Polymer-derived SiOC aerogel with hierarchical porosity through HF etching

Silicon oxycarbide (SiOC) aerogels have been synthesized from preceramic polymers via pyrolysis in inert atmosphere at 1200 and 1300 °C. The as synthesized materials have a typical colloidal microstructure with mesoporosity in the range 10–50 nm and no microporosity. HF acid attack of the SiOC aerogels dissolves preferentially the SiO₂-rich phase and creates micro-and (small)mesopores (<10 nm) in the aerogels microstructure finally leading to a materials with hierarchical porosity. The HF post-pyrolysis treatment is more efficient for the SiOC aerogels pyrolyzed at the maximum temperature, i.e. 1300 °C, leading to a maximum value of specific surface area of 530 m²/g and total porosity of 0.649 cc/g.     

Large size and low density SiOC aerogel monolith prepared from triethoxyvinylsilane/tetraethoxysilane

Crack-free silicon oxycarbide (SiOC) aerogel monolith was fabricated by pyrolysis of precursor aerogel prepared from triethoxyvinylsilane/tetraethoxysilane (VTES/TEOS) using sol-gel process and ambient drying. Effects of different precursors, the amount of base catalyst (NH₄OH) and the heating rate during pyrolysis on the properties such as monolithicity, bulk density, surface area and pore size distribution of aerogels were investigated. The results show that the crack-free SiOC aerogel can be easily obtained from VTES/TEOS as compared to that of methyltriethoxysilanes/tetraethoxysilane (MTES/TEOS) and phenyltriethoxysilanes/tetraethoxysilane (PhTES/TEOS) precursors. The influence of heating rate during pyrolysis process on shrinkage rate, ceramic yield and surface area of the SiOC aerogels could be ignored, while the variation in the amount of NH₄OH exerted a strong impact on the properties of SiOC aerogels. Increasing the amount of NH₄OH resulted in the decrease of bulk density and surface area of SiOC aerogels from 0.335 g/cm³ and 488 m²/g to 0.265 g/cm³ and 365 m²/g. The resultant SiOC aerogels exhibit high compressive strength (1.45–3.17 MPa). ²⁹Si MAS NMR spectra revealed the retention of Si-C bond in the SiOC aerogels after pyrolysis at 1000 °C. The present work demonstrates VTES/TEOS is a promising co-precursors to easily and low cost synthesize large size SiOC aerogel monolith.     

On the mechanical,thermophysical and dielectric properties of Nextel™ 440 fiber reinforced nitride matrix (N440/Nitride) composites

The Nextel? 440 fiber reinforced nitride matrix (N440/Nitride) composites were fabricated by precursor infiltration and pyrolysis (PIP) route. The results demonstrated that the original N440 fiber had a phase composition of amorphous SiO₂ and γ-Al₂O₃. Its single filament tensile strength was 3.03 GPa (at room temperature), while it dropped to 72.6% and 35.1% at 1200 °C and 1400 °C, respectively. The phase content of N440/Ntride composites was mainly γ-Al₂O₃ and amorphous BN, as well as mullite phase (formed at > 1100 °C). The composites owned a flexural strength up to 76.0 MPa at room temperature. The stair-stepping decrease in the load-displacement curve and fiber pull-outs in the fracture surface indicated a good fiber/matrix interface and toughness. By heating at 1400 °C, the composites still possessed 67.4% of original bending strength. It was found that the high temperatures caused strong fiber-matrix bonding and severe fiber degradation. The specific heat, CTE and thermal conductivity of the composites were 0.325–0.586 J g^?1 K^?1, (3.2–4.0) × 10^?6 K^?1 and 0.78–3.47 W m^?1 K^?1, respectively. The composites possessed a dielectric constant of 4.25–4.35 and loss tangent of 0.004–0.01 at 8–12 GHz. The good overall performances enabled the N440/Nitride composites advanced high-temperature wave-transparent applications.     

