1200 °C in air for up to 100 h resulted in the formation of an outer TiO₂ layer, an intermediate SiO₂-rich layer and an inner (TiO₂ + SiO₂) mixed layer. During oxidation, Ti diffused outwards to form the outer TiO₂ layer, and oxygen transported inwards to form the inner (TiO₂ + SiO₂) mixed layer. At the same time, the carbon in Ti₃SiC₂ escaped into the air. Below the scale, there was a narrow oxygen-affected zone, The oxidation at the scale-matrix interface proceeded by the disintegration of the lamellar Ti₃SiC₂ grains to form crystallites with a size of a few tens of nanometers containing oxygen. The detailed scale characteristics and oxidation mechanism are described.     

Al/Ti扩散层形成的扩散溶解机制

分别在铝组元熔点之下和之上对Al/Ti镶嵌式扩散偶进行退火热处理,形成固-固和固-液扩散偶.利用光学显微镜、扫描电子显微镜和电子探针显微分析仪观察和分析Al/Ti固-固和固-液扩散层的形态和结构,并对其形成微观机理进行了研究.结果表明,Al/Ti固-固扩散层由一层TiAl₃构成;固-液扩散层由TiAl₃单相层与TiAl₃和Al(Ti)固溶体双相层两层构成,双相层TiAl₃和Al(Ti)固溶体的形态自铝向钛呈现规律性变化.Al/Ti固-固TiAl₃扩散层和固-液TiAl₃单相层的形成都是铝扩散溶解到钛中形成以钛为溶剂的Al-Ti固溶体结晶形成的;而Al/Ti固-液TiAl₃和Al(Ti)固溶体双相层是钛先溶解再扩散到液态铝中形成的Al-Ti液溶体结晶形成的.铝液中Ti原子浓度自铝向钛逐渐升高,导致了双相层TiAl₃和Al(Ti)固溶体形态的规律性变化.     

Effect of arc re-melting on microstructure,mechanical and tribological properties of commercial 390A alloy

To investigate the effect of the arc re-melting on the microstructure, mechanical and tribological properties of the 390A alloy, its ingot produced by the conventional induction melting method was subjected to the arc re-melting process. The microstructure of the 390A alloy was examined by OM and SEM. Mechanical properties of the 390A alloy were determined by the Brinell method and tensile tests. Tribological properties were investigated with a ball-on-disc type tester. It was observed that the microstructure of both conventional induction melted and arc re-melted 390A alloys consisted of α(Al), eutectic Al–12Si, primary silicon particles, θ-CuAl₂, β-Al₅FeSi, δ-Al₄FeSi₂, and α-Al₁₅(FeMnCu)₃Si₂ phases. Re-melting with the arc process caused grain refinement in these phases. In addition, after this process, the α(Al) phase and primary silicon particles were dispersed more uniformly, and sharp edges of primary silicon particles became round. The arc re-melting process resulted in an increase in the hardness of the 390A alloy produced by the conventional method from 102 HB to 118 HB and the tensile strength from 130 to 240 MPa. It also caused an increase in the wear resistance of the 390A alloy and a decrease in the friction coefficient.     

Influence of copper and aluminum substitution on high-temperature oxidation of the FeCoCrNiMn “Cantor” alloy

In this study, the oxidation behavior of FeCoCrNiMn (HEA + Mn) is compared to three modified HEAs manufactured by substituting Mn with Al, Cu, or Al + Cu. Oxidation tests were conducted between 600°C and 800°C for up to 500 h in synthetic air. Substitution of Mn leads to a significant improvement in the oxidation resistance for the three modified HEAs. For FeCoCrNiCu (HEA + Cu), a local attack of a Cu-rich phase was observed, leading to the formation of CuO blisters on the surface. The FeCoCrNiAl (HEA + Al) alloy was characterized by the formation of a thin Al₂O₃ surface layer for all temperatures. However, for the HEA + Al alloy the formation of AlN was observed after 300 h at 800°C, leading to a partial breakdown of the protective scale. FeCoCrNiCuAl (HEA + Cu + Al) by far showed the best oxidation resistance, characterized by the formation of a highly protective Al₂O₃ scale that effectively inhibited nitrogen penetration into the metal subsurface and local attack of the Cu-rich phase.     

Processing and microstructure control of (α2+B2+O) alloy sheet in Ti–Al–Nb system

Rolling processing and microstructure evolution during rolling and heat treatment for two typical α₂+B2+O alloys, Ti–24Al–14Nb–3V and Ti–23Al–17Nb (at%), were investigated. The experimental results showed that the alloys have good workability for rolling at temperatures both in the α₂+B2 and in α₂+B2+O fields. The thickness reduction up to 99% was obtained for the sheets rolled above 900°C in a quasi-isothermal condition without cracking. A typical duplex microstructure of the α₂+B2+O phases formed when the sheets were rolled and then solution treated at temperatures in the α₂+B2 phase field plus aging in the O+B2 field. Such duplex microstructure was proved to have good mechanical properties both in room and elevated temperatures. A microstructure of fine equiaxed α₂ and O phases distributed in B2 matrix was obtained for the sheets rolled and then solution treated at the temperatures in the α₂+B2+O phase field, which possess excellent room temperature ductility and superplasticity in temperatures of 900∼1000°C. An advanced cold rolling processing plus a proper vacuum heat-treatment used for the production of high-quality foils of Ti–24Al–14Nb–3V (at%) alloy are also reported.     

