Micromechanical properties and microstructural evolution of Amosic-3 SiC/SiC composites irradiated by silicon ions

In this work, Amosic-3 SiC/SiC composites were irradiated to 10 dpa and 115 dpa with 300 keV Si ions at 300 °C. To evaluate its irradiation behaviour and investigate the underlying mechanism, nanoindentation, AFM, Raman and electron microscopy were utilized. Nanoindentation showed that although micromechanical properties declined after irradiation, hardness and Young’s modulus were maintained better under 115 dpa. AFM manifested differential swelling among PyC interface, fiber and matrix and SEM showed irradiation-induced partial interface debonding, which are both more obvious under 115 dpa. TEM revealed the generation and proliferation of amorphous regions, which is according with the decline and broadening of peaks in Raman spectra. The material was almost completely amorphous after irradiated to 10 dpa while recrystallization occurred under 115 dpa. All results mentioned above contribute to the decline of hardness and Young’s modulus and may explain why the micromechanical degradation was more significant under 10 dpa.     

Microstructure response of Amosic-3 SiC/SiC composites under self-ion irradiation

Amosic-3 SiC/SiC composites were irradiated at 300 °C using 6 MeV Si ions to peak doses of 13 and 55 displacements per atom (dpa). The loss of amorphous carbon packets and the growth of SiC grains were simultaneously observed in Amosic-3 SiC fibers, using a combination of transmission electron microscopy (TEM) and Raman spectroscopy. A mechanism based on the grain growth theory was proposed to expound the relationship between the loss of carbon packets and the growth of SiC grains. Small and curved SiC grains can absorb surrounding carbon packets to grow themselves; at some point, these grains further grow at the expense of adjacent small SiC grains until their grain boundary became straight. TEM images were found to support the above mechanism.     

Structural characterization of exfoliated graphite nanofibers

Structural characterization of exfoliated graphite nanofibers (EGNFs) with transmission electron microscopy (TEM) and high-angle annular dark-field-scanning TEM (HAADF-STEM) indicates exfoliation has led to structural expansion along the fiber axis, with discrete domains of graphitic nanocones separated by gaps ranging from 50 to 500 Å. Image contrast in HAADF-STEM demonstrates that structural expansion dominates over chemical etching. Raman spectroscopy indicates the EGNF is more graphitic than the precursor, and the disappearance of the characteristic defect (D) peak with multi-wavelength excitation is inconsistent with the presence of amorphous carbon. The highly expanded EGNF structure oxidizes at two distinct rates at 750 °C in CO₂, leading to a highly-disordered graphitic fiber, with apparent collapse of the expanded structure as no gaps or discrete graphitic domains are observed after oxidation. Variation in the heat input per intercalant mass during thermal shock leads to changes in fiber morphology, including the extent of fiber expansion, the number of defects and pores observable within the fiber via TEM, and the surface area measured by nitrogen adsorption.     

Microstructures formed by secondary growth of fired ZSM-5 seed crystals

Oriented ZSM-5 seed crystals on an α-Al₂O₃ porous substrate were hydrothermally treated in a raw sol. The ZSM-5 membranes were fabricated via secondary growth of the seed crystals. For some samples, the seed-applied substrate was fired at 300 or 600 °C before the secondary growth in order to enhance adhesion between the substrate and the seed crystals. The influence of the firing on the subsequent secondary growth of the seed crystals was examined by XRD, SEM, and TEM. The TEM images of the sample fired at 300 °C showed that the resulting membrane was continuous, and in the membrane, large ZSM-5 particles were distributed in a porous matrix. The ZSM-5 particles were slightly smaller than the used seed crystals. HR-TEM observations showed that the porous matrix is comprised of ZSM-5 micro-crystals, and the part adjacent to the large ZSM-5 crystals has the same crystallographic orientation as the large crystals. The TEM images of the sample fired at 600 °C showed that the resulting layer is comprised of particles with a core-shell structure. The core consisted of ZSM-5 micro-crystals, whereas the shell was composed of large ZSM-5 rod-like crystals. It is inferred that the formation of these interesting microstructures is related to the degradation of the template agent, NPr₄OH, in the seed crystals by firing at 300 and 600 °C. The part including no template is dissolved by a hydrothermal treatment, and the dissolved species is re-crystallized via reaction with a template agent in the used raw sol, resulting in the formation of interesting microstructures.     

