碳化硼加入量对氧化镁-氮化硅铁浇注料力学性能的影响

以97烧结镁砂为主要原料,加入3%质量分数的氮化硅铁细粉,以硅微粉作为结合剂,研究了外加不同量碳化硼(其质量分数分别为0、0.1%、0.2%、0.3%、0.4%、0.5%)对镁质浇注料常温物理性能和高温力学性能的影响,并借助扫描电镜对浇注料的显微结构进行了分析。结果表明:随着碳化硼加入量的增加,浇注料烘干强度下降,中、高温处理后强度变大,高温抗折强度下降。原因在于碳化硼在加热过程中氧化产生液相,促进材料烧结,使得材料致密,冷态强度增大;而由于液相的产生降低了镁质材料的直接结合程度,使得高温抗折强度减小。     

Structural and electronic properties of poly(3-thiophen-3-yl-acrylic acid)

This work presents a combined theoretical and experimental study of poly(3-thiophene-3-yl acrylic acid), a new polythiophene derivative soluble in polar solvents. Quantum chemical calculations on small oligomers were performed to propose a structural model for this polymer. Specifically, the minimum energy conformations and the rotational profiles of the different isomeric derivatives constructed for a model system formed by two monomeric units were calculated. The resulting model, which shows head-to-tail polymer linkages and the acrylic acid side group arranged in trans-conformation, were used to predict the π-π^∗ lowest transition energy of an infinite polymer chain. On the other hand, the polymer was prepared by chemical oxidative coupling using anhydrous ferric chloride and subsequent alkaline hydrolysis. The synthetized material, which is soluble in aqueous base and acetone solutions, was characterized by FTIR, ¹H NMR and UV-vis experiments. Both the structural information and electronic properties derived from such experiments are fully consistent with the theoretical model obtained using quantum mechanical calculations.     

Effects of interface bonding properties on cyclic tensile behavior of unidirectional C/Si3N4 and SiC/Si3N4 composites

In this paper, the effect of fiber/matrix interface bonding properties on the cyclic loading/unloading tensile stress?strain hysteresis loops of 2 different ceramic‐matrix composites (CMCs), ie, C/Si₃N₄ and SiC/Si₃N₄, has been investigated using micromechanical approach. The relationships between the damage mechanisms (ie, matrix multicracking saturation, fiber/matrix interface debonding and fibers failure), hysteresis dissipated energy and internal frictional damage parameter have been established. The damage evolution processes under cyclic loading/unloading tensile of C/Si₃N₄ and SiC/Si₃N₄ composites corresponding to different fiber/matrix interface bonding properties have been analyzed through damage models and interface frictional damage parameter. For the C/Si₃N₄ composite with the weakest fiber/matrix interface bonding, the composite possesses the lowest tensile strength and the highest failure strain; the hysteresis dissipated energy increases at low peak stress, and the stress?strain hysteresis loops correspond to the interface partially and completely debonding. However, for the SiC/Si₃N₄ composite with weak interface bonding, the composite possesses the highest tensile strength and intermediate failure strain; and the hysteresis dissipated energy increases faster and approaches to a higher value than that of composite with the strong interface bonding.     

Preparation and mechanical properties of Si3N4 nanocomposites reinforced by Si3N4@rGO particles

A new type of reduced graphene oxide-encapsulated silicon nitride (Si₃N₄@rGO) particle was synthesized via an electrostatic interaction between amino-functionalized Si₃N₄ particles and graphene oxide (GO). Subsequently, the Si₃N₄@rGO particles were incorporated into a Si₃N₄ matrix as a reinforcing phase to prepare nanocomposites, and their influence on the microstructure and mechanical properties of the Si₃N₄ ceramics was investigated in detail. The microstructure analysis showed that the rGO sheets were uniformly distributed throughout the matrix and firmly bonded to the Si₃N₄ grains to form a three-dimensional carbon network structure. This unique structure effectively increased the contact area and load transfer efficiency between the rGO sheets and the matrix, which in turn had a significant impact on the mechanical properties of the nanocomposites. The results showed that the nanocomposites with 2.25 wt.% rGO sheets exhibited mechanical properties that were superior to monolithic Si₃N₄; the flexural strength increased by 83.5% and reached a maximum value of 1116.4 MPa, and the fracture toughness increased by 67.7% to 10.35 MPa·m^1/2.     

