Fluoride evaporation and crystallization behavior of CaF2–CaO–Al2O3–(TiO2) slag for electroslag remelting of Ti-containing steels

To elucidate the behavior of slag films in an electroslag remelting process, the fluoride evaporation and crystallization of CaF₂–CaO–Al₂O₃–(TiO₂) slags were studied using the single hot thermocouple technique. The crystallization mechanism of TiO₂-bearing slag was identified based on kinetic analysis. The fluoride evaporation and incubation time of crystallization in TiO₂-free slag are found to considerably decrease with decreasing isothermal temperature down to 1503 K. Fish-bone and flower-like CaO crystals precipitate in TiO₂-free slag melt, which is accompanied by CaF₂ evaporation from slag melt above 1503 K. Below 1503 K, only near-spherical CaF₂ crystals form with an incubation time of less than 1 s, and the crystallization is completed within 1 s. The addition of 8.1wt% TiO₂ largely prevents the fluoride evaporation from slag melt and promotes the slag crystallization. TiO₂ addition leads to the precipitation of needle-like perovskite (CaTiO₃) crystals instead of CaO crystals in the slag. The crystallization of perovskite (CaTiO₃) occurs by bulk nucleation and diffusion-controlled one-dimensional growth.     

Morphology of α-Si3N4 in Fe–Si3N4 prepared via flash combustion

The state and formation mechanism ofα-Si3N4 in Fe–Si3N4 prepared by flash combustion were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The results indicate thatα-Si3N4 crystals exist only in the Fe–Si3N4 dense areas. When FeSi75 particles react with N2, which generates substantial heat, a large number of Si solid particles evaporate. The prod-uct between Si gas and N2 is a mixture ofα-Si3N4 andβ-Si3N4. At the later stage of the flash combustion process,α-Si3N4 crystals dissolve and reprecipitate asβ-Si3N4 and theβ-Si3N4 crystals grow outward from the dense areas in the product pool. As the temperature decreases, the α-Si3N4 crystals cool before transforming into β-Si3N4 crystals in the dense areas of Fe–Si3N4. The phase composition of flash-combustion-synthesized Fe–Si3N4 is controllable through manipulation of the gas-phase reaction in the early stage and theα→βtrans-formation in the later stage.     

Morphology of α-Si_3N_4 in Fe–Si_3N_4 prepared via flash combustion

The state and formation mechanism of α-Si3N4 in Fe–Si3N4 prepared by flash combustion were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The results indicate that α-Si3N4 crystals exist only in the Fe–Si3N4 dense areas. When FeS i75 particles react with N2, which generates substantial heat, a large number of Si solid particles evaporate. The product between Si gas and N2 is a mixture of α-Si3N4 and β-Si3N4. At the later stage of the flash combustion process, α-Si3N4 crystals dissolve and reprecipitate as β-Si3N4 and the β-Si3N4 crystals grow outward from the dense areas in the product pool. As the temperature decreases, the α-Si3N4 crystals cool before transforming into β-Si3N4 crystals in the dense areas of Fe–Si3N4. The phase composition of flash-combustion-synthesized Fe–Si3N4 is controllable through manipulation of the gas-phase reaction in the early stage and the α→β transformation in the later stage.     

The influence of clusters in the melt of Fe80Si10B10 alloy on the subsequent glass-formation

The structure of Fe80Si10B10 alloy melt was investigated by ab initio molecular dynamic simulation from the local atomic environments. It presents that Fe80Si10B10 alloy can be considered as the combination of B-centered prism-like clusters and bcc-like Fe-Si solid solution. The poor glass-forming ability of the alloy has been investigated and can be attributed to the bcc-like environment around Si atoms and the relative high content of pure Fe clusters.     

