Residual Silicon Content Research Articles

Thermodynamic modeling of interphase distribution of chromium and boron in slags of AOD reduction period

The paper presents the results of a thermodynamic modeling of the chromium and boron reduction from slags of reduction period of argon-oxygen decarburization (AOD) by a complex reducing agent containing silicon and aluminum. Using the simplex lattice method, an experiment planning matrix is constructed containing 16 compositions of the oxide system СаО – SiO2 – (3 – 6 %) В2О3 – 12 % Cr2O3 – 3 % Al2O3 – 8 % MgO of variable basicity 1.0 – 2.5. The results of thermodynamic modeling are graphically presented in form of dependence of equilibrium distribution of chromium and boron on the slag composition at temperatures of 1600 and 1700 °C. The constructed diagrams make it possible to quantify the influence of the temperature, basicity and B2O3 in the slag on equilibrium interphase distribution of chromium and boron. It is established that increasing the slag basicity from 1.0 to 2.5 improves the process of chromium reduction, but restores the boron stability. With an increase in B2O3 content in the slag, a slight deterioration of chromium reduction process occurs, while the boron content in the metal increases. With a simultaneous increase in basicity up to 2.5 and a decrease in boron oxide in the slag from 5 to 3 %, the interphase distribution coefficient of chromium is reduced to 1.5·10–3. Changing the process temperature from 1600 to 1700 °C does not have a negative effect on the process of chromium reduction, but worsens the boron reduction conditions. Based on analysis of the formed slag phases and thermodynamics of the reactions of their formation, it is established that chromium is mainly reduced by aliminum with only partial development of silicothermy. The residual silicon content reduces boron, thereby limiting its concentration in the metal. The results of high-temperature experiments showed high correspondence with the results of thermodynamic studies.

Preparation of high-density green body based on binder jetting 3D printing using spheroidized SiC powder

Silicon carbide (SiC) ceramic stands as a critical material in the realm of high-performance engineering ceramics. However, Crafting SiC ceramics with intricate structures and superior mechanical properties presents notable challenges in shaping, sintering, and processing. Binder jetting (BJ) additive manufacturing has the outstanding advantages of high forming efficiency and no thermal deformation, especially suitable for printing complex structure SiC components.; however, BJ printed green bodies often exhibit low density, resulting in high residual silicon content and diminished strength of the final components. In this work, we introduce a novel strategy to fabricate high-strength SiC components with complex geometries by improving the density of printed SiC green bodies. This method involves modifying the morphology of SiC powder through the molten salt method to increase the density of BJ 3D printed green bodies from 1.24 ± 0.13 g/cm³ to 2.01 ± 0.03 g/cm³, followed by a reactive melt infiltration process. The resulting RB-SiC ceramics display exceptional flexural strength, averaging 280.60 ± 33.05 MPa, and an elastic modulus of 294.67 ± 4.90 GPa. These values represent some of the highest for flexural strength and elastic modulus reported among 3D-printed SiC composites. With its robust mechanical performance and streamlined fabrication process, this strategy holds substantial promise for the production of structural SiC ceramics.

Modelling of the microstructure and thermal conductivity of SiC-bonded diamond materials

Materials with high thermal conductivity are required in a wide range of thermal management applications. Silicon carbide (SiC) bonded diamond materials, which can be produced without pressure, are a possible candidate for such applications. They exhibit thermal conductivities >650 W/(m·K) depending on the diamond content, diamond grain size and residual silicon content. It is difficult to experimentally determine the influence of these factors on the thermal conductivity separately, as changing one of these parameters affects the other parameters. Therefore, a method for generating digital microstructures of SiC- bonded diamond materials was developed and the thermal conductivity was calculated as a function of the grain size These data were compared with real structures.

Preparation and interfacial microstructure of high thermal conductivity diamond/SiC composites

Diamond/SiC composites offer valuable applications in thermal management because of their exceptional thermal properties. Currently, the predominant method employed for crafting diamond/SiC composites is the reaction sintering approach. However, it encounters the challenge of a high residual silicon content. In this study, we introduced techniques such as bimodal diamond particles and high-density carbon sources (submicron diamond powder) to enhance the diamond content and reduce the residual silicon, optimizing the phase composition. The results indicated the diamond/SiC composite demonstrated a thermal conductivity of 666 W/m·K, a thermal expansion coefficient of 2.73 × 10−6 K−1, and an elastic modulus of 753 GPa. Furthermore, the meticulous assessment of the interface microstructure of diamonds in the diamond/SiC composite was conducted using transmission electron microscopy. The formation of nanocrystal-SiC and interface defects were elucidated by the mechanism of carbon dissolution saturation.

