Microwave dielectric properties of mineral sillimanite obtained by conventional and cold sintering process

The sillimanite (Al₂SiO₅) mineral has been sintered by conventional ceramic route and by cold sintering methods. The mineral has very poor sinterability and transformed to mullite on sintering above 1525 °C. The dielectric properties of sillimanite mineral (Al₂SiO₅) are investigated at radio and microwave frequency ranges. The mineral sintered at 1525 °C has low ε_r of 4.71 and tanδ of 0.002 at 1 MHz and at microwave frequency ε_r = 4.43, Q_u × f = 41,800 GHz with τ_f = −17 ppm/°C. The sintering aid used for cold sintering Al₂SiO₅ is sodium chloride (NaCl). The Al₂SiO₅NaCl composite was cold sintered at 120 °C. XRD analysis of the composite revealed that there is no additional phase apart from Al₂SiO₅ and NaCl. The densification of the Al₂SiO₅NaCl composite was confirmed by using microstructure analysis. The Al₂SiO₅NaCl composite has ε_r of 5.37 and tanδ of 0.005 at 1 MHz whereas at microwave frequency it has ε_r = 4.52, Q_u × f = 22,350 GHz with τ_f = −24 ppm/°C. The cold sintered NaCl has ε_r = 5.2, Q_u × f = 12,000 GHz with τ_f = −36 ppm/°C.     

Phase composition,crystal structure and microwave dielectric properties of Mg2−xCuxSiO4 ceramics

In this work, the Mg_2-xCu_xSiO₄(x = 0–0.40) microwave dielectric ceramics were prepared using solid-state reaction method. Compared with the Mg₂SiO₄ sample, the Cu-substituted Mg samples could be sintered at a lower temperature. The Mg_2?xCu_xSiO₄ ceramics exhibit the composite phases of Mg₂SiO₄ and a small quantity of MgSiO₃. The Cu²⁺ ion presented a solid solution with the Mg₂SiO₄ phase and preferentially occupy Mg(1) site. The distortion of MgO₆ octahedron was modified by Cu²⁺ ions, resulting in a positive change in the temperature coefficient of resonance frequency (τ_f) values. Excellent microwave dielectric properties of ε_r = 6.35, high Qf of ～ 188,500 GHz and near zero τ_f = ?2.0 ppm/°C were achieved at x = 0.08 under sintering at 1250 °C for 4 h. Thus, the fabricated ceramics were considered as possible candidates for millimeter-wave device applications.     

Phase equilibria in the CaO·SiO2Na2O·SiO2Na2O·Al2O3·6SiO2 system

Equilibrium phase relations in the system CaO·SiO₂Na₂O·SiO₂Na₂O·Al₂O₃·6SiO₂ at 40–80 wt% Na₂O·Al₂O₃·6SiO₂ composition range have been experimentally studied at temperatures between 800 °C and 1200 °C. The liquidus temperature was determined with differential scanning calorimetry. The equilibrated samples were quenched with pressurized nitrogen, and examined with electron probe X-ray microanalysis and X-ray diffraction for identification of microstructure and phase relations. Five primary phase fields, CaO·SiO₂, Na₂O·SiO₂, Na₂O·2CaO·3SiO₂, 2Na₂O·CaO·3SiO₂ and Na₂O·Al₂O₃·6SiO₂ were established. The ternary eutectic point of CaO·SiO₂, Na₂O·2CaO·3SiO₂ and Na₂O·Al₂O₃·6SiO₂ was determined to be at 1030 °C with the composition of 29.0 wt% CaO·SiO₂, 12.0 wt% Na₂O·SiO₂ and 59.0 wt% Na₂O·Al₂O₃·6SiO₂. Peritectic reaction of Na₂O·2CaO·3SiO₂, 2Na₂O·CaO·3SiO₂ and Na₂O·Al₂O₃·6SiO₂ occurred at 930 °C with the composition of 13.0 wt% CaO·SiO₂, 29.0 wt% Na₂O·SiO₂ and 58.0 wt% Na₂O·Al₂O₃·6SiO₂. The liquidus surface projection of the ternary system has been constructed in the composition region important for the bottom ash application.     