B_4C外加量对Al_2O_3-SiC-Si_3N_4铁沟浇注料性能的影响

研究了B4C外加量(外加质量分数为0~0.6%)对Al2O3-SiC-Si3N4铁沟浇注料常温物理性能和高温抗折强度的影响。用X射线衍射仪、扫描电镜和能谱仪测定了试样的物相组成和显微结构。结果表明:随着B4C加入量的增大,浇注料体积密度和常温强度先增大后减小,显气孔率先减小后增大,高温抗折强度先增大后减小;B4C外加质量分数为0.4%时,浇注料综合性能达到最佳。B4C在材料中的作用主要是促进烧结和防氧化。与未添加B4C试样相比,添加B4C的试样中生成了更多纤维状的O’-SiAlON,且长径比更大。O’-SiAlON的生长机制推断为气-固机制。     

Research progress on modification strategy of g-C3N4 and g-C3N4/Ti3C2 heterojunction

Graphite phase carbon nitride (g-C₃N₄) is a kind of metal-free semiconductor material with a forbidden band width of about 2.7 eV and has visible light response capability. Attributed to its good thermal and chemical stability, adjustable morphology and chemical structure, it is widely used in the field of photocatalysis. However, due to its low specific surface area and wide band gap, its response range to visible light is narrow and the recombination rate of photogenerated carriers is high, resulting in a low photocatalytic efficiency, which can be effectively improved by modification. The two-dimensional material Ti₃C₂ has a narrower band gap compared with other semiconductor materials, and the heterogeneous junction between Ti₃C₂ and g-C₃N₄ is expected to obtain a wider range of visible light absorption and higher photocatalytic efficiency. This article reviews the modification methods of g-C₃N₄ including morphology control, doping and constructing heterojunctions, as well as the action mechanism, preparation methods and applications of g-C₃N₄/Ti₃C₂ heterojunction in photocatalytic hydrogen evolution, organics degradation and synthesis, etc.     

g-C3N4的改性策略以及g-C3N4/Ti3C2异质结研究进展

石墨相氮化碳（g-C₃N₄）禁带宽度约为2.7 eV,具有可见光响应能力。由于其良好的热和化学稳定性,且形貌和化学结构可调,在光催化领域应用广泛。但由于其带隙宽,对可见光响应范围窄,且光生载流子的复合率高,导致其光催化效率低,可通过改性来改善。本文综述了对g-C₃N₄形貌调控、掺杂和构建异质结等改性策略,以及g-C₃N₄/Ti₃C₂异质结的作用机理、制备方法和在光催化析氢、有机物降解及合成等领域的应用。     

Microstructure and mechanical properties of Si3N4f/Si3N4 composites with different coatings

The Si₃N₄ coating and Si₃N₄ coating with Si₃N₄ whiskers as reinforcement (Si₃N_4w-Si₃N₄) were prepared by chemical vapor deposition (CVD) on two-dimensional silicon nitride fiber reinforced silicon nitride ceramic matrix composites (2D Si₃N_4f/Si₃N₄ composites). The effects of process parameters of as-prepared coating including the preparation temperature and volume fraction of Si₃N_4w on the microstructure and mechanical properties of the composites were investigated. Compared with Si₃N₄ coating, Si₃N_4w-Si₃N₄ coating shows more significant effect on the strength and toughness of the composites, and both strengthening and toughening mechanism were analyzed.     

Structural and electronic properties of bilayer and trilayer graphdiyne

Stimulated by the recent experimental synthesis of a new layered carbon allotrope-graphdiyne film, we provide the first systematic ab initio investigation of the structural and electronic properties of bilayer and trilayer graphdiyne and explore the possibility of tuning the energy gap via a homogeneous perpendicular electric field. Our results show that the most stable bilayer and trilayer graphdiyne both have their hexagonal carbon rings stacked in a Bernal way (AB and ABA style configuration, respectively). Bilayer graphdiyne with the most and the second most stable stacking arrangements have direct bandgaps of 0.35 eV and 0.14 eV, respectively; trilayer graphdiyne with stable stacking styles have bandgaps of 0.18-0.33 eV. The bandgaps of the semiconducting bilayer and trilayer graphdiyne generally decrease with increasing external vertical electric field, irrespective of the stacking style. Therefore, the possibility of tuning the electronic structure and optical absorption of bilayer and trilayer graphdiyne with an external electric field is suggested.     