Microstructure and mechanical properties of WC–C nanocomposite films

WC–C nanocomposite film was prepared by using a hybrid deposition system of r.f.-PACVD and DC magnetron sputtering. W concentration in the film was varied from 5.2 to 42 at.% by changing the CH₄ fraction of the mixture sputtering gas of Ar and CH₄. Hardness, residual compressive stress and electrical resistivity were characterized as a function of W concentration. Raman spectroscopy, XRD and high resolution TEM were employed to analyze the structural change in the film for various W concentrations. In the present W concentration range, the film was composed of nano-sized WC particles of diameter less than 5 nm and hydrogenated amorphous carbon matrix. Content of the WC particles increased with increasing W concentration. However, the mechanical properties of the film increased only when the W concentration was higher than 13 at.%. Structural analysis and electrical conductance measurements evidently showed that the increase in hardness and residual stress occurred as the WC particles were in contact with each other in the amorphous carbon matrix.     

V掺杂TiO2纳米粒子的制备及其光催化研究

溶胶-凝胶法制备5at.％V掺杂的TiO2和纯TiO2,然后在500℃煅烧6 h。 XRD谱图显示,样品均是锐钛矿型TiO2,还有一些无定型成分,平均晶粒大小分别为6.8 nm和9.7 nm。 TEM照片显示的纳米粒子大小分别在8.0-18.7 nm和21.6-30.2 nm范围内,比XRD计算结果大,这是因为样品未能充分分散所造成。 EDS谱图显示V的掺杂量是6.5at.％,红外光谱也证实V元素的存在。拉曼光谱表明, V元素均匀地分散在TiO2中。 Rh. B的光催化降解实验表明, V掺杂TiO2的光催化效率比纯TiO2低,这是由于较高的掺杂浓度导致电子-空穴复合中心增加,从而降低光催化效率。     

TiO_2纳米管的制备与表征

用化学处理法制备TiO2纳米管时,溶液的温度应大于80℃,碱液浓度应控制在8～12mol/L,反应时间为8～24h。通过TEM、XRD、FT-IR、Raman光谱和BET、GT-DTA等技术对TiO2纳米管进行了表征,结果发现:TiO2纳米管都是长约300～500nm的直管,有的是双层管,有的是多层管。TiO2纳米管为无定型结构。400℃煅烧后,TiO2纳米管的管状结构被破坏,变为锐钛矿型的实心结构。当TiO2由粉体形成TiO2纳米管后,TiO2的Ti—O键的振动特性发生改变。合成的TiO2纳米管具有很大的比表面积(403 7900m2/g)和孔体积(0 6740cm3/g)。     

Hydrothermal synthesis of silicon oxide clad uranium oxide nanowires

A facile method to synthesize silicon oxide clad uranium oxide nanowires is presented. U₃Si₂, used as a precursor, was oxidized to produce uranium oxide nanocrystallites and amorphous silicon oxide under hydrothermal conditions at 300°C and a pressure of 7.8 × 10⁶ Pa. The growth of uranium oxide nanowires was assisted by silicon oxide via assembling the uranium oxide nanocrystallites in an amorphous silicon oxide matrix. The microstructure and composition of silicon oxide clad uranium oxide nanowires were characterized by XRD, SEM, TEM, and EDS. The uranium oxide in the nanowires was determined as UO_2.34 with a fluoride cubic structure.     