The synergistic mechanism of thermally reduced graphene oxide and antioxidant in improving the thermo-oxidative stability of polypropylene

The feasibility of using thermally reduced graphene oxide (TrGO) to improve the antioxidative efficiency of commercial antioxidant (3,5-di-tert-butyl-4-hydroxycinnamic acid, AO) on unstabilized polypropylene (PP) was evaluated in terms of the oxidation induction time (OIT) and the initial degradation temperature (T_i). It was found that a synergistic effect exist between AO and TrGO in retarding the degradation of PP in oxygen-containing atmosphere. Compared with that of PP/AO (100/0.5) sample, the OIT value of PP/AO/TrGO (100/0.5/1) composite was almost doubled at 180 °C and the value of T_i in air was improved by 37.2 °C. As verified by using radical scavenging assay with the 1,1-diphenyl-2-picrylhydrazyl radical, the TrGO sheets exhibited a good radical scavenging capacity. The synergistic stabilization mechanism was attributed to the enhanced dispersion of TrGO sheets in the PP matrix in the presence of 0.5 wt.% AO, which could improve the oxygen barrier effect and radical scavenging efficiency of TrGO. This synergistic effect between AO and TrGO can efficiently reduce the concentrations of oxygen and peroxy radicals in the PP matrix, leading to the significant improvement in thermo-oxidative stability of PP/AO/TrG composite.     

Preparation of SiO2–SiC composites with a precursor method

SiO₂–SiC composite particles were prepared through a hybrid sol–gel precursor process. Compacts were prepared by using a conventional sintering process. The techniques of DSC–TG, SEM and XRD were use to characterize the composite particles and the sintered compacts. It was found that a core–shell structure was constructed in the composite particles with cores of SiC and shells of amorphous SiO₂. Nucleation of SiO₂ occurred at about 1200 °C. The optimized sintering temperature for 30SiO₂–70SiC (vol.%) composites was about 1400 °C with a relatively homogeneous microstructure. The maximum density was about 2.03 g cm^?3.     

Densification and mechanical properties of cBN–TiN–TiB2 composites prepared by spark plasma sintering of SiO2-coated cBN powder

cBN–TiN–TiB₂ composites were fabricated by spark plasma sintering at 1773–1973 K using cubic boron nitride (cBN) and SiO₂-coated cBN (cBN(SiO₂)) powders. The effect of SiO₂ coating, cBN content and sintering temperature on the phase composition, densification and mechanical properties of the composites was investigated. SiO₂ coating on cBN powder retarded the phase transformation of cBN in the composites up to 1873 K and facilitated viscous sintering that promoted the densification of the composites. Sintering at 1873 K, without the SiO₂ coating, caused the relative density and Vickers hardness of the composite to linearly decrease from 96.2% to 79.8% and from 25.3 to 4.4 GPa, respectively, whereas the cBN(SiO₂)–TiN–TiB₂ composites maintained high relative density (91.0–96.2%) and Vickers hardness (17.9–21.0 GPa) up to 50 vol% cBN. The cBN(SiO₂)–TiN–TiB₂ composites had high thermal conductivity (60 W m⁻¹ K⁻¹ at room temperature) comparable to the TiN–TiB₂ binary composite.     

Densification of SiO2–cBN composites by using Ni nanoparticle and SiO2 nanolayer coated cBN powder

Cubic boron nitride (cBN) powder was coated with Ni nanoparticle and SiO₂ nanolayer (abbreviated as cBN/Ni and cBN/SiO₂, respectively) by rotary chemical vapor deposition (RCVD), and compacted with SiO₂ powder by spark plasma sintering at 1473–1973 K for 0.6 ks. The effects of Ni and SiO₂ coatings on the densification, phase transformation of cBN and hardness of SiO₂–cBN composites were compared. The phase transformation of cBN to hBN was identified at 1973 K in SiO₂–cBN/SiO₂ composites, 300 K higher than that in SiO₂–cBN/Ni composites, indicating that SiO₂ retarded the transformation of cBN. The relative density of SiO₂–cBN/SiO₂ with 50 vol% cBN sintered at 1873 K was 99% with a hardness of 14.5 GPa.     

