Sol-gel assisted synthesis of TiB2-B4C composite powder

Composite powders containing titanium diboride and boron carbide have been prepared by sol-gel method at 1450°C using titanium isopropoxide (titanium precursor), boric acid (Boron precursor), sucrose (carbon source), and acetic acid (AcOH) as a solvent. The effect of boron source (trimethyl borate and boric acid) and B₂O₃/TiO₂, C/B₂O₃ mole ratios of starting materials on the final phases has been studied. The progress of reactions was determined using thermal analysis (TGA-DTA). The resultant powders were characterized by X-ray diffraction (XRD) analysis and field-emission scanning electron microscope (FESEM). XRD patterns confirmed the formation of TiB₂, B₄C, and TiC phases after heat treatment at 1450°C at mole ratio of B₂O₃/TiO₂ = 4.5, C/B₂O₃ = 2.4. With increasing the content of boron oxide, the unwanted phases such as TiC and C were reduced. TiB₂ and B₄C composite powders (~5 µm diameter) containing residual carbon (<4 wt%) were synthesized using the mole ratio of B₂O₃/TiO₂ = 10 and C/B₂O₃ = 1.9 at low temperature of 1450°C.     

碳热还原TiO2与B2O3合成硼化钛粉体

在碳管炉内,碳热还原TiO2与B2O3合成了TiB2粉体.采用XRD、SEM、TG-DSC等分析技术,研究了碳热还原法合成TiB2时B2O3的加入量、还原剂C的加入量及还原剂的种类对合成TiB2产率的影响.研究表明,为提高TiB2的合成产率,原料配比中B2O3和C应适当过量,最佳的原料配比(物质的量)为:TiO2∶ B2O3∶C=1∶2∶5.5;在炭黑、活性炭和石墨三种碳源的选择上,以炭黑的还原效果最佳.     

Combustion synthesis of B4C/Al2O3/C composite powders and their effects on properties of low carbon MgO-C refractories

To improve the dispersity and oxidation resistance of nano carbon black (CB) in low carbon MgO-C refractories, B₄C/Al₂O₃/C composite powders were prepared by a combustion synthesis method using B₂O₃, CB and Al powders as the raw materials. The phase compositions and microstructures of the synthesized products were characterized by X-ray diffraction (XRD), Raman spectroscopy, and a scanning electron microscopy/energy dispersive spectrometry (SEM/EDS). The results show that an 80 wt% excess of CB is the maximum amount of CB that can be added under the condition of a self-propagating combustion wave, and the phase compositions of the products are B₄C, α-Al₂O₃ and CB. B₄C particles with uniform sizes and cubic polyhedral structures are embedded in the Al₂O₃ matrix. The combustion-synthesized B₄C/Al₂O₃/C powders and mechanically mixed B₄C/Al₂O₃/C powders were added to the low carbon MgO-C refractories, and their corresponding properties were compared. The apparent porosity (AP) of the refractories with the synthesized powders (labelled as M3) is lower than those of the refractories with mechanically mixed powders (labelled as M2) and without composite powders (labelled as M1). The oxidation ratio and slag erosion depth of M3 were lower than those of M2 and M1. The thickness of the decarburized layer of M3 was 10.2% and 22.4% less than that of M2 and M1, respectively. The penetration depth of M3 was 12.0% and 27.9% less than that of M2 and M1, respectively. The thermal shock resistance of M3 was better than that of M2 and M1. The residual strength ratio of M3 was 15.8% and 17.2% more than that of M2 and M1, respectively. These results suggest that the combustion-synthesized B₄C/Al₂O₃/C composite powders can be used as new and promising additives for low carbon MgO-C refractories.     

Phase equilibria in the La2O3-Sm2O3-ZrO2 system: Experimental studies and thermodynamic modeling

A series of ceramic samples were prepared to experimentally investigate sub-solidus phase relations in the La₂O₃-Sm₂O₃-ZrO₂ system at 1873 K and 1673 K. No ternary compounds have been observed, while the binary La₂Zr₂O₇ and Sm₂Zr₂O₇ pyrochlore phases form a continuous solid solution La_2?xSm_xZr₂O₇ in the ternary system at the selected temperatures. X-ray diffraction and microstructure results demonstrated that the pyrochlore phase is stable in the ZrO₂-rich corner. The homogeneity range of the pyrochlore phase was carefully determined and the phase boundary of the cubic ZrO₂ (fluorite phase) which extends into the ternary system was also constructed via electron probe microanalysis. The as-obtained data were adopted to determine the mixing parameters for the pyrochlore and fluorite phases in the present thermodynamic modeling. A self-consistent database of the La₂O₃-Sm₂O₃-ZrO₂ system was accordingly established for the first time and the calculations agree well with the experimental data in the current work.     