Improvement of oxidation resistance of unidirectional Cf/SiO2 composites by the addition of SiCp

Unidirectional carbon fiber reinforced fused silica composites (uni-C_f/SiO₂) with addition of different contents of SiC particle (SiC_p) were prepared by slurry infiltrating and hot-pressing. The model of oxygen infiltrating into the composite was supposed according to the characterization of fiber/matrix interface observed by transmission electronic microscope (TEM). The oxidation process of the composite was analyzed by thermo-gravimetry and differential scanning calorimeter (TG-DSC) method and the oxidation resistance was evaluated by the residual flexural strength and the fracture surface of the composite after heat treatment at elevated temperatures method. The results showed that the oxidation of carbon fiber started at 480 °C and ended at 800 °C and the oxidation of SiC_p started at above 1000 °C in the composite. The addition of 20 wt.% SiC_p had a better oxidation resistance. According to the characterization of fiber/matrix interface observed by TEM, gaps existed at the fiber/matrix interface which resulted from the CTE mismatch of carbon fiber and SiO₂ matrix. While the CTE mismatch between SiC_p and SiO₂ matrix could also result in the pre-existing gaps in the matrix. The oxygen penetrated along the gaps and simultaneously reacted with carbon fiber ends and SiC_p, which filled the gaps at the fiber/matrix interface and the pre-existing gaps in the matrix and subsequently prevented oxygen from infiltrating inward.     

Raman/Cr3+ fluorescence mapping of a melt-grown Al2O3/GdAlO3 eutectic

The paper reports on the Raman/fluorescence study of a melt-grown Al₂O₃/GdAlO₃ eutectic composite. Raman bands from the α-alumina and gadolinium perovskite phases identified by X-ray diffraction were systematically observed together in the optically visible domains, even when the latter were much larger than the Raman probe. This suggests a more complex interlocking pattern than appearing on SEM or optical microscopy images. The polarization of alumina and GdAlO₃ Raman bands evidenced the preferential orientation of Al₂O₃ phase with respect to the sample growth direction, in agreement with TEM results. In addition, the position of chromium impurity fluorescence bands was used to map the residual stress in alumina phase. It is a compression in the 200–300 MPa range.     

A comprehensive study on the influence of the polyorganosilazane chemistry and material shape on the high temperature behavior of titanium nitride/silicon nitride nanocomposites

The high temperature crystallization behavior of polytitanosilazane-derived amorphous SiTiN ceramics was investigated in a nitrogen atmosphere using XRD, Raman spectroscopy, TEM, SEM and BET. At 1400 °C, TiN is the first phase to nucleate in SiTiN ceramics forming nanocomposites with a homogeneous distribution of TiN nanocrystals within an amorphous Si₃N₄ matrix. Above 1400 °C, XRD indicates that the temperature at which Si₃N₄ crystallizes depends on the volume fraction of TiN present in nanocomposites. This is closely related to the chemistry of the polyorganosilazanes used to synthesize polytitanosilazanes. The use of perhydridopolysilazane, the most reactive polyorganosilazane, allows preparing TiN/Si₃N₄ nanocomposites with a remarkable stability of the amorphous matrix up to 1800 °C as mesoporous materials and powders. Dense monoliths crystallize earlier than the powder analogs because of the use of an ammonia pre-treatment before polymer warm-pressing.     

Synthesizing and Comparing the Photocatalytic Properties of High Surface Area Rutile and Anatase Titania Nanoparticles

Rutile titania nanocrystalline particles with high specific surface areas were directly prepared by thermal hydrolysis of titanium tetrachloride aqueous solution. The as-prepared rutile titania powder was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer–Emmett–Teller surface area analysis, and Fourier transform Raman and IR spectroscopies. Neither anatase nor amorphous titania could be detected in this titania powder by XRD, Raman spectroscopy, and high-resolution TEM. In the phenol degradation reaction, the rutile titania powder with an initial crystalline size of 7 nm was found to have higher photocatalytic activity than that of anatase titania with the same specific surface area. The rutile titania powders calcined at 300° and 450°C also showed a relatively high photocatalytic property. The high activity of the as-prepared rutile titania was attributed to the abundance of hydroxy groups in the powder, as was proven by thermogravimetric analysis data, which provided more active sites for the degradation reaction.     