Structural and electronic properties of Eu- and Pd-doped ZnO

Doping ZnO with rare earth and 4d transition elements is a popular technique to manipulate the optical properties of ZnO systems. These systems may also possess intrinsic ferromagnetism due to their magnetic moment borne on 4f and 4d electrons. In this work, the structural, electronic, and magnetic properties of Eu- and Pd-doped ZnO were investigated by the ab initio density functional theory methods based on generalized gradient approximation. The relative stability of incorporation sites of the doped elements in the ZnO host lattice was studied. The ground state properties, equilibrium bond lengths, and band structures of both the ZnO:Eu and ZnO:Pd systems were also investigated. The total and partial densities of electron states were also determined for both systems. It was found that in the ZnO:Eu system, ambient ferromagnetism can be induced by introducing Zn interstitial which leads to a carrier-mediated ferromagnetism while the ZnO:Pd system possesses no ferromagnetism.PACS 31.15.E-, 75.50.Pp, 75.30Hx.     

立方C3N4陶瓷第一性原理的计算

本文采用第一性原理的密度泛函理论平面波赝势法,通过广义梯度近似电子结构计算对立方C3N4进行了研究,结果表明立方C3N4属于间接能隙的半导体,带宽为2.92eV,C和N的电荷分别为0.44和-0.33,键长为0.14771nm,此外,吸收长波限值为147nm,静态介电常数为4.6。通过计算揭示了立方C3N4不仅有较高的硬度、良好的化学稳定性,而且具有较强的红外线穿透性,对材料在耐磨方面及光学领域的应用具有一定的指导意义。     

β-Si3N4对MgO-C砖高温性能的影响

研究了β-Si3N4对镁碳砖高温性能的影响及其作用机理.研究表明由于β-Si3 N4呈针状结构,热膨胀系数低,对多数熔渣和金属的润湿性小,加入β-Si3N4的镁碳砖,其高温抗折强度提高,热膨胀率降低,抗渣侵蚀性提高;另外,在反应层与原砖层之间发现有富硅层形成,这有利于抑制石墨和氮化硅的氧化以及渣的渗透.     

The electronic properties of superatom states of hollow molecules

Electronic and optical properties of molecules and molecular solids are traditionally considered from the perspective of the frontier orbitals and their intermolecular interactions. How molecules condense into crystalline solids, however, is mainly attributed to the long-range polarization interaction. In this Account, we show that long-range polarization also introduces a distinctive set of diffuse molecular electronic states, which in quantum structures or solids can combine into nearly-free-electron (NFE) bands. These NFE properties, which are usually associated with good metals, are vividly evident in sp(2) hybridized carbon materials, specifically graphene and its derivatives. The polarization interaction is primarily manifested in the screening of an external charge at a solid/vacuum interface. It is responsible for the universal image potential and the associated unoccupied image potential (IP) states, which are observed even at the He liquid/vacuum interface. The molecular electronic properties that we describe are derived from the IP states of graphene, which float above and below the molecular plane and undergo free motion parallel to it. Rolling or wrapping a graphene sheet into a nanotube or a fullerene transforms the IP states into diffuse atom-like orbitals that are bound primarily to hollow molecular cores, rather than the component atoms. Therefore, we named them the superatom molecular orbitals (SAMOs). Like the excitonic states of semiconductor nanostructures or the plasmonic resonances of metallic nanoparticles, SAMOs of fullerene molecules, separated by their van der Waals distance, can combine to form diatomic molecule-like orbitals of C(60) dimers. For larger aggregates, they form NFE bands of superatomic quantum structures and solids. The overlap of the diffuse SAMO wavefunctions in van der Waals solids provides a different paradigm for band formation than the valence or conduction bands formed by interaction of the more tightly bound, directional highest occupied molecular orbitals (HOMOs) or the lowest unoccupied molecular orbitals (LUMOs). Therefore, SAMO wavefunctions provide insights into the design of molecular materials with potentially superior properties for electronics. Physicists and chemists have thought of fullerenes as atom-like building blocks of electronic materials, and superatom properties have been attributed to other elemental gas-phase clusters based on their size-dependent electronic structure and reactivity. Only in the case of fullerenes, however, do the superatom properties survive as delocalized electronic bands even in the condensed phase. We emphasize, however, that the superatom states and their bands are usually unoccupied and therefore do not contribute to intermolecular bonding. Instead, their significance lies in the electronic properties they confer when electrons are introduced, such as when they are excited optically or probed by the atomically sharp tip of a scanning tunneling microscope. We describe the IP states of graphene as the primary manifestation of the universal polarization response of a molecular sheet and how these states in turn define the NFE properties of materials derived from graphene, such as graphite, fullerenes, and nanotubes. Through low-temperature scanning tunneling microscopy (LT-STM), time-resolved two-photon photoemission spectroscopy (TR-2PP), and density functional theory (DFT), we describe the real and reciprocal space electronic properties of SAMOs for single C(60) molecules and their self-assembled 1D and 2D quantum structures on single-crystal metal surfaces.     