Small amount TiB2 addition into B4C through sputter deposition and hot pressing

Small amount of TiB₂ (<5 wt%) was added into B₄C through a novel method that combines the use of sputter deposition and hot pressing. Sputter deposition provided more uniform dispersion of TiB₂ grains with smaller grain sizes as compared to the conventional particulate mixing. Small amount TiB₂ addition demonstrated to be an effective way for improving the fracture behavior and toughness of B₄C while not sacrificing its outstanding lightweight property to a large extent: 2.3 wt% TiB₂ addition brought 15% improvement in indentation fracture toughness while resulting in less than 2% increase in density. The improvement can be attributed to the combination of crack impeding by TiB₂ grains and crack deflection at the B₄C–TiB₂ interfaces. TiB₂ also played as grain growth inhibitor resulting in a slight increase (2%) in Vickers hardness. Another intention of employing sputter deposition was to modify the grain boundary of B₄C; however, neither formation of Ti-containing phase nor Ti segregation has been observed at grain boundaries likely due to the poor wettability of B₄C.     

Addressing amorphization and transgranular fracture of B4C through Si doping and TiB2 microparticle reinforcing

Over the last two decades, many studies have contributed to improving our understanding of the brittle failure mechanisms of boron carbide and provided a road map for inhibiting the underlying mechanisms and improving the mechanical response of boron carbide. This paper provides a review of the design and processing approaches utilized to address the amorphization and transgranular fracture of boron carbide, which are mainly based on what we have found through 9 years of work in the field of boron carbides as armor ceramics.     

固体超强酸S_2O_8~(2-)/TiO_2-Al_2O_3催化合成乙酸戊酯的动力学研究

研究了以固体超强酸S2O82-/TiO2-A l2O3为催化剂合成乙酸戊酯的反应,在反应温度分别为100,108,116℃下,测出合成乙酸戊酯的动力学方程参数,建立了动力学方程式,并与无催化剂酯化反应的活化能及动力学方程式进行了比较。结果表明,最佳合成条件为:醇酸摩尔比1.3∶1,催化剂用量1 g,带水剂用量10 mL。固体超强酸S2O82-/TiO2-A l2O3使反应活化能明显降低,是合成乙酸戊酯的有效催化剂。     

燃烧合成法制备TiB2-Al2O3复相陶瓷的研究

采用自蔓延燃烧合成法在室温下的空气中制备出了TiB2-Al2O3复相陶瓷,通过X射线衍射(XRD)和扫描电镜(SEM)分析表明合成的产物纯净,无中间相,TiB2的形貌为规则的块状,晶粒细小,平均尺寸为(2～5μm),弥散的分布在晶粒较大的Al2O3(40～50μm)四周,而Al2O3的形状不是很规则.     

Novel combustion synthesis of La3+-substituted MnFe2O4

La³⁺-substituted MnFe₂O₄ compounds have been prepared by using a novel combustion synthesis method. This process was found to yield homogeneous, finely crystalline powders without intermediate decomposition and/or calcination steps. Combustion-synthesized powders were sintered at 1000°C, and structural features of thus prepared materials were characterized by XRD analysis and FT-IR spectroscopy. The dc electrical conductivity of synthesized materials has been measured as a function of temperature up to 1000°C. The materials have shown semiconducting behavior at elevated temperatures. The ac electrical conductivity of synthesized samples was found to increase with increasing applied frequency. The dielectric constant and dielectric loss tangent have also been characterized. The article is published in the original.     

Al-TiO2-C体系热力学分析及Al2O3-TiC复相陶瓷的燃烧合成

对Al-TiO2-C燃烧合成体系进行了热力学计算,并利用Al-O-N、Ti-O-N、C-O-N三个体系的叠加优势区相图分析了该燃烧合成体系的平衡产物相.结果表明,Al-TiO2-C燃烧合成体系的绝热燃烧温度为2398 K,燃烧合成平衡相为Al2O3和TiC.XRD检测结果与热力学分析结果相吻合,说明该燃烧合成反应进行得较为彻底,证实热力学分析结果可信.原位生成的Al2O3和TiC两相分布较均匀,燃烧合成产物疏松多孔,易于通过球磨方式达到破碎、磨细的目的.     