Preparation of low residual silicon content Si-SiC ceramics by binder jetting additive manufacturing and liquid silicon infiltration

Complex silicon carbide (SiC) ceramic components are difficult to fabricate due to their strong covalent bonds. Binder jetting (BJ) additive manufacturing has the outstanding advantages of high forming efficiency and no thermal deformation, especially suitable for printing complex structure SiC components. This study tried to obtain low silicon content silicon carbide ceramics by binder jetting followed by phenolic resin impregnation and pyrolysis (PRIP) and liquid silicon infiltration (LSI). BJ was used for the SiC green parts fabrication, and the highest compressive strength (7.7 ± 0.3 MPa) and lowest dimensional deviations (1.2–1.6 mm) were obtained with the printing layer thickness of 0.15 mm. Subsequently, PRIP treatments were introduced to increase the carbon content for the following LSI process. As the number of PRIP cycles increased, the carbon density of SiC/C preform increased and the porosity decreased. After the LSI treatment, the final Si-SiC composites processed with 2 PIRP cycles reached the highest flexural strength (257 ± 14.26 MPa) and the best wear resistance. This was attributed to the low residual silicon content (10.2 vol%) and almost no residual carbon. Furthermore, several complex structural components were fabricated using these methods. The preparation of complex components verifies the feasibility of BJ and LSI for manufacturing high-strength and high-precision SiC ceramics. Besides, this work hopes to provide technical guidance for the preparation of complex SiC composites in the future.

High-strength and low-silicon SiC ceramics prepared by extrusion molding 3D printing

Material extrusion is a promising additive manufacturing technique for fabricating high-performance SiC composites with complex structures. In this work, a novel strategy for fabricating SiC composites via material extrusion combined with solvent debinding and gaseous-liquid two step silicon infiltration was developed. The mixture used for material extrusion was composed of an organic binder, such as high-density polyethylene, ethylene vinyl acetate, paraffin wax and a C/SiC inorganic powder. The experimental results revealed that 89 wt% of the soluble components could be removed after debinding at 40 °C for 10 h in kerosene solvent, and the morphology was satisfactory after subsequent thermal debinding. After reactive sintering, the density of the SiC composite reached 3.12 ± 0.02 g/cm3, with a theoretical residual silicon content of 10.13 vol%. The flexural strength and elastic modulus reached the maximum values of 465 ± 35.35 MPa and 425 ± 11.78 GPa, respectively.

Improved selectivity and anti-aging ability for 6FDA type carbon molecular sieve membranes by mixing silicon from macro-phase separation to molecule doping

Good gas separation performance and anti-aging ability are important for the applications of carbon molecular sieve membrane (CMSM). In this work, silicon atoms in the form of siloxane-Cl are introduced into 6FDA-DABA type polyimide (PI) precursor membrane, and benzimidazoles (BI) is copolymerized into PI to effectively improve the compatibility between PI and siloxane-Cl. By varying the content of siloxane-Cl, the composite membrane changes from macro-phase separation to molecule level miscibility, which leads to the formation of silicon-rich interface layer and silicon molecule doping after high temperature pyrolysis, respectively. The residual silicon content in CMSM could be as high as 1 wt%. The high content silicon doped CMSM exhibits much improved H2 permeability retention degree (3617 Barrer of H2 permeability, 62% higher) and H2/CH4 selectivity (138, 51% higher) as compared to control CMSM after 45 days of physical aging. This work proves that the incorporation of silicon in CMSMs in proper forms could significantly improve their molecular sieving and anti-aging performances; a higher content of residual silicon and molecule level doping are highly desired. The heteroatom doping is expected to pave a new way for finely tuning the micro-structures of CMSMs and improving gas separation performances.