Structural and electronic properties of Ce-doped Ti4O7 based on experiments and first-principles calculations

A series of Ti₄O₇ powders with different Ce-cation doping concentrations were successfully prepared through a new strategy combining the wet chemical method and hydrogen thermal reduction. It is shown that Ce, entering the lattice of Ti₄O₇ during the reduction process, only occurs in the form of Ce³⁺, and the solubility of Ce is equal to 8.93 at.%. Furthermore, the electrical conductivity of Ce-doped Ti₄O₇ powders was tested for the first time and theoretically explained by the first-principles calculations. It was revealed that Ce provides a negative effect on the electrical conductivity of Ti₄O₇ powders, which is due to the decrease in the number of electronic states near the Fermi energy level caused by the introduction of Ce.     

Synthesis and properties of nanocomposites of WO3 and exfoliated g-C3N4

The nanocomposites of WO₃ nanoparticles and exfoliated graphitized C₃N₄ (g-C₃N₄) particles were prepared and their properties were studied. For this purpose, common methods used for characterization of solid samples were completed with dynamic light scattering (DLS) method and photocatalysis, which are suitable for study of aqueous dispersions.The WO₃ nanoparticles of monoclinic structures were prepared by a hydrothermal method from sodium tungstate and g-C₃N₄ particles were prepared by calcination of melamine forming bulk g-C₃N₄, which was further thermally exfoliated. Its specific surface area (SSA) was 115 m² g⁻¹.The nanocomposites were prepared by mixing of WO₃ nanoparticles and g-C₃N₄ structures in aqueous dispersions acidified by hydrochloric acid at pH = 2 followed by their separation and calcination at 450 °C. The real content of WO₃ was determined at 19 wt%, 52 wt% and 63 wt%. It was found by the DLS analysis that the g-C₃N₄ particles were covered by the WO₃ nanoparticles or their agglomerates creating the nanocomposites that were stable in aqueous dispersions even under intensive ultrasonic field. Using transmission electron microscopy (TEM) the average size of the pure WO₃ nanoparticles and those in the nanocomposites was 73 nm and 72 nm, respectively.The formation of heterojunction between both components was investigated by UV–Vis diffuse reflectance (DRS) and photoluminescence (PL) spectroscopy, high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), photocatalysis and photocurrent measurements. The photocatalytic decomposition of phenol under the LED source of 416 nm identified the formation of Z-scheme heterojunction, which was confirmed by the photocurrents measurements. The photocatalytic activity of the nanocomposites decreased with the increasing content of WO₃, which was explained by shielding of the g-C₃N₄ surface by bigger WO₃ agglomerates. This study also demonstrates a unique combination of various characterization techniques working in solid and liquid phase.     

Synthesis and luminescence properties of novel Y2Si4N6C:Sm3+ carbonitride phosphor

Novel Y₂Si₄N₆C:Sm³⁺ phosphors for white light-emitting diodes (w-LEDs) were prepared by a carbothermal reduction and nitridation method. X-ray diffraction (XRD) and photoluminescence spectra were utilized to characterize the structure and luminescence properties of the as-synthesized phosphors. The emission spectrum obtained by excitation into 291 nm contains exclusively the characteristic emission of Sm³⁺ at 568, 607 and 654 nm which correspond to the transitions from ⁴G_5/2 to ⁶H_5/2, ⁶H_7/2, and ⁶H_9/2 of Sm³⁺, respectively. The strongest one is located at 607 nm due to ⁴G_5/2–⁶H_7/2 transition of Sm³⁺. It was found that concentration quenching occurred as a result of dipole–dipole interaction according to Dexter's theory. The temperature dependence of photoluminescence properties was investigated from 25 to 300 °C and the prepared Y₂Si₄N₆C:Sm³⁺ phosphors showed superior thermal quenching properties.     