Effects of P addition on the microstructure and mechanical properties of Mg–5%Sn–1.25%Si alloy

The effects of Al-P addition on the microstructure and mechanical properties of as-cast Mg–5%Sn–1.25%Si magnesium alloy were investigated. The results show that the phases of the as-cast alloy are composed of α-Mg, Mg2 Sn, Mg2 Si, little P, and AlP. The Chinese character shape Mg2 Si phase changes into a granular morphology by P addition because AlP can act as a heterogeneous nucleation core for the Mg2 Si phase. When 0.225wt% of Al–3.5%P alloy is added, the mechanical properties of the Mg–5%Sn–1.25%Si alloy are greatly improved, and the tensile strength increases from 156 to 191 MPa, an increase of 22.4% compared to the alloy without P addition. When the amount of Al–3.5%P reaches 0.300wt%, a segregation phenomenon occurs in the granular Mg2 Si phase, and the tensile strength and hardness decrease though the elongation increases.     

Effect of arsenic content and quenching temperature on solidification microstructure and arsenic distribution in iron–arsenic alloys

The solidification microstructure, grain boundary segregation of soluble arsenic, and characteristics of arsenic-rich phases were systematically investigated in Fe–As alloys with different arsenic contents and quenching temperatures. The results show that the solidification microstructures of Fe–0.5wt%As alloys consist of irregular ferrite, while the solidification microstructures of Fe–4wt%As and Fe–10wt%As alloys present the typical dendritic morphology, which becomes finer with increasing arsenic content and quenching temperature. In Fe–0.5wt%As alloys quenched from 1600 and 1200°C, the grain boundary segregation of arsenic is detected by transmission electron microscopy. In Fe–4wt%As and Fe–10wt%As alloys quenched from 1600 and 1420°C, a fully divorced eutectic morphology is observed, and the eutectic Fe2 As phase distributes discontinuously in the interdendritic regions. In contrast, the eutectic morphology of Fe–10wt%As alloy quenched from 1200°C is fibrous and forms a continuous network structure. Furthermore, the area fraction of the eutectic Fe2 As phase in Fe–4wt%As and Fe–10wt%As alloys increases with increasing arsenic content and decreasing quenching temperature.     

Saturation phenomenon of Ce and Ti in the modification of Al–Zn–Si filler metal

Cerium and titanium were added to an Al–42Zn–6.5Si brazing alloy, and the subsequent microstructures of the brazing alloy and the 6061 Al alloy brazing seam were investigated. The microstructures of filler metals and brazed joints were characterized by scanning electron microscopy and X-ray energy dispersion spectrometry. A new Ce–Ti phase formed around the silicon phase in the modified filler metal and this saturation phenomenon was analyzed. Interestingly, following brazing of the 6061 alloy, there is no evidence of the Ce–Ti phase in the brazing seam. Because of the mutual solubility of the brazing alloy and base metal, the quantity of the solvent increases, and the solute Ce and Ti atoms assume an undersaturated state.     

Influence of microstructure on the corrosion resistance of Fe–44Ni thin films

An Fe–44Ni nanocrystalline (NC) alloy thin film was prepared through electrodeposition. The relation between the microstructure and corrosion behavior of the NC film was investigated using electrochemical methods and chemical analysis approaches. The results show that the NC film is composed of a face-centered cubic phase (γ-(Fe,Ni)) and a body-centered cubic phase (α-(Fe,Ni)) when it is annealed at temperatures less than 400℃. The corrosion resistance increases with the increase in grain size, and the corresponding corrosion process is controlled by oxygen reduction. The NC films annealed at 500℃ and 600℃ do not exhibit the same pattern, although their grain sizes are considerably large. This result is attributed to the existence of an anodic phase, Fe_0.947Ni_0.054, in these films. Under this condition, the related corrosion process is synthetically controlled by anodic dissolution and depolarization.     