Electrochemical and thermal characterization of doped ceria electrolyte with lanthanum and zirconium

Nanocomposites electrolytes consisting of La³⁺ and Zr⁴⁺ doped with ceria labelled as La_0.2 Ce_0.8 O_2-δ (LDC), Zr_0.2Ce_0.8O_2-δ (ZDC) and Zr_0.2La_0.2Ce_0.6O_2-δ (ZLDC) have been synthesized via a co-precipitation route. DC conductivity was studied with a four-probe method in the range of temperature 450–650 °C and maximum conductivity was found to be 0.81 × 10^?2 S.cm^?1 (LDC) > 0.32 × 10^?2 S.cm^?1 (ZLDC) > 0.15 × 10^?2 S.cm^?1 (ZDC) at a temperature of 650 °C, respectively. Further, electric behavior of doped and co-doped ceria electrolytes was investigated by A.C electrochemical impedance spectroscopy (frequency range ~ 0.1 Hz?4 MHz). The phase/structural identification of the material prepared was studied using X-ray diffraction and found ceria to possess a cubic fluorite structure. Scanning electron microscopy (SEM) was carried out to study its morphology and particle size (~ 90–120 nm). Thermal behavior on its change in weight and length with the temperature were studied by thermogravimetric analysis (TGA) and dilatometry respectively. Furthermore, thermal expansion coefficients (TECs) of prepared electrolytes are calculated and found as follows: 13.4 × 10^?6 °C^?1, 13.6 × 10^?6 °C^?1and 15.3 × 10^?6 °C^?1 for LDC, ZDC and ZLDC, respectively, in the temperature range 150–1150 °C.     

(Al3+, Nb5+) co–doped CaCu3Ti4O12: An extended approach for acceptor–donor heteroatomic substitutions to achieve high–performance giant–dielectric permittivity

Substitution of (Al³⁺, Nb⁵⁺) co–dopants into TiO₆ octahedral sites of CaCu₃Ti₄O₁₂ ceramics, which were prepared by a solid state reaction method and sintered at 1090 °C for 18 h, can cause a great reduction in a low–frequency loss tangent (tanδ≈0.045–0.058) compared to those of Al³⁺ or Nb⁵⁺ single–doped CaCu₃Ti₄O₁₂. Notably, very high dielectric permittivities of 2.9 ? 4.1 × 10⁴ with good dielectric–temperature stability are achieved. The room–temperature grain boundary resistance (R_gb≈0.37–1.17 × 10⁹ Ω.cm) and related conduction activation energy (E_gb≈0.781–0.817 eV), as well as the non–Ohmic properties of the co–doped ceramics are greatly enhanced compared to single–doped ceramics (R_gb≈10⁴–10⁶ Ω cm and E_gb≈0.353–0.619 eV). The results show the importance of grain boundary properties for controlling the nonlinear–electrical and giant–dielectric properties of CaCu₃Ti₄O₁₂ ceramics, supporting the internal barrier layer capacitor model of Schottky barriers at grain boundaries.     

Improved electrical and thermal conductivities of polysiloxane-derived silicon oxycarbide ceramics by barium addition

The electrical and thermal conductivities of bulk barium-added silicon oxycarbide (SiOC-Ba) ceramics are investigated. The SiOC-Ba ceramics exhibited improved electrical and thermal conductivities upon increasing the sintering temperature from 1450 °C to 1650 °C. Precipitation of graphitic carbon clusters observed by Raman spectroscopy and high-resolution transmission electron microscopy is attributed to the phase separation during the fabrication process. The increase in the electrical conductivity can be rationalized in terms of an increase in the density of the sp² CC bonds within the carbon clusters. The increase in the thermal conductivity is mainly attributed to the formation of interconnected graphitic clusters in the SiOC matrix and SiC embedded in the clusters. The electrical and thermal conductivities of the SiOC-Ba ceramics sintered at 1650 °C are 14.0 Ω^?1 cm^?1 and 5.6 W/m K, respectively, at room temperature. The electrical conductivity of SiOC-Ba sintered at 1550 °C is 5.3 Ω^?1 cm^?1 and 7.0 Ω^?1 cm^?1 at 2 and 300 K, respectively.     