Structural and electronic properties of highly photoconductive amorphous carbon nitride

We have studied highly photoconductive amorphous carbon nitride (a-CN_x) films prepared by RF-reactive magnetron sputtering. a-CN_x is attractive as a potentially high performance photoconductive semiconductor suited to apply for such as an electron photography, ultraviolet (UV) detector and electron emitter, etc. In this paper, it is reported about the effects of high magnetic field on the sputtering process of a-CN_x films. The experimental results show that films prepared in the higher magnetic field made by samarium cobalt magnets have less CN triple bonding states, less electron spin density N_S=10¹⁸ cm⁻³ and smoother surface morphology than that made by the usual magnetron sputtering using ferrite magnets. From these results, high magnetic field is effective to prepare hard and stable a-CN_x films. We will also report a model of electronic density of states of a-CN_x especially stressed on the Urbach energy region. A preliminary experiment on electroluminescence is also reported.     

氮化硅/环氧复合电子基板材料制备及性能

以Si_3N_4粉末作为增强组分与环氧树脂进行复合,采用模压法制备了氮化硅/环氧树脂复合电子基板材料。研究了Si_3N_4含量对复合材料导热性能和介电性能的影响。研究结果表明,随着Si_3N_4含量的增加,复合材料中填料形成导热网络,复合材料的热导率也随之增加,当体积填充量为35%时,导热系数达到1．71 W/m·K。复合材料的介电常数随Si_3N_4含量的增加而增加,但在氮化硅陶瓷颗粒的体积分数达到35%时仍维持在较低的水平(7．08,1 MHz)。     

g-C3N4/CQDs光催化材料的制备及性能

采用高温热解法制备了石墨相氮化碳(g-C_3N_4),将其与碳量子点(CQDs)进行水热复合,得到g-C_3N_4/CQDs复合光催化剂。采用SEM、TEM、FTIR、XRD、UV-Vis/DRS、XPS、N2吸附-脱附等温线手段对制备的复合光催化剂进行了表征,以罗丹明B(Rh B)为模拟污染物,考察了g-C_3N_4/CQDs的可见光催化活性及稳定性。结果表明:与g-C_3N_4相比,g-C_3N_4/CQDs对可见光吸收强度增加,同时其吸收波长向可见光区发生红移;当CQDs含量为1.5%(以g-C_3N_4质量为基准)时,所得g-C_3N_4/CQDs光催化材料的催化活性最佳,其对Rh B的光催化降解率是54.5%,是g-C_3N_4光催化降解率的1.38倍,化学反应动力学拟合相关系数R2=0.9982。且g-C_3N_4/CQDs循环使用3次后,其催化降解率仍保持在50%以上。光催化机理研究表明,空穴(h+)、超氧阴离子自由基(·O2–)、过氧化氢分子(H2O2)和羟基自由基(·OH)都是光催化过程中的主要活性物种,四者氧化作用大小依次为:h+·O2– H2O2·OH。     

纳米Si_3N_4/氰酸酯树脂电子封装材料的研究

采用硅烷偶联剂(KH-560)对nano-Si3N4进行表面处理,然后以此作为4,4′-二氰酸酯基二苯基甲烷(BCE)的改性剂,制备了nano-Si3N4/BCE电子封装材料,并研究了该体系的静态力学性能、动态力学性能以及介电性能。结果表明:nano-Si3N4的加入提高了材料的冲击强度和弯曲强度,当w(nano-Si3N4)=3%时,冲击强度、弯曲强度分别由纯BCE的10.1 kJ/m2和94.11 MPa提高到14.58 kJ/m2和112.13 MPa;Nano-Si3N4/BCE体系的储能模量在低温区略低于纯BCE体系,在高温区则略高于纯BCE体系;改性体系的介电常数高于纯BCE体系,但介电损耗因子则低于纯BCE体系。