Sintering behavior and microwave dielectric characteristics of BaO–Sm2O3–4TiO2 ceramics with B2O3 and BaB2O4 addition

We studied the low temperature sintering and the reaction in BaO–Sm₂O₃–4TiO₂ ceramics with boron-based additives for the application to microwave dielectric devices. The amount of the boride glasses of B₂O₃ and BaB₂O₄ was varied from 1 to 10 wt.% and the green compacts were sintered in the temperature range of 900–1200 °C for 2 h. When B₂O₃ was added, second phases of Sm₂Ti₂O₇, BaTi(BO₃)₂, Ba₂Ti₉O₂₀, and TiO₂ were formed, while BaB₂O₄ addition resulted in the formation of BaSm₂Ti₄O₁₂ single phase without second phases. On the basis of these results, it is regarded that the B₂O₃ is a reactive glass and the BaB₂O₄ is a non-reactive glass. The second-phase development, sintering behavior and microwave dielectric characteristics of BaO–Sm₂O₃–4TiO₂ ceramics were examined.     

固载型杂多酸盐催化剂HPAS/TiO2-Al2O3的制备及催化性能研究

制备了固载型杂多酸盐催化剂HPAS/TiO2-Al2O3,用IR、XRD、TG-DTA等对催化剂进行了表征。在DOP的合成反应中考查了催化剂的催化作用。实验表明：HPAS/TiO2-Al2O3稳定性好,再生性能优良,是一种低温高效型催化剂。     

Solution combustion synthesis of crystalline V2O3 and amorphous V2O3/C as anode for lithium-ion battery

In this paper, crystalline V₂O₃ and amorphous V₂O₃/C products are synthesized via one-pot solution combustion synthesis (SCS) method (completed within 2 minutes). The characteristics of combustion products could be tuned by changing the amounts of glucose. The as-synthesized crystalline V₂O₃ nanopowder consists of nanoparticles with average size of ~100 nm. Amorphous V₂O₃/C composite exhibits large porous microsheet structure in which oxygen vacancy-enabled amorphous V₂O₃ particles are embedded into N-doped carbon microsheets. The existence of oxygen vacancies can promote energetics for the transport of electrons and ions and maintain the integrity of sample surface morphology. Moreover, N-doping can enhance electrical conductivity and promote the diffusion of electrons and lithium ions. Amorphous V₂O₃/C composite possesses high reversible capacity and superior cycling stability (833 mAh g⁻¹ at 1 A g⁻¹ after 250 cycles, 867 mAh g⁻¹ at 0.1 A g⁻¹ after 100 cycles), indicating its potential as excellent anode material for lithium-ion battery. The proposed one-step, time- and energy-efficient SCS method has the potential to prepare other oxygen vacancy-enabled transition metal oxides for energy storage.     

Experimental studies and modeling of a fixed bed reactor for Fischer-Tropsch synthesis using biosyngas

The aim of this work was to study the Fischer-Tropsch (FT) synthesis of a model biosyngas (33% H₂, 17% CO and 50% N₂) in a single tube fixed-bed FT reactor. The FT reactor consisted of a shell and tube with high-pressure boiling water circulating throughout the shell. A spherical unpromoted cobalt catalyst was used with the following reaction conditions: a wall temperature of 473 K, a pressure of 20 bars and a gas hour space velocity (GHSV) of 37 to 180 NmL.g_cat^− 1.h^− 1. The performance of the FT reactor was also validated by developing a 2D pseudo-homogeneous model that includes transport equations and reaction rate equations. Good agreement between the model predictions and experimental results were obtained. This developed model was extended to predict and quantify the influence of the FT kinetics as well as determine the influence of the tube diameter and the wall temperature. The predicted behaviors for CO and H₂ conversion, productivity of hydrocarbons (mainly CH₄ and C₅₊) and fluid temperature along the axis of the reactor have been analyzed.     

Effect of B4C content and annealing on complex permittivity and microwave-absorption properties of B4C/Al2O3 coatings

The B₄C/Al₂O₃ coatings were fabricated by air plasma spraying technology, and their complex permittivity and microwave absorption properties in the X-band were investigated before and after annealing (500 °C/2 h). Both the real and imaginary parts of the complex permittivity of the coatings decreased after annealing, which can be attributed to the weakening of polarization relaxation intensity and the reduction of electrical conductivity caused by the escape of carbon atoms. In addition, the density of B₄C/Al₂O₃ coatings decreased from 3.01 to 2.16 g/cm³ with increasing B₄C content. The B₄C/Al₂O₃ coatings exhibit a minimum reflection loss (RL) value of ?39.58 dB and the effective absorption bandwidth (RL＜?10 dB, EAB) covers 1.9 GHz at a thickness of 1.6 mm. After annealing, the above coatings still had an EAB of 1 GHz. Therefore, the B₄C/Al₂O₃ coatings can be considered as a promising microwave-absorption candidate with good high-temperature microwave-absorbing performance and low density.     