Influence of processing conditions in TEOS/PDMS derived silicon oxycarbide materials. Part 1: Microstructure and properties

Fully dense bulk silicon oxycarbide (SiOC) derived materials have been prepared using the conventional ceramic route. Tetraethylortosilicate/Polydimethylsiloxane (TEOS/PDMS) organic–inorganic hybrids were used as starting materials. These hybrids were thermal treated, attrition milled and pyrolyzed at 1100 °C. SiOC powders were shaped employing uniaxial and/or isostatic pressing and finally were sintered up to 1550 °C for 4, 8 and 16 h. Bulky defect free SiOC ceramics without porosity were obtained displaying enhanced both mechanical properties and oxidation resistance compared to silica glasses. These SiOC materials present maximum values of microindentation hardness and flexural strength of 11.7 GPa and 153 MPa, respectively, and a high oxidation resistance at 1550 °C for 100 h, a very low coefficient of thermal expansion of 1.35 × 10^?6 °C^?1, a high glass transition temperature of 1325 °C, and an electrical resistivity of 3.15 × 10⁵ Ω m.     

Structural,thermal, dielectric and ferroelectric properties of K0.5Bi0.5TiO3 ceramics

Dense K_0.5Bi_0.5TiO₃ (KBT) lead-free ceramics were prepared by conventional solid reaction route. Their temperature behavior (up to 600 °C) was investigated by X-ray diffraction, DSC, dielectric spectroscopy and electric field-polarization technique. The first temperature dependent Raman scattering studies were also performed. X-ray and Raman scattering results show that samples exhibit a single perovskite structure with cubic symmetry at temperatures higher than approximately 400 °C and with coexistence of the cubic and tetragonal phases below this temperature. Two structural phase transitions between tetragonal phases in temperature range 200–225 °C and between tetragonal and cubic ones near 400 °C are observed. The content of the tetragonal phase increases with decreasing temperature and at room temperature it reaches more than 70%. Temperature- dependent P-E loops and pyroelectric data revealed a polar behavior in KBT up to about 400 °C, which means that the intermediate phase (～270–380 °C) is rather ferroelectric than antiferroelectric.     

Separation and characterisation of fused alumina obtained from aluminium-chromium slag

Aluminium-chromium slag is a by-product of the thermal reduction of aluminium during chromium smelting, which is generally considered solid waste with a low utilisation rate. In this work, a fused carbonisation reduction method has been proposed to separate the Al₂O₃ and Cr₂O₃ from the slag and produce fused alumina and chromium carbide materials for refractory applications. The thermodynamic parameters of this process were determined using a standard thermal analysis method. In the molten slag, Cr₂O₃ reacts with C to produce high-density chromium carbide, which effectively precipitates at the bottom of the reaction vessel, while Al₂O₃ is converted into the corundum phase during cooling. The results of chemical analysis showed that the Al₂O₃ content in fused alumina was greater than 95 wt%, while its main crystalline phase was the corundum with a bulk density of 3.57 g cm^?3, thermal conductivity of 6.4–7.4 W m^?1 K^?1 (at temperatures above 600 °C), and average thermal expansion coefficient of about 7.5–8.2 × 10^?6/°C (in the temperature range of 800–1300 °C).     

Effect of SNNWS content on the microstructure and properties of SNNWS/Si-C-N ceramic composites via PIP

Si-C-N ceramic composites containing well distributed silicon nitride nanowires (SNNWs) were fabricated by die-pressing and precursor infiltration and pyrolysis process at a low temperature. The structure, composition, mechanical and thermophysical properties of the composites were investigated. The results show that the composites consisted of amorphous SiCN, α-Si₃N₄ and α-cristobaslite. The composites with different contents of SNNWs possessed a density of 2.02–2.07 g cm^?3 and open porosity of 7.9–9.9%. SNNWs can effectively restrain the contraction of matrix with a decrease by 25% in linear shrinkage. The composites with 3 wt% SNNWs owned the highest flexural strength (83.7 MPa) and elastic modulus (54.0 GPa) at room temperature, which increase by 13.2% and 62.3% respectively, compared with pure SiCN ceramics. The SNNWs displayed good reinforcement function at high temperature due to the fact that the composites with 7 wt% SNNWs had a 96.8% retention rate of bending strength at 1200 °C. The composites had relatively low coefficient of thermal expansion and thermal diffusivity which were less than 2.2 × 10^?6 K^?1 and 0.62 mm² s^?1, respectively.     