Preparation and characterization of porous,biomorphic SiC ceramic with hybrid pore structure

Bio-carbon template (charcoal) was prepared by carbonizing pine wood at 1200 °C under vacuum, and was impregnated with phenolic resin/SiO₂ sol mixture by vacuum/pressure processing. Porous SiC ceramics with hybrid pore structure, a combination of tubular pores and network SiC struts in the tubular pores, were fabricated via sol–gel conversion, carbonization and carbothermal reduction reaction at elevated temperatures in Ar atmosphere. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM) were employed to characterize the phase identification and microstructural changes during the C/SiO₂ composites-to-porous SiC ceramic conversion. Experimental results show that the density of C/SiO₂ composite increases with the number of impregnation procedure, and increases from 0.32 g cm⁻³ of pine-derived charcoal to 1.5 g cm⁻³ of C/SiO₂ composite after the sixth impregnation. The conversion degree of charcoal to porous SiC ceramic increases as reaction time is lengthened. The resulting SiC ceramic consists of β-SiC with a small amount of α-SiC. The conversion from pine charcoal to porous SiC ceramic with hybrid pore structure improves bending strength from 16.4 to 42.2 MPa, and decreases porosity from 76.1% to 48.3%.     

Microstructure and elastic modulus of electrospun Al2O3-SiO2-B2O3 composite nanofibers with mullite-type structure prepared at elevated temperatures

In the present work, Al₂O₃-SiO₂-B₂O₃ composite nanofibers with mullite-type structure were prepared using electrospinning technique. The microstructure and elastic modulus of the composite nanofibers obtained at elevated temperatures were studied. The results showed that Al₄B₂O₉ phase formed at 900 °C and then transformed to Al₁₈B₄O₃₃ at 1100 °C. Mullite was also detected in the nanofibers prepared at 1100 °C. Amorphous SiO₂ existed in all samples even the calcination temperature reached up to 1400 °C. The continuous and uniform structure of the composite nanofibers was kept after calcining at different temperatures, while rougher surface was evident due to the growth of the grain caused by the elevated temperature. An increase of elastic modulus of the samples from 9.47 ± 1.91 GPa to 27.30 ± 2.61 GPa was observed when calcination temperatures increased from 800 °C to 1400 °C.     

Utilization of recycled paper processing residues and clay of different sources for the production of porous anorthite ceramics

Production of porous anorthite ceramics from mixtures of paper processing residues and three different clays are investigated. Suitability of three different clays such as enriched clay, commercial clay and fireclay for manufacturing of anorthite based lightweight refractory bricks was studied. Porous character to the ceramic was provided by addition of paper processing residues (PPR). Samples with 30–40 wt% PPR fired at 1200–1400 °C contained anorthite (CaO·Al₂O₃·2SiO₂) as major phase and some minor secondary phases such as mullite (3Al₂O₃·2SiO₂) or gehlenite (2CaO·Al₂O₃·SiO₂), depending on the calcite to clay ratio. Anorthite formation for all clay types was quite successful in samples with 30–40 wt% of paper residues fired at 1300 °C. A higher firing temperature of 1400 °C was needed for the fireclay added samples to produce a well sintered product with large pores. Gehlenite phase occurred mostly at lower temperatures and in samples containing higher amount of calcium (50 wt% PPR). Compressive strength of compacted and fired pellets consisting of mainly anorthite ranged from 8 to 43 MPa.     