Effects of density and heat treatment of C/C preforms on microstructure and mechanical properties of C/C–SiC composites

AbstractTwill multidirectional carbon‐fiber‐reinforced carbon and silicon carbide composites (i.e., C/C–SiC) were prepared via chemical vapor infiltration combined with reactive melt infiltration process. The effect of heat treatment (HT) on the microstructure and mechanical properties of C/C–SiC composites obtained by C/C preforms with different densities was thoroughly investigated. The results show that as the bulk density of C/C preforms increases, the thickness of the pyrolytic carbon (PyC) layer increases and open pore size distribution narrows, making the bulk density and residual silicon content of C/C–SiC composites decrease. Moreover, the flexural strength and tensile strength of the C/C–SiC composites were improved, which can be attributed to the increased thickness of the PyC layer. The compressive strength reduces due to the decrease of the ceramic phase content. HT improves the graphitization degree of PyC, which reduces the silicon–carbon reaction rate and thereby the content of the SiC phase. HT induces microcracks and porosity but not obviously affects the mechanical properties of C/C–SiC composites. However, the negative impact of HT can be compensated by the increased density of the C/C preforms.

Effect of Carbon Content on Mechanical Properties of Boron Carbide Ceramics Composites Prepared by Reaction Sintering.

In this study, different reaction-bonded boron carbide (RBBC) composites with a free carbon addition from 0 to 15 wt% were prepared, and the effect of the carbon content on the mechanical properties was discussed. With the free carbon addition increase from 0 to 15 wt%, the residual silicon content in the RBBC composite decreased first and then increased. Meanwhile, the strength of the RBBC composite improved first and then worsened. In the RBBC composite without free carbon, the B4C grains are obviously dissolved, the grains become facet-shape, and the grain boundary becomes straight. The microstructure of the composite was tested by SEM, and the phase composition of the composite was tested by XRD. The RBBC composite with the addition of 10 wt% free carbon has the highest flexural strength (444 MPa) and elastic modulus (329 GPa). In the composite with a 10 wt% carbon addition, the phase distribution is uniform and the structure is compact.

Defining the features of structural and phase transformations in the recycling of anthropogenic metallurgical waste containing refractory elements

This paper reports a study into the features of the phase composition and microstructure of a master alloy obtained by using the reduction melting of oxide man-made waste. That was necessary to define those technological indicators that provide for an increase in the degree of extraction of alloying elements during the recycling of anthropogenic raw materials and the subsequent use of the alloying material. It has been determined that the phase composition of the alloy at a Si:C ratio in the charge of 0.11 mainly consisted of a solid solution of elements in α-Fe, as well as carbides Fe3C and Fe3W3C. At the Si:C ratios in the charge of 0.28 and 0.52, along with a solid solution of the elements in α-Fe, Fe8Si2C, Fe5Si3, and FeSiC, FeSi2 manifested themselves, respectively. The microstructure of the alloy demonstrated a clear manifestation of several phases with different content of alloying elements. Changing a Si:C ratio in the charge from 0.11 to 0.28 and 0.52 led to an increase in the residual silicon content (wt %) in the studied areas, from 0.00–0.25 to 0.12–1.79 and 0.20–2.11, respectively. At the same time, the carbon content (wt %) in the examined areas varied from 0.25–2.12 to 0.24–2.52 and 0.45–2.68, respectively. The content of alloying elements in the investigated areas varied within (wt %): W – 0.00–43.06, Mo – 0.00–32.72, V – 0.19–20.72, Cr – 0.69–33.94, Co – 0.00–3.96. Analysis of the study’s results reveals that the most acceptable ratio of Si:C in the charge is 0.52. In this case, there is a certain content of residual silicon along with carbon in the form of carbosilicide and silicide compounds. Such indicators of the alloy provide sufficient reducing capacity of the alloy when used. The properties of the alloy make it possible, when smelting steels, to replace part of those standard ferroalloys that do not have strict carbon restrictions.