Erosion–corrosion behavior of austenitic cast iron in an acidic slurry medium

A series of austenitic cast iron samples with different compositions were cast and a part of nickel in the samples was replaced by manganese for economic reason. Erosion–corrosion tests were conducted under 2wt% sulfuric acid and 15wt% quartz sand. The results show that the matrix of cast irons remains austenite after a portion of nickel is replaced with manganese.(Fe,Cr)3C is a common phase in the cast irons, and nickel is the main alloying element in high-nickel cast iron; whereas,(Fe,Mn)3C is observed with the increased manganese content in low-nickel cast iron. Under erosion–corrosion tests, the weight-loss rates of the cast irons increase with increasing time. Wear plays a more important role than corrosion in determining the weight loss. It is indicated that the processes of weight loss for the cast irons with high and low nickel contents are different. The erosion resistance of the cast iron containing 7.29wt% nickel and 6.94wt% manganese is equivalent to that of the cast iron containing 13.29wt% nickel.     

Fine structure and phase composition of Fe–14Mn–1.2C steel:influence of a modified mixture based on refractory metals

The effect of TiO_2,ZrO_2 and Na_3AlF_6 ultrafine powders on the fine structure and the phase composition of Fe–14Mn–1.2C steel was investigated.The introduction of the ultrafine powders into the melt influenced the grain size,the quantity,and the character of distribution of nonmetallic inclusions in the railroad frogs.The microstructure of castings was improved significantly because of the refinement of the grain structure and an increase of the grain-boundary area.After the modifying mixture was introduced into the melt,either the microtwins of one or two intersecting systems or the precipitations of ε-martensite of different types,or simultaneously the microtwins and wafers of ε-martensite,were present in each grain.     

Crystallization behavior of Fe78Si13B9 metallic glass under high magnetic field

The effects of high magnetic field on the crystallization behavior of the Fe₇₈Si₁₃B₉ metallic glass ribbon were studied. The samples were isothermal annealed for 30 min under high magnetic field and no field,respectively. Microstructure transformation during crystallization was identified by X-ray diffraction and transmission electron microscopy. It was found that the crystallizations of Fe₇₈Si₁₃B₉ metallic glass processed under different conditions were that the precipitation of dendrite α-Fe(Si) and spherulite (Fe,Si)₃B phases forms amorphous matrix and then the metastable (Fe,Si)₃B phase transforms into the stable Fe₂B phase. The grain size of the crystals is smaller and more homogeneous for the isothermal annealed samples under high magnetic field in comparison with that under no field indicating that the crystallization behavior of Fe₇₈Si₁₃B₉ metallic glass is suppressed by high magnetic field.     

Preparation of in situ and ex situ reinforced Fe–10Cr–1Cu–1Ni–1Mo–2C containing NbC particles by milling and hot pressing

An in situ and ex situ reinforced powder metallurgy(PM) steel was prepared by the combination of high-energy ball milling and subsequent hot pressing of elemental mixed powders of Fe–10Cr–1Cu–1Ni–1Mo–2C by mass with the addition of Nb C particles. A 40-h milling pretreatment makes the powder particles nearly equiaxed with an average diameter of ~8 μm, and the ferrite grain size is refined to ~6 nm. The sintered density reaches 99.0%–99.7% of the theoretical value when the sintering is conducted at temperatures greater than 1000°C for 30 min. In the sintered bulk specimens, the formation of an in situ M7C3(M = Cr, Fe, Mo) phase is confirmed. M7C3 carbides with several hundred nanometers in size are uniformly distributed in the matrix. Some ultra-fine second phases of 50–200 nm form around the ex situ Nb C and in situ M7C3 particles. The sintered steel exhibits an excellent combination of hardness( Hv 500) and compressive strength(2100–2420 MPa).     

Effects of composition and microstructure on intergrain interactions of nanocomposite Pr2 Fe14B/α-Fe material

The effects of contents of Fe and B and microstructure on the intergrain interactions in the nanocomposite Pr2Fe14 B/a-Fe permanent magnetic materials are investigated by measuring the δM-H curves. The intergrain interactions become stronger with the increase in the content of Fe. The larger δM value of the ribbon samples corresponds to the smaller grain size and uniform grain size distribution, which are favorable factors strengthening the intergrain interactions and exchange-coupling. The non-ferromagnetic phase Pr1.1Fe4B4 is found in grain boundaries when the content of B is larger, which weakens the intergrain interactions.     