Microwave dielectric properties of porous Mg2SiO4 filling with TiO2 prepared by a liquid phase deposition process

Forsterite (Mg₂SiO₄) possesses a high quality factor (Q·f) of 270,000 GHz and a low dielectric constant ɛ_r of 6.8. However, it shows a relatively large negative temperature coefficient of resonant frequency τ_f of −73 ppm/°C. For microwave telecommunication, a τ_f of nearly 0 ppm/°C is desirable to keep the frequency stability. In order to improve τ_f, we have tried to produce pure Mg₂SiO₄–TiO₂ composite ceramics with no secondary phases using a liquid phase deposition (LPD) method. Porous Mg₂SiO₄ ceramics was prepared by sintering Mg₂SiO₄ with polymethyl methacrylate (PMMA) particles, and then TiO₂ was filled in the pores of Mg₂SiO₄ by the LPD method. The porosity and microstructure of porous Mg₂SiO₄ was controlled by amount and particle sizes of PMMA and formation process. τ_f of Mg₂SiO₄ filled with TiO₂ by LPD method was improved to −46 ppm/°C.     

Crystallization kinetics and magnetic properties of iron oxide contained 25Li2O–8MnO2–20CaO–2P2O5–45SiO2 glasses

With crystallization at 850 °C for 4 h, LiMn₂O₄, β-wollastonite (β-CaSiO₃), lithium silicate (Li₂SiO₃), Ca(Ca, Mn)Si₂O₆ and Li₂Ca₄Si₄O₁₃ phases were found in 25Li₂O–8MnO₂–20CaO–2P₂O₅–45SiO₂ (LMCPS) glass ceramics. The (Li, Mn)ferrite phase was obtained in the iron oxide contained LMFCPS glass ceramic and Li₂FeMn₃O₈ phase was found in that containing 8 at.% Fe₂O₃. TEM investigations showed that (Li, Mn)ferrite particles dispersed in the β-wollastonite matrix (Li, Mn)ferrite particles, with an average size of 40 nm, were found in the glass ceramics containing 4 at.% Fe₂O₃. The (Li, Mn)ferrite particle sizes in the glass ceramics containing 8 at.% Fe₂O₃ varied from a few μm to 5 nm. The SQUID result showed that only the glass ceramic containing 4 at.% Fe₂O₃ exhibited super-paramagnetic behavior at temperature 300 K and ferromagnetic behavior at 4 K. The LMCPS glass ceramic containing 8 at.% Fe₂O₃ exhibited ferromagnetic behavior at both temperatures.     

Photoluminescence of (ZnO)X-Z(SiO2)Y:(MnO)Z green phosphors prepared by direct thermal synthesis: The effect of ZnO/SiO2 ratio and Mn2+ concentration on luminescence

Green light emitting Zn₂SiO₄:Mn²⁺ phosphors have been synthetised by the solid-state reaction in ambient atmosphere at 1300 °C for 2 h, with ZnO, SiO₂ and MnO₂ as the reagents. The ZnO/SiO₂ molar ratio varied from 2 to 0.5. The doping level was in a lower concentration range (0.01≤x≤0.05). The effect of both the Mn²⁺ concentration and ZnO/SiO₂ molar ratio on luminescence intensity and decay was investigated in detail. The microstructure and phase composition of prepared phosphors were characterised by scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). XRD results indicate that the pure α-Zn₂SiO₄ phase with rhombohedral structure was obtained after heat treatment. The prepared phosphors exhibit a strong green emission centred at 525 nm from the ⁴T₁→⁶A₁ forbidden transition. The highest emission intensity was observed for phosphors with ZnO/SiO₂ molar ratio equal to 1.0, and the Mn²⁺ concentration x=0.03 (ZSMn3). The emission intensity of the ZSMn3 phosphor is comparable with the commercial Zn₂SiO₄:Mn²⁺ phosphor. The decay curves can be characterised by double exponential function. After fitting a fast component τ₁∼2 ms and a slow component τ₂∼10 ms were obtained. The decay times decrease significantly with increasing Mn²⁺ concentration. The decay time and luminescence mechanism depend on the excitation light wavelength. Temperature dependent luminescence of the ZSMn3 phosphor in the temperature range of 25–200 °C was studied.     