Synthesis and temperature-dependent evolution of the phase composition in palladium-containing silicon oxycarbide ceramics

Palladium-containing silicon oxycarbide (SiPdOC) ceramics were synthesized using polymethylsilsesquioxane modified with palladium acetate as a single-source precursor. Thus, pyrolysis in argon at 1100 °C led to nanocomposites consisting of Pd₂Si nanocrystallites dispersed in an amorphous SiOC matrix. Exposure of SiPdOC to higher temperatures resulted in the precipitation of PdSi in addition to Pd₂Si. The temperature-dependent evolution of the phase composition and microstructure in SiPdOC were analyzed using XRD and TEM respectively and rationalized by a ThermoCalc-based thermodynamic assessment showing the feasibility of the possible reactions. The formation of PdSi was perceived because of the shift in the Pd-Si atomic composition towards the higher Si side, caused by the diffusion of Si present in the matrix into the Pd-Si melt, formed upon the heat-treatment above the melting point (1390 °C) of Pd₂Si. Further, Raman spectroscopic investigation indicated that Pd catalytically enhanced the graphitization of the free carbon in SiPdOC ceramics.     

Lanthanum cobaltite nanoparticles using the polymeric precursor method

The present study reports the evolution of reactive lanthanum cobaltite nanoparticles obtained by a polymeric precursor route, using citric acid as chelating agent. The crystallization from amorphous precursor, particle growth and the formation of nanoparticle agglomerates at different calcination temperatures was carried out by conventional and high-resolution electron microscopy, electron diffraction and energy-dispersive X-ray analysis and Raman spectroscopy. Microstructure measurements were compared with X-ray diffraction and chemical analysis results. Electron diffraction, combined with TEM, was used to determine the proportion of amorphous phase. The presence of amorphous carbon during the decomposition of the amorphous precursor was analyzed by Raman spectroscopy. The coherent crystalline domain size and the particle size have been monitored by XRD and electron microscopy in order to determine the evolution of both crystal size and the temperature onset for the formation of polycrystalline aggregates.The results demonstrate that at 550 °C we obtain pure single-phase equiaxed nanopowders of LaCoO₃ with crystal size of 20 nm, free of amorphous carbon and without the presence of polycrystalline aggregates.     

Influence of sintering temperature on the morphology of ceramic hollow fibers prepared from niobium pentoxide

Ceramic hollow fibers were prepared by the phase inversion and sintering method using niobium pentoxide (Nb₂O₅) as an innovative starting material. X-ray diffraction and Raman analyses revealed the same monoclinic crystalline phase for the ceramic material, H-Nb₂O₅, at all the evaluated sintering temperatures. According to SEM images, the starting material was composed of polydisperse particles of irregular size and shape with sizes ranging from 12.5 to 89.7 μm. The increase in the sintering temperature caused particles agglomeration. In the hollow fiber precursor (without sintering), Nb₂O₅ grains were surrounded by the coagulated polymer. The polymeric phase was eliminated when the fibers were sintered at temperatures above 600°C. When sintered at 1350°C, the outer surface of the fiber presented elongated crystals of well-defined shape, while agglomerated round shape grains were observed at the inner surface of the fiber. Formation of these elongated crystals was probable due to the material sintering at high temperatures (up to 1350°C) for more than 300 minutes. This study demonstrated the potential for general applicability of niobium pentoxide to fabricate ceramic hollow fiber membranes.     

A novel 3D network nanostructure constructed by single-crystal nanosheets of B4C

Three-dimensional (3D) network nanostructure boron carbide was successfully synthesized via the carbothermic method. The carbon source and template was carbonized bacterial cellulose (CBC) with a 3D network nanostructure, and the boron source was B₂O₃ and amorphous B powder. X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and X-ray photoelectron spectra (XPS) were used to study the morphology and structure of the samples. XRD and Raman spectra confirm that they belong to the B₄C crystalline phase. The FESEM images show that the synthetic B₄C retains the 3D network nanostructure of the template CBC well and consists of B₄C nanosheets with an average thickness of less than 100 nm. The analytical results of high-resolution TEM (HRTEM) and Selected Area Electron Diffraction (SAED) indicate that the B₄C takes the shape of hexagonal single crystals with a rhombohedral structure. These B₄C single crystal nanosheets alternate, forming the 3D network nanostructure. The mechanism of formation can be accounted for by in situ reduction reactions along the carbon nanofibers of CBC.     