The Effect of Pressure on the Combustion Synthesis of a Functionally-Graded Material: TiB2-Al2O3-Al Ceramic- Metal Composite System

This article describes some recent research on the synthesis of functionally-graded materials (FGM using combustion synthesis or self- propagating high-temperature synthesis (SHS). A model ceramic-metal SHS system was investigated based on the reaction system: 3TiO₂ + 3B₂O₃ + (10 + x)Al = 3TiB₂ + 5Al₂O₂ + xAl in which x was varied between 0 and 17 to achieve the required composition and phase gradients in the FGM. The effects of combustion mode, reactant stoichiometry (xAl), green density, and applied loads on the stability of the SHS reaction and density of the FGM product are described.     

Phase composition and luminescent properties of strontium aluminate long persistence phosphor synthesized by combustion synthesis method with different Sr/Al ratios

Strontium aluminate long persistence phos phors are synthesized by combustion method. By control- ling the raw material ratio （Sr/Al）, the effects of phase composition on subsequent spectroscopic properties of phosphors are studied. Results show that the phase com-position changes from strontium-rich phase to aluminum- rich phase with the decrease of Sr/AI： when the rate of Al/Sr changes from 3：1 to 1：1, the main crystal phase of samples is Sr3Al206, and it exhibits the characteristic fluorescence of Eu^3＋ in the lattice of Sr3Al206; when the rate of Al/Sr is between 1：2 and 2：7, phase composition is the mixture of SrAl204 and SrAl4OT, and it emits the characteristic fluorescence of Eu^2＋ in SrAl204 but not in SrAl4OT; when Al/Sr decreases to 1：4 or even 1：12, the main crystal phase of samples transform into SrAl12019, and the characteristic emission peak is about 470 nm, which corresponds to the characteristic emission of Eu2＋ in SrAl12019. At the end of the article, the influence laws of two different synthesis methods on phase composition of samples between high-temperature solid method and combustion method are compared. Compared with the high-temperature solid method, the rule of influence is similar, but the mole ratio of Al/Sr in products is always higher than the initial ratio of the raw material, and com-pounds like Sr4Al14025 are not obtained by combustion method.     

Thermite reduction of Ta2O5/SiO2 powder mixtures for combustion synthesis of Ta-based silicides

Tantalum silicides (including TaSi₂, Ta₅Si₃, Ta₂Si, and Ta₃Si) were prepared by solid state combustion of the Ta-Si reaction system involving thermite reduction of Ta₂O₅ and SiO₂. The thermite-based combustion is self-sustaining and contributes to the in situ formation of tantalum silicides along with Al₂O₃. The combustion front temperature and propagation velocity increased with the extent of thermite reactions for the systems adopting the thermite mixture of Al-Ta₂O₅, while both of them decreased for those using Al, Ta₂O₅, and SiO₂ as the thermite reagents. Among four silicide compounds, a better degree of phase evolution was observed for TaSi₂ and Ta₅Si₃ when compared to that of Ta₂Si and Ta₃Si. The XRD analysis indicated the presence of a small amount of Ta₅Si₃ in the TaSi₂-Al₂O₃ composite. On the formation of Ta₅Si₃ with Al₂O₃, the minor phase was Ta₂Si for the Al-Ta₂O₅-containing system. In addition to Ta₂Si, an intermediate phase TaSi₂ was detected when the Al-Ta₂O₅-SiO₂ mixture was used. However, combustion yielded comparable amounts of Ta₂Si and Ta₅Si₃ in the synthesis of the Ta₂Si-Al₂O₃ composite. Moreover, instead of forming Ta₃Si the reaction produced Ta₂Si as the dominant phase along with unreacted Ta.     

Modification of the oxidation behavior of high-purity austenitic Fe-14Cr-14Ni by the addition of silicon

The oxidation behavior of Fe-14Cr-14Ni (wt.%) and of the same alloy with additions of 1 and 4% silicon was studied in air over the range of 900-1100° C. The presence of silicon completely changed the nature of the oxide scale formed during oxidation. The base alloy (no silicon) formed a thick outer scale of all three iron oxides and an internally oxidized zone of (Fe,Cr,Ni) spinels. The alloy containing 4% silicon formed an outer layer of Cr₂O₃ and an inner layer of either (or possibly both) SiO₂ and Fe₂SiO₄. The formation of the iron oxides was completely suppressed. The oxidation rate of the 4% silicon alloy was about 200 times less than that of the base alloy, whereas the 1% silicon alloy exhibited a rate intermediate to the other two alloys. The actual ratio of the oxidation rates may be less than 200 due to possible weight losses by the oxidation of Cr₂O₃ to the gaseous phase CrO₃. The lower oxidation rate of the 4% silicon alloy was attributed to the suppression of iron-oxide formation and the presence of Cr₂O₃, which is a much more protective scale.