The precipitation strengthening behavior of Cu-rich phase in Nb contained advanced Fe–Cr–Ni type austenitic heat resistant steel for USC power plant application

Copper has been used as a strengthening element in newly developed Fe–Cr–Ni type austenitic heat resistant steel for inducing Cu-rich phase precipitation to meet high temperature strength requirement for 60°C Ultra Super-Critical (USC) coal fired power plants for many years. However, the precipitation behavior and strengthening mechanism of Cu-rich phase in these advanced austenitic heat resistant steels is still unclear. In order to understand the precipitation strengthening behavior of Cu-rich phase and to promote high strength austenitic heat resistant steel development, 18Cr9 NiCuNb steel which is a Cu-added Nb contained advanced Fe–Cr–Ni type austenitic heat resistant steel has been selected for this study to be aged at 650°C till to 10,000 h. Micro-hardness and room temperature tensile test were conducted after long-time aging. SEM,TEM, HRTEM and three dimensional atom probe (3DAP) technology accompanying with thermodynamic calculation have been used to investigate the Cu-rich phase precipitation behavior during 650°C aging. The experimental results showed that Cu atoms can quickly concentrate in clusters at very early precipitation stage to form the fine nano-size Cu-rich ‘‘segregation areas’within less than 1 h at 650°C. With increasing aging time at 650°C Cu atoms continuously concentrate to Cu-rich segregation areas (clusters) and simultaneously other kinds of atoms such as Fe, Cr and Ni diffuse away from Cu-rich segregation areas to austenitic matrix, and finally to complete the transformation from Cu-rich segregation areas to Cu-rich phase. However, there is only Cu atoms concentration but not crystallographic transformation from early stage of Cu-rich clusters forming to the final Cu-rich phase formation. Even the Cu atom becomes the main composed element after 500 h aging at 650°C the Cu-rich phase still keeps coherent relationship with austenitic matrix. According the experimental results in this study, Cu-rich phase precipitation sequence which starts from the Cu atom segregation followed by the Cu diffusing from matrix to segregation areas and Fe, Cr and Ni atoms diffuse out from Cu-rich areas to matrix without crystallographic transformation is proposed. The Cu-rich phase is the most dispersed phase and contributes the most important strengthening effect among all precipitated phases (M23C6, MX and Cu-rich phase). It has been found that Cu-rich phase is very stable and still keeps in nano-size even for 10,000 h aging at 650°C. The unique precipitation strengthening of Cu-rich phase in combination with nano-size Nb-rich MX phase and grain-boundary M23C6carbide contributes excellent strengthening effect to 18Cr9 NiCuNb austenitic heat resistant steel.     

Thermal stability and magnetic properties of Fe–Co–M–Zr–Nb–Ge–B(M=Mo,Cr) bulk metallic glasses

Fe62Co8 xMxZr6Nb4Ge1B19(M=Mo, Cr) bulk metallic glasses were synthesized in the diameter range up to 2 mm by copper mold casting,which exhibit high thermal stability and large glass-forming ability. The super-cooled liquid region diminishes by the dissolution of Mo. The addition of 2 at% Cr leads to the broading of the liquid region remarkably, resulting in the improvement of thermal stability. The crystallization takes place through a single exothermic reaction, accompanying the precipitation of more than three kinds of crystallized phases such as α-Fe,Fe2Zr and ZrB2. The Fe-based alloys show soft ferromagnetic properties. The saturation magnetization(ss) decreases with increasing Mo or Cr content while the saturated magnetostriction increases with raising Mo or Cr content. There is no evident change in the ssand coercive force(Hc)with annealing temperature below the crystallization temperature, which suggests a more relaxed atomic configuration the glasses have. The crystallization causes a substantial enhancement in both ssand Hc. Each soft magnetic property of the glasses containing Cr with higher thermal stability is superior to that of the alloys containing Mo.     