Fabrication of Porous SiC by Direct Selective Laser Sintering Effect of Boron Carbide

Additive manufactured porous SiC is a promising material applied in extreme conditions characterised by high temperatures, chemical corrosion, and irradiation etc. However, residual Si’s existence deteriorates its performance and limits its application in harsh environments. In this study, B4C was introduced into the selective laser sintering process of SiC, and its effects on forming ability, pore parameters, microstructure, and phases were investigated. The results showed that when B4C was added, the processing window was enlarged. The minimum energy density was reduced from 457 J/cm2 to 214 J/cm2 when the content of B4C reached 15 wt%. Microstructure orientation was enhanced, and the residual silicon content was decreased from 38 at.% to about 8 at.%. Small pores were turned into large pores with the increase of B4C addition. The findings indicate that the addition of B4C increases the amount of liquid phase during the laser sintering process of silicon carbide, improving the SiC struts’ density and reducing the residual silicon by reacting with it. Therefore, the addition of B4C will help improve the application performance of selected laser-sintered silicon carbide under extreme conditions.

SiC-IrSi3 for High Oxidation Resistance.

SiC is a material with excellent mechanical and thermal properties but with a high production cost. Obtaining SiC by reactive infiltration is an attractive method with a much lower cost than the traditional sintering process. However, the reactive infiltration process presents a serious problem, which is the high residual silicon content, which decreases its applicability. The replacement of silicon with silicides is a widely used alternative. The present investigation shows the good mechanical properties of the SiC-IrSi3 composite material obtained by reactive infiltration of SiC-C preforms with Ir–Si alloys. The thermomechanical analysis shows a high compatibility of silicide with SiC. The presence of the silicide shows a substantial improvement against the oxidation of the SiC-Si composites.

Performance optimization of complicated structural SiC/Si composite ceramics prepared by selective laser sintering

Combining reaction-bonded (RB) process and selective laser sintering (SLS) method is an effective approach to prepare ceramic components with complex shapes. The purpose of this paper is to find efficient ways to improve the performance of SiC/Si composites prepared by SLS/RB technologies. Effects of epoxy resin binder on the performance and microstructure of preforms and sintered bodies were studied first. Then, based on the above results, graphite with low reactivity was used as an alternative slow-release carbon source to promote sintering densification process and improve the carbon density of preforms. When the added amount of graphite increased, clusters of nanometer-sized SiC grains formed and the silicon phase transformed into pieces, which reduced the content and dimension of silicon phase. Furthermore, by applying a two-step sintering method, the residual silicon content of SiC/Si composites decreased further and the flexural strength at high temperatures increased.

Controllability of the pore characteristics of B4C/C preform prepared by gel-casting and the properties of RBBC composites

A new type of pore structure of B4C/C preform was fabricated by a resorcinol-formaldehyde (RF) hydrogel gel-casting system. Pore structure controllability of the B4C/C preform was achieved by adjusting the content of the catalyst Na2CO3. Increasing the content of Na2CO3 could achieve accurate control of the B4C/C preform from a single macroporous or mesoporous structure to a hierarchical macroporous-mesoporous structure. The reaction bonded boron carbide (RBBC) composites were prepared by the infiltration of B4C/C preforms of different pore structures with liquid silicon. The residual silicon content and mechanical properties of the RBBC composites were studied. The residual silicon content was controlled by the modification of the open porosity and pore structure of the B4C/C preforms, and the lowest residual silicon content was 33 vol%. Sample S300, which was prepared through liquid silicon infiltration of a B4C/C preform with a single mesoporous structure (with the optimum aperture size of 49 nm), had the best mechanical properties, including a flexural strength and fracture toughness of 419 ± 17 MPa and 4.12 ± 0.12 MPa·m1/2, respectively.

Microstructural development and factors affecting the performance of a reaction-bonded silicon carbide composite

Abstract Due to its near net-shape forming characteristic, reaction-bonded silicon carbide (RBSC) is an ideal sintering material to prepare complicated structural SiC-based ceramics when combined with selective laser sintering (SLS). With this understanding, various factors affecting RBSC composites and the performance control methods were analyzed in this work. By studying the microstructural development and reaction mechanism during the reaction-bonded process, the main factor affecting the performance was found to be the carbon density of SiC/C preform. The residual silicon content decreased with the increase in the carbon density of preform, thereby improving the performance. When the carbon density of preform exceeded the maximum value, some unreacted carbon existed in the sintered body, resulting in the degradation of performance. In order to break the limit of maximum carbon density of the preform, two effective approaches, namely the slow-release carbon source and new-style structure capillary channel were proposed in this work.