Preparation and characterisation of mixed matrix Al2O3- and TiO2-based ceramic membranes prepared using polymeric synthesis route

Al₂O₃- and TiO₂-based ceramic membranes prepared using polymeric synthesis route were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR) and gas permeability tests. The influence of the final calcination temperature and the systematic investigation of the properties of the membranes are provided. The calcination temperature affected morphological, structural and chemical properties, as well as the gas permeability of the ceramic membranes. XRD analysis revealed rhombohedral and tetragonal structures of Al₂O₃ and TiO₂-based ceramic, respectively, prepared at calcination temperatures of 1100 and 1200 °C. The TiO₂-based ceramic matrix calcined at temperatures of 1100 and 1200 °C exhibited a well-defined crystalline microstructure with the grains increasing in size as a function of temperature. FTIR analysis revealed that phosphorus additives in orthoclase clay tend to form phosphonate groups during the calcination process. The decomposition of organic source was not fulfilled as tested at calcination temperatures of 1000, 1100 and 1200 °C.     

Thermodynamic modeling and experimental investigation of the MgO-Y2O3-ZrO2 system

Solid-state phase equilibria in the MgO-Y₂O₃-ZrO₂ system as well as the equilibria including liquid were investigated in the whole-compositional range using high-temperature differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM/EDX). Isothermal sections at 1493, 1573, 1693, and 1923 K were constructed based on experimental studies. The presence of tie line between MgO and Y₄Zr₃O₁₂ in the temperature range between 1493 and 1573 K was confirmed. The eutectic melting in the MgO-Y₂O₃-ZrO₂ system was established using DTA followed by SEM/EDX microstructure investigation. Based on the obtained experimental results, the thermodynamic database was derived.     

Synergistic effects of TiB2 and graphene nanoplatelets on the mechanical and electrical properties of B4C ceramic

Monolithic B₄C, B₄C–TiB₂, and B₄C–TiB₂–graphene nanoplatelets (GNPs) were fabricated by hot pressing (HP) at 1900 °C for 1 h under an axial pressure of 30 MPa. The microstructures and mechanical and electrical properties of the B₄C composites were investigated. The results show that the GNPs are distributed homogeneously in B₄C-based ceramic composites. Compared with monolithic B₄C, the TiB₂–GNPs-containing B₄C composite exhibits an approximately 68 % increase in flexural strength and a 169 % increase in fracture toughness due to the synergistic effects of TiB₂ particles and GNPs. The toughening mechanisms mainly include TiB₂ crack deflection, crack branching, transgranular fracture and GNPs crack deflection, crack bridging, and GNPs pull-out. Additionally, the electrical conductivity of the B₄C composite reinforced with dual fillers is three orders of magnitude higher than that of monolithic B₄C due to the establishment of a conductive network. The addition of GNPs can efficiently connect the isolated conductive TiB₂ particles in the B₄C matrix and provides an additional channel for electron migration.     

Synthesis and properties of conductive B4C ceramic composites with TiB2 grain network

High electrical resistance and low fracture toughness of B₄C ceramics are 2 of the primary challenges for further machining of B₄C ceramics. This report illustrates that these 2 challenges can be overcome simultaneously using core‐shell B₄C‐TiB₂&TiC powder composites, which were prepared by molten‐salt method using B₄C (10 ± 0.6 μm) and Ti powders as raw materials without co‐ball milling. Finally, the near completely dense (98%) B₄C‐TiB₂ interlayer ceramic composites were successfully fabricated by subsequent pulsed electric current sintering (PECS). The uniform conductive coating on the surface of B₄C particles improved the mass transport by electro‐migration in PECS and thus enhanced the sinterability of the composites at a comparatively low temperature of 1700°C. The mechanical, electrical and thermal properties of the ceramic composites were investigated. The interconnected conductive TiB₂ phase at the grain boundary of B₄C significantly improved the properties of B₄C‐TiB₂ ceramic composites: in the case of B₄C‐29.8 vol% TiB₂ composite, the fracture toughness of 4.38 MPa·m^1/2, the electrical conductivity of 4.06 × 10⁵ S/m, and a high thermal conductivity of 33 W/mK were achieved.