Graphenothermal reduction synthesis of MnO/RGO composite with excellent anodic behaviour in lithium ion batteries

Mn(II) oxide/graphene oxide (MnO/RGO) composites were synthesized by an easy and cost-effective graphenothermal reduction method. The surface morphology, structure, chemical composition and electrochemical behaviour of the resulting composites were investigated in detail. The MnO/RGO composite exhibited a high surface area (115.7 m²/g), which led to the high discharge capacity, enhanced cycling stability, and outstanding rate capability as anode in Li-ion batteries (LIBs). The MnO/RGO composite exhibited an higher initial discharge capacity of 1607 mA h/g at a current density of 100 mA/g and maintained 94% of its reversible capacity over 100 consecutive cycles. Furthermore, MnO/RGO composite could preserve a significantly higher capacity of 847 mA h/g for 150 cycles even at a high current density of 250 mA/g. The excellent electrochemical properties result from the existence of highly conductive RGO and a short transportation span for both Li-ions and electrons. The developed MnO/RGO composite materials hold highly promising prospects in LIBs.     

Sintering,microstructure and hardness of Y-TZP- 64S bioglass ceramics

3 mol% yttria-partially stabilized zirconia (Y-TZP) powder and a sol-gel derived CaO- P₂O₅- SiO₂ (64S) bioglass, were used to produce Y-TZP- 64S slip cast compacts. The compacts with 10.5 and 19.9 vol% 64S were sintered at different temperatures up to 1500 °C using 5 and 10 °C/min heating/cooling rates. The densification behaviour, crystalline phase formation and zirconia grain growth were investigated as a function of sintering temperature and 64S glass content. Ca₃(PO₄)₂ along with SiO₂ as a major phase were obtained from thermal decomposition of the 64S glass at 950–1500 °C. Both 64S additions, 10.5 and 19.9 vol%, promoted the sintering process at a lower temperature with respect to Y-TZP (1500 °C); the SiO₂ phase markedly increased the Y-TZP solid state sintering rate at the intermediate stage. The rapidly cooling at 10 °C/min inhibited the t-m transformation of Y-TZP and markedly reduced that of Y-TZP- 64S at 1300–1500 °C. Sintered Y-TZP with 10.5 vol% 64S, nearly fully densified at 1300–1400 °C, was constituted by polygonal ZrSiO₄ particles and elongated Ca₂P₂O₇ particles uniformly distributed in the tetragonal zirconia fine grain matrix. This ceramic exhibited similar hardness to that of Y-TZP sintered at 1500 °C; the in situ formation of calcium phosphate will have the potential to improve the Y-TZP biological properties without significantly affecting its hardness.     

Temperature-induced changes in morphology and microstructure of electrospun mullite nanofibers fabricated from a hybrid mullite sol

Mullite nanofibers with small diameter and high surface area are an ideal candidate as the reinforcements in composite materials, and have promising applications in the fields of catalysis, filtration, thermal storage and so forth. In this work, electrospun mullite nanofibers were successfully synthesized using a hybrid mullite sol. The morphology and microstructure of fibers calcined at different temperatures were investigated. The morphology of fibers synthesized at 900 °C is porous with coarse surface, and after crystallization it becomes compact with smooth surface. The densities of fibers increase with the increasing temperatures. At 1200 °C the surface of fibers becomes coarse again, as a result of the grain growth of mullite. The crystallization path of fibers was revealed that the Al-rich mullite (4Al₂O₃·SiO₂) together with amorphous silica formed at 1000 °C, changed into mullite with higher silica contents as temperature further increased, and finally transformed into a stable 3Al₂O₃·2SiO₂ phase at 1200 °C. During this crystallization process, the flow of amorphous silica phase and the formation of mullite crystal structure benefit the densification of fibers, leading to the resultant fibers with fine and compact microstructure. The present findings can provide a guideline for the preparation of the promising high-mechanical mullite nanofibers and the synthesized nanofibers display great potential as reinforcements in structural ceramic composites.     