Reaction bonding of silicon carbides by Binder Jet 3D-Printing, phenolic resin binder impregnation and capillary liquid silicon infiltration

Abstract Fabrication process of Reaction Bonded Silicone Carbides (RBSC) including Binder Jet (BJ) 3D-Printing, additional carbonization by Phenolic Resin Binder Impregnation (PRBI) and Capillary Liquid Silicon Infiltration (CLSI) has been examined. An effect of additional carbonization by PRBI of BJ 3D-printed porous SiC on the residual Si content after the CLSI and on the microstructure of secondary SiC has been investigated. It has been shown that 50% of the required carbon content can be obtained by this carbonization method in the BJ 3D-printed porous “green” body before the CLSI. The method of additional carbonization allows significant decreasing of the residual silicon content. High efficiency of the CLSI for full filling of complex geometric thin-walled shapes has been confirmed experimentally. This three-steps technology allows fabricating of the RBSC of complex geometric shapes with the wall thickness less than 1 mm and the residual Si less than 10–15%.

Effects of random chopped short carbon fibers on microstructure and mechanical properties of joints for Cf/SiC composites by reaction bonding process

Random chopped short carbon fibers (Csf)/phenol-formaldehyde resin (PF)/SiC powder mixtures are used as filler for the joining of Cf/SiC composites to obtain SiC interlayer at the joining region. The influences of Csf on the microstructure and mechanical properties have been investigated. Research shows that the introduction of Csf can improve the microstructure uniformity of the joint and reduce residual silicon content in the interlayer. The joint achieve a high flexural strength of 232 ± 33 MPa as the carbon fiber content is 30 wt.%, which is similar to that of the Cf/SiC composites (220 ± 21 MPa). The decrease in residual silicon content and the formation of nano-sized SiC particles are the main reasons for high joining strength.

Direct laser sintering of reaction bonded silicon carbide with low residual silicon content

Additive manufacturing (AM) techniques are promising manufacturing methods for the production of complex parts in small series. In this work, laser sintering (LS) was used to fabricate reaction bonded silicon carbide (RBSC) parts. First, silicon carbide (SiC) and silicon (Si) powders were mixed in order to obtain a homogeneous powder. This powder mixture was subsequently laser sintered, where the Si melts and re-solidifies to bind the primary SiC particles. Afterwards, these SiSiC preforms were impregnated with a phenolic resin. This phenolic resin was pyrolysed yielding porous carbon, which was transformed into secondary reaction formed SiC when the preforms were infiltrated with molten silicon in the final step. This resulted in fully dense RBSC parts with up to 84 vol% SiC. The optimized SiSiC combined a Vickers hardness of 2045 HV, an electrical conductivity of 5.3 × 103 S/m, a Young's modulus of 285 GPa and a 4-point bending strength of 162 MPa.

Effects of Fe addition on the mechanical and thermo-mechanical properties of SiC/FeSi2/Si composites produced via reactive infiltration

Remaining silicon in SiC-based materials produced via reactive infiltration limits their use in high-temperature applications due to the poor mechanical properties of silicon: low fracture toughness, extreme fragility and creep phenomena above 1000°C. In this paper SiC–FeSi2 composites are fabricated by reactive infiltration of Si–Fe alloys into porous Cf/C preforms. The resulting materials are SiC/FeSi2 composites, in which remaining silicon is reduced by formation of FeSi2. For the richest Fe alloys (35wt% Fe) a nominal residual silicon content below 1% has been observed. However this, the relatively poor mechanical properties (bending strength) measured for those resulting materials can be explained by the thermal mismatch of FeSi2 and SiC, which weakens the interface and does even generate new porosity, associated with a debonding phenomenon between the two phases.

Development of SiC–SiC joint by reaction bonding method using SiC/C tapes as the interlayer

SiC/C tapes with different compositions and thicknesses were used to join pressureless sintered silicon carbide ceramics by reaction bonding method. The microstructure of the joints and the influences of joint thickness and residual silicon content in joint layer on the 4-point flexural strength of as joined SiC ceramics have been investigated. Specimens with high flexural strength can be achieved through the control of the composition and the thickness of the joint layer. The highest flexural strength of the joined specimens with the joint thickness of 13 μm can reach 346 ± 35 MPa and 439 ± 31 MPa at room temperature and 1250 °C, respectively. The microstructure development and the reaction bonding mechanism were also studied.