The effect of annealing on electrical properties of fluorinated amorphous carbon films

Fluorinated amorphous carbon (a–C:F) films have been deposited by electron cyclotron resonance chemical vapor deposition (ECR–CVD) at room temperature using C₄F₈ and CH₄ as precursor gases. The chemical compositions and electrical properties of a–C:F films have been studied by X-ray photoelectron spectroscopy (XPS), capacitance–voltage (C–V) and current-voltage (I–V) measurements. The results show that C–CF_x and C–C species of a–C:F films increase and fluorine content decreases after annealing. The dielectric constant of the annealed a–C:F films increases as a result of enhancement of film density and reduction of electronic polarization. The densities of fixed charges and interface states decrease from 1.6 × 10¹⁰ cm^− 2 and (5–9) × 10¹¹ eV^− 1 cm^− 2 to 3.2 × 10⁹ cm^− 2 and (4–6) × 10¹¹ eV^− 1 cm^− 2 respectively when a–C:F films are annealed at 300 °C. The magnitude of C–V hysteresis decreases due to reduced dangling bonds at the a–C:F/Si interfaces after heat treatment. The conduction of a–C:F films shows ohmic behavior at lower electric fields and is explained by Poole–Frankel (PF) mechanism at higher electric fields. The PF current increases indicative of reduced trap energy when a–C:F films are subjected to higher annealing temperatures.     

A novel aerogels/porous Si3N4 ceramics composite with high strength and improved thermal insulation property

A novel ZrO₂-SiO₂ aerogels/porous Si₃N₄ ceramics composite with high strength, low density, good dielectric properties and low thermal conductivity was synthesized by filling ZrO₂-SiO₂ aerogels into the porous Si₃N₄ ceramics through vacuum sol-impregnating. The effects of aerogels on the microstructure and properties of composite were discussed. The results show that aerogels could form a mesoporous structure and significantly decrease the thermal conductivity from 9.8 to 7.3 W m^?1 K^?1. Meanwhile, the density, mechanical and dielectric properties of the porous Si₃N₄ ceramics could not be affected after introducing ZrO₂-SiO₂ aerogels. The composite exhibits high porosity (62.6%), high flexural strength (53.86 MPa) and low dielectric constant (2.86). The ZrO₂-SiO₂ aerogels/porous Si₃N₄ ceramics composite shows great potential as radome materials applied in the fields of aerospace.     

Advanced visible-light photocatalytic property of biologically structured carbon/ceria hybrid multilayer membranes prepared by bamboo leaves

Biologically structured carbon/cerium dioxide materials are synthesized by biological templates. The microscopic morphology, structure and the effects of different oxidation temperatures on materials are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) ultraviolet-visible light spectrum (UV–Vis) and X-ray Photoelectron Spectroscopy (XPS). Moreover, by splitting water under visible light irradiation, the hydrogen production is measured to test the photocatalytic property of these materials. The results show that materials made with bamboo biological templates which are immersed in 0.1 mol L^?1 of cerium nitrate solution, then carbonizated in nitrogen (700 °C) and oxidized in air (500–600 °C), can obtain the biological structure of bamboo leaves. The product is in the composition of hybrid multilayer membrane, which one is carbon membrane form plant cell carbonation and another is ceria membrane by nanoparticle self assembly. The best oxidation temperature is 550 °C and the band gap of carbon/cerium dioxide materials synthesized at this optimum oxidation temperature could be reduced to 2.75 eV. After exposure to visible light for 6 h, the optimal hydrogen production is about 302 μmol g^?1, which is much higher than that of pure CeO₂.     

Electrical behavior of the Ruddlesden–Popper phase, (Nd0.9La0.1)2 Ni0.75Cu0.25O4 (NLNC) and NLNC- x wt% Sm0.2Ce0.8O1.9 (SDC) (x = 10, 30 and 50), as intermediate‐temperature solid oxide fuel cells cathode