Nanostructured Sn–Ti–C composite anodes for lithium ion batteries

Nanostructured Sn–Ti–C composites have been synthesized by a facile, inexpensive high energy mechanical milling process and investigated as an anode material for lithium-ion cells. Characterization data collected with X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) reveal an uniform dispersion of Sn nanoparticles within the conductive, amorphous (or poorly crystalline) TiC + C matrix. Among the three Sn–Ti–C compositions investigated, the Sn₁₁Ti₃₁C₅₈ composite exhibits the best electrochemical performance, with a capacity of ∼370 mAh/g and excellent capacity retention over 300 cycles studied. It also exhibits excellent cycle life with LiMn₂O₄ spinel cathode, suggesting a tolerance of the Sn–Ti–C anodes toward poisoning by the manganese leached out from the spinel cathode. The superior electrochemical performance of Sn₁₁Ti₃₁C₅₈ composite is attributed to a homogeneous distribution of the electrochemically active amorphous Sn, suppression of Sn grain growth, and the mechanical buffering effect provided by the conductive TiC + C matrix toward the volume expansion-contraction occurring during cycling.     

氮化镓纳米纤维的静电纺制备及光催化性能研究

以聚乙烯吡咯烷酮(PVP)和Ga(NO3)3为前驱体,利用静电纺丝和热处理技术制备了直径在100～300 nm左右的单斜结构的Ga2O3纳米纤维,并通过氨气氮化技术制备了GaN纳米纤维。XRD结果表明GaN样品为六方纤锌矿结构,且最佳氮化温度为850℃,氮化时间为2 h。Raman光谱发生了红移,并再次确定了GaN样品的结构,TGA结果表明GaN纤维在700℃以下在空气和氮气气氛下具有较好的稳定性,SEM和TEM表明纤维直径大约在100～200 nm之间,光催化测试表明GaN纤维对罗丹明6G有很好的降解效果。     

Structure of heat-treated Nylon 6 and 6.6 fibers. I. The shrinkage mechanism

Nylon 6 and 6.6 fibers were submitted to thermal annealing in a wide range of temperatures (below and above their glass transition temperatures) under inert atmosphere and slack condition, allowing free shrinkage. The structural changes due to the heat settings were analyzed by several techniques (differential scanning calorimetry analysis, wide- and small-angle X-ray scattering, and birefringence). The results revealed different recrystallization responses of the fibers to the applied thermal annealings and consequently different shrinkage mechanisms. In the recrystallization of the Nylon 6 fibers were involved a generation of nuclei crystallites in the interfibrillar regions, as well as growth and perfection of these new crystallites and preexisting ones. But, recrystallization of the Nylon 6.6 fiber was accompanied only by growth and perfection of the preexisting crystals. The existence of the nuclei crystallites at temperatures of heat treatments above 120°C was the major commanding factor for the Nylon 6 fiber to undergo less shrinkage than the Nylon 6.6 fiber. These very tiny crystallites worked as crosslinking points that would impose restrictions in the mobility of the chains segments, inhibiting subsequent disorientation of the amorphous regions and consequently intense shrinkage, thus resulting in recrystallization in a preferred direction of the fiber axis. The Nylon 6.6 fiber experienced an instantaneous shrinkage at the annealing temperature around 70°C. That was the temperature necessary to release its hydrogen bonds and the starting temperature for presenting its major structural changes, including global disorientation of the amorphous and crystalline regions. Thus, its recrystallization occurred with no preferred orientation. Also, it was suggested that the occurrence of so different shrinkage mechanisms reside in the different crystalline morphology that these fibers originally possessed before the heat treatments. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 441–452, 1998     

In-situ TEM investigations on the microstructural evolution of SiC fibers under ion irradiation: Amorphization and grain growth

SiC/SiC composites are attractive candidates for many nuclear systems. As reinforcements, SiC fibers are critical to the in-service performance of composites. In this work, the temperature effects on the irradiation-induced microstructural evolution of Cansas-III SiC fibers were investigated using in-situ transmission electron microscopy (TEM). With in-situ 800 keV Kr ion irradiation, at room temperature (RT) the SiC fiber experienced heterogeneous amorphization and became completely amorphous at ～2.6 dpa. Above the critical temperature of crystalline-to-amorphous (T_c), SiC fibers underwent a simultaneous process of carbon packet disappearance and nano-grain growth at 300 °C and 800 °C. Possible mechanisms were discussed.