Effect of Fe_2O_3 on the crystallization behavior of glass-ceramics produced from naturally cooled yellow phosphorus furnace slag

CaO–Al_2O_3–SiO_2(CAS) glass-ceramics were prepared via a melting method using naturally cooled yellow phosphorus furnace slag as the main raw material.The effects of the addition of Fe_2O_3 on the crystallization behavior and properties of the prepared glass-ceramics were studied by differential thermal analysis,X-ray diffraction,and scanning electron microscopy.The crystallization activation energy was calculated using the modified Johnson–Mehl–Avrami equation.The results show that the intrinsic nucleating agent in the yellow phosphorus furnace slag could effectively promote the crystallization of CAS.The crystallization activation energy first increased and then decreased with increasing amount of added Fe_2O_3.At 4wt% of added Fe_2O_3,the crystallization activation energy reached a maximum of 676.374 k J×mol-1.The type of the main crystalline phase did not change with the amount of added Fe_2O_3.The primary and secondary crystalline phases were identified as wollastonite(CaSiO_3) and hedenbergite(Ca Fe(Si_2O_6)),respectively.     

A Ti–Zr–Cu–Ni–Co–Fe–Al–Sn amorphous filler metal for improving the strength of Ti–6Al–4V alloy brazing joint

Ti_(50)Zr_(27)Cu_8Ni_4Co_3Fe_2Al_3Sn_3(at%) amorphous filler metal with low Cu and Ni contents in a melt-spun ribbon form was developed for improving mechanical properties of Ti–6Al–4V alloy brazing joint through decreasing brittle intermetallics in the braze zone. Investigation on the crystallization behavior of the multicomponent Ti–Zr–Cu–Ni–Co–Fe–Al–Sn amorphous alloy indicates the high stability of the supercooled liquid against crystallization that favors the formation of amorphous structure. The Ti–6Al–4V joint brazed with this Ti-based amorphous filler metal with low total content of Cu and Ni at 1203K for 900s mainly consists of α-Ti, β-Ti,minor Ti–Zr-rich phase and only a small amount of Ti_3Cu intermetallics, leading to the high shear strength of the joint of about 460 MPa. Multicomponent composition design of amorphous alloys is an effective way of tailoring filler metals for improving the joint strength.     

The hidden disintegration of cluster heterogeneity in Fe-based glass-forming alloy melt

The evolution of liquid metal at high temperature is known much less than their solid states. This is partially due to that the message concerning clusters, metastable phase or heterogeneity in liquid is usually too slight to be traced. Here, we shed some light on the nature of structural evolution of Fe-based glass-forming alloy during overheating process by the investigation of high-temperature melt viscometry and first principles simulations. It was found that a structural transition around 1400 ℃ occurred in the melts of initial homogeneous ingot, heterogeneous ingot and amorphous ribbons jointly, and was confirmed by the results from differential scanning calorimeter(DSC), and ab initio molecular dynamics(AIMD). Combining these results with Fe-Si-B ternary phase diagram and the melting characteristics of Fe-B compounds, it is safe to conclude that the disintegration of Fe_2B type clusters to Fe_3B-type clusters leads to the observed transition. These results offer a significant reference for the preparation and property control of Fe-based amorphous alloys.     

Growth in solution of hooked Ni–Fe fibers by oriented rotation and attachment approaches

Inspired by the curved branches of fractal trees, hooked Ni–Fe fibers were grown in situ in Ni–Fe composite coatings on a spheroidal graphite cast iron substrate. These hooked Ni–Fe fibers exhibited inclination angles of about 39°, which was in accordance with the theoretical prediction of 37°. Ni–Fe nanostructures self-assembled to form dendrites and evolved into hooked fibers by an oriented attachment reaction. The orientation rotation of Ni–Fe nanostructures played an important role in the growth of curved hooked Ni–Fe fibers. During sliding wear tests, the volume loss of the spheroidal graphite cast iron substrate was 2.2 times as large as that of the Ni–Fe coating reinforced by hooked fibers. The good load-transferring ability of hooked Ni–Fe fibers led to an improvement in their wear properties during wear tests.