In the present work, a new Ruddlesden-Popper phase, (Nd_0.9La_0.1)₂ Ni_0.75Cu_0.25O₄ (NLNC) has been synthesized by solid state reaction for intermediate-temperature solid oxide fuel cells (IT-SOFCs) applications. The effect of sintering temperature on the microstructure and electrical properties of the NLNC cathode material is investigated. Likewise, composite cathode materials were also prepared by mixing the NLNC with 10, 30 and 50 wt% of Sm_0.2Ce_0.8O_1.9 (SDC) powders, and firing in the temperature range of 1000–1300 °C. The crystal structure and chemical compatibility of NLNC and SDC, and their microstructures were studied by XRD and SEM, respectively. Electrical conductivity and performance of monolithic and composite electrodes as a function of the electrode composition is investigated experimentally through four probe method and electrochemical impedance spectroscopy (EIS). The results proved that no reaction occur between NLNC and SDC compounds even at a temperature as high as 1300 °C. Maximum total electrical conductivity of 114.36 S cm^?1 at 500 °C is recorded for the pure NLNC material sintered at 1300 °C. The polarization resistance of pure NLNC cathode was 0.43 Ω cm² at 800 °C; the NLNC–SDC composite cathodes including 10, 30 and 50 wt% SDC displayed Rp value of 0.27 Ω cm², 0.11 Ω cm², and 0.19 Ω cm² at 800 °C, respectively.     

Process-tolerant pressureless-sintered silicon carbide ceramics with alumina-yttria-calcia-strontia

Process-tolerant SiC ceramics were prepared by pressureless sintering at 1850–1950 °C for 2 h in an argon atmosphere with a new quaternary additive (Al₂O₃-Y₂O₃-CaO-SrO). The SiC ceramics can be sintered to a > 94% theoretical density at 1800–1950 °C by pressureless sintering. Toughened microstructures consisting of relatively large platelet grains and small equiaxed grains were obtained when SiC ceramics were sintered at 1850–1950 °C. The presently fabricated SiC ceramics showed little variability of the microstructure and mechanical properties with sintering within the temperature range of 1850–1950 °C, demonstrating process-tolerant behavior. The thermal conductivity of the SiC ceramics increased with increasing sintering temperature from 1800 °C to 1900 °C due to decreases of the lattice oxygen content of the SiC grains and residual porosity. The flexural strength, fracture toughness, and thermal conductivity of the SiC ceramics sintered at 1850–1950 °C were in the ranges of 444–457 MPa, 4.9–5.0 MPa m^1/2, and 76–82 Wm^?1 K^?1, respectively.     

Fabrication of dense Ce0.9Mg0.1P2O7-PmOn composites by microwave heating for application as electrolyte in intermediate-temperature fuel cells

In the present work, we report a method of fabrication of dense 10 mol% Mg²⁺-doped cerium pyrophosphate-phosphate (Ce_0.9Mg_0.1P₂O₇-P_mO_n; CMP-P) composites by microwave heat-treatment of the preformed Ce_0.9Mg_0.1P₂O₇ substrates in the presence of phosphoric acid. The composite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). The microwave heating at 375 °C for 5 min resulted in the formation of dense CMP-P composites which retained most of the pyrophosphate phase. The electrical conductivity was extracted from the EIS data and for the CMP-P composite prepared by H₃PO₄ loading for 10 h and microwave heat-treatment for 5 min it was found to be >10^?2 S m^?1 in 100–250 °C range with a maximum of 0.062 S cm^?1 at 190 °C, which was significant for its application as electrolyte in intermediate temperature fuel cells.     

High-pressure spark plasma sintering of silicon nitride with LiF additive

High-pressure spark plasma sintering of Si₃N₄ with Y₂O₃, Al₂O₃ and LiF additives was employed to fabricate high quality dense ceramics comprising approximately 92% α-Si₃N₄ phase and 8% β-Si₃N₄ phase. The relatively high pressure applied (up to 650 MPa) had a substantial effect on densification by enhancing particle rearrangement, making it possible to obtain dense Si₃N₄ at a significantly lower sintering temperature (1350 °C). Consequently, virtually no α to β phase transformation transpired during the liquid phase sintering process. The LiF additive had an indispensable influence on the densification process by lowering the viscous glass formation temperature, which also contributed to enhanced particle rearrangement. The nearly fully dense samples (theoretical density ≥99%) obtained displayed a good combination of mechanical properties, namely elastic modulus (304–316 GPa), hardness (1720–1780 HV2) and fracture toughness (6.0 MPa m^1/2).     