High capacity Li storage in sulfur and nitrogen dual-doped graphene networks

Three-dimensional (3D) networks composing of S and N dual-doped graphene (SNG) were synthesized by a chemical vapor deposition approach using MgSO₄-containing whiskers as templates and S source and NH₃ as N source. Energy dispersive spectrometer mapping and X-ray photoelectron spectroscopy coupled with Raman analysis have revealed that S and N atoms with concentrations of 5.2 and 1.8 atom%, respectively, have been substitutionally incorporated into the graphene networks via covalent bonds. The SNG, as an anode material for lithium ion batteries (LIBs), exhibits extremely high capacity (3525 mAh/g at the current density of 50 mA/g) and superior rate capability (870 mAh/g at 1000 mA/g) with excellent cycling stability (remaining a reversible capacity of 400 mAh/g at 10 A/g after 2500 cycles). The enhanced conductivity, the 3D porous network with many disorders and the intrinsically high Li storage capacity of S and N-doped carbon segments have led to the excellent electrode performance of the SNG networks. The effects of binder content and calendaring pressure on the electrode performance have been investigated. The full LIB with SNG as anode and LiCoO₂ as cathode can afford a high reversible capability (164 mAh/g at 0.2 C) and good cycling stability.     

Mechanical properties of nano-grain SiO2 glass prepared by spark plasma sintering

Silicon carbide (SiC) layers were deposited on silica (SiO₂) glass powder by rotary chemical vapor deposition (RCVD) to form SiO₂ glass (core)/SiC (shell) powder; this powder was consolidated by spark plasma sintering (SPS). SiO₂ glass powder with a particle size of 250 nm was coated with 5–10-nm-thick SiC layers. The resultant SiO₂ glass (core)/SiC (shell) powder was consolidated to form a nano-grain SiO₂ glass composite at a relative density above 90% by SPS in the sintering temperature range of 1573–1823 K. The Vickers hardness and fracture toughness of the SiO₂ glass composite at 1723 K were found to be 14.2 GPa and 5.4 MPa m^1/2, respectively.     

Additive manufacturing of zirconia parts by indirect selective laser sintering

Thermally induced phase separation (TIPS) was used to produce spherical polypropylene–zirconia composite powder for selective laser sintering (SLS). The influence of the composition of the composite starting powder and the SLS parameters on the density and strength of the composite SLS parts was investigated, allowing realizing SLS parts with a relative density of 36%. Pressure infiltration (PI) and warm isostatic pressing (WIPing) were applied to increase the green density of the ZrO₂–PP SLSed parts. Infiltrating the SLS parts with an aqueous 30 vol.% ZrO₂ suspension allowed to increase the sintered density from 32 to 54%. WIPing (135 °C and 64 MPa) of the SLS and SLS/infiltrated complex shape green polymer–ceramic composite parts prior to debinding and sintering allowed raising the sintered density of the 3 mol Y₂O₃ stabilized ZrO₂ parts to 92 and 85%, respectively.     

Improved electromagnetic absorbing properties of Si3N4–SiC/SiO2 composite ceramics with multi-shell microstructure

Porous Si₃N₄–SiC composite ceramic was fabricated by infiltrating SiC coating with nano-scale crystals into porous β-Si₃N₄ ceramic via chemical vapor infiltration (CVI). Silica (SiO₂) film was formed on the surface of rod-like Si₃N₄–SiC grains during oxidation at 1100 °C in air. The as-received Si₃N₄–SiC/SiO₂ composite ceramic attains a multi-shell microstructure, and exhibits reduced impedance mismatch, leading to excellent electromagnetic (EM) absorbing properties. The Si₃N₄–SiC/SiO₂ fabricated by oxidation of Si₃N₄–SiC for 10 h in air can achieve a reflection loss of ?30 dB (>99.9% absorption) at 8.7 GHz when the sample thickness is 3.8 mm. When the sample thickness is 3.5 mm, reflection loss of Si₃N₄–SiC/SiO₂ is lower than ?10 dB (>90% absorption) in the frequency range 8.3–12.4 GHz, the effective absorption bandwidth is 4.1 GHz.