Optical properties of ferroelectric lanthanum lithium niobate

Fine structures (ferroelectric domains), ferroelectricity and Second Harmonic Generation results were found and studied as a function of laser linearly and circularly polarization dependent polarized excitations in ferroelectric stoichiometric La_0.05Li_0.85NbO₃ nanocrystals ceramic material. Scanning Electron Microscope images are taken as a comparison to Second Harmonic Generation intensity profiles revealed fine structures. By using laser polar measured response we are able to find the angle orientation from 0° to 90° angles of ferroelectric domains with highly good definition contrast obtained in blue/gray colors. It shows ferroelectric hysteresis loops at room temperature with a polarization saturation of (0.247 μC/cm²), remnant polarization of (0.15 μC/cm²) and coercitivity field of (1.31 kV/cm). X-ray Diffraction, Atomic Force Microscope, Raman spectroscopy and X-ray Photoelectron Spectroscopy, revealed well formed of ferroelectric ABO₃ perovskite crystal structure, piezoelectric image response indicate ferroelectric pattern domain structure, new vibrations modes on LaO₆, LiO₆ and NbO₆ octahedral sites and binding energies of electronic structure of La⁵⁷, Nb⁴¹, O⁸, Li³ from the surface of the ferroelectric stoichiometric La_0.05Li_0.85NbO₃ nanocrystals ceramic material, respectively.     

Field induced metastable ferroelectric phase in Pb0.97La0.03(Zr0.90Ti0.10)0.9925O3 ceramics

Pb_0.97La_0.03(Zr_0.9Ti_0.1)_0.9925O₃ (PLZT 3/90/10) ceramics prepared by solid-state reaction with the compositions near the antiferroelectric/ferroelectric (FE/AFE) phase boundary were studied. From the polarization–electric field P(E) dependence and ex situ X-ray study, an irreversible electric field induced AFE-to-FE phase transition is verified at room temperature. Dielectric and in situ temperature dependent X-ray analysis evidence that the phase transition sequence in PLZT 3/90/10-based ceramics can be readily altered by poling. A first order antiferroelectric-paraelectric (AFE-to-PE) transition occurred at?～190 °C in virgin sample and at?～180 °C in poled sample. In addition, a FE-to-AFE transition occurs in the poled ceramic at much lower temperatures (～120 °C) with respect to the Curie range (～190 °C). The temperature-induced FE-to-AFE transition is diffuse and takes place in a broad temperature range of 72–135 °C. The recovery of AFE is accompanied by an enhancement in the piezoelectric properties.     

Decomposition behavior of CaSO4 during potassium extraction from a potash feldspar-CaSO4 binary system by calcination

The extraction of potassium from a tablet mixture of K-feldspar ore and CaSO_4by roasting was studied with a focus on the effects of the decomposition behavior of CaSO_4on the potassium extraction process.The roasted slags were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),energy-dispersive X-ray spectroscopy,and thermogravimetric(TG)analysis.The XRD analysis revealed that hydrosoluble mischcrystal K_2Ca_2(SO_4)_3was obtained by ion exchange of Ca~(2+)in CaSO_4and K~+in KAlSi_3O_8.Meanwhile,the intermediate product,SiO_2,separated from KAl Si_3O_8and reacted with CaSO_4to decompose CaSO_4.The SEM results showed that some blowholes emerged on the surface of the CaSO_4particles when they reacted with SiO_2at 1200°C,which indicates that SO_2and O_2gases were released from CaSO_4.The TG curves displayed that pure CaSO_4could not be decomposed below 1200°C,while the mixture of K-feldspar ore and CaSO_4began to lose weight at 1000°C.The extraction rate of potassium and decomposition rate of CaSO_4were 62%and 44%,respectively,at a mass ratio of CaSO_4to K-feldspar ore of 3:1,temperature of 1200°C,tablet-forming pressure of6 MPa,and roasting time of 2 h.The decomposition of CaSO_4reduced the potassium extraction rate;therefore,the required amount of CaSO_4was more than the theoretical amount.However,excess CaSO_4was also undesirable for the potassium extraction reaction because a massive amount of SO_2and O_2gas were derived from the decomposition of CaSO_4,which provided poor contact between the reactants.The SO_2released from CaSO_4decomposition can be effectively recycled.