Metal nitride cluster fullerenes: their current state and future prospects

The world of endohedral fullerenes was significantly enlarged over the past seven years by the cluster fullerenes, which contain structures such as the M(2)C(2) carbides and the M(3)N nitrides. While the carbide clusters are generated under the standard arc-burning conditions according to stabilization conditions, the nitride cluster fullerenes (NCFs) are formed by varying the composition of the cooling gas atmosphere in the arc-burning process. The special conditions for NCF synthesis is described in detail and the optimum conditions for the production of NCFs as the main product in fullerene syntheses are given. A general review of all NCFs reported to date consists of the structures, properties, and stability of the NCFs as well as the abundance of the NCFs in the fullerene soot. It is shown that all cages with even carbon atoms from C(68) to C(98) are available as endohedral nitride cluster structures (with the exception of C(72), C(74), and C(76)). Specifically, the NCFs form the largest number of structures that violate the isolated pentagon rule (IPR). Finally some practical applications of these cluster fullerenes are illustrated and an outlook is given, taking the superior stability of these endohedral fullerenes into account.     

Mixed nitrogen source effect in the hydrothermal synthesis of cubic BN

Mixed nitrogen source effect was applied in the synthesis of boron nitride (BN) by hydrothermal method. The experimental results revealed that, compared to those obtained by using only two kinds of nitrogen sources, when three kinds of nitrogen sources were used during the synthesis of BN, it was more easier to obtain BN samples with cBN as the dominant phase. Furthermore, if this effect was applied together with the two-step reaction method, nearly pure cBN can be obtained. The results of X-ray diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR), transmission electron microscopy (TEM), selective area electron diffraction (SAED), high-resolution transmission electron microscope (HRTEM) and X-ray photoelectron spectroscopy (XPS) measurements proved that the major phases in the samples are cBN.     

Fabrication of silicon nitride nanoceramics—Powder preparation and sintering: A review

Fine-grained silicon nitride ceramics were investigated mainly for their high-strain-rate plasticity. The preparation and densification of fine silicon nitride powder were reviewed. Commercial sub-micrometer powder was used as raw powder in the “as-received” state and then used after being ground and undergoing classification operation. Chemical vapor deposition and plasma processes were used for fabricating nanopowder because a further reduction in grain size caused by grinding had limitations. More recently, nanopowder has also been obtained by high-energy milling. This process in principle is the same as conventional planetary milling. For densification, primarily hot pressing was performed, although a similar process known as spark plasma sintering (SPS) has also recently been used. One of the advantages of SPS is its high heating rate. The high heating rate is advantageous because it reduces sintering time, achieving densification without grain growth. We prepared silicon nitride nanopowder by high-energy milling and then obtained nanoceramics by densifying the nanopowder by SPS.     

氨解草酸氧钒制备纳米氮化钒粉体

首次采用氨解草酸氧钒（VOC2O4·H2O）前驱体的方法成功制备出了平均粒径50nm左右的立方相VN粉体.通过X射线衍射测试分析了温度、时间和氨气流量对氮化钒形成的影响。用透射电镜（TEM）观察和分析了氮化钒粉体的形貌和结构。实验结果表明，在600-850℃前驱体均能氨解戌VN，随氨解温度的升高，VN形成的时间显著缩短，750℃的温度下，10min就可以氨解完全。氨气流量可控制在40ml／min以上，表明该方法具有氨解温度低、氨气流量少和产物纯度高的特点。     

AZ31镁合金基材非平衡磁控溅射镀膜工艺研究

采用中频孪生靶非平衡磁控溅射技术在AZ31镁合金基底上制备出氮化硅薄膜。利用傅里叶变换红外光谱仪、电子探针、X射线衍射仪等研究了氮气流量比率对氮化硅薄膜的成分、微观结构的影响。通过对薄膜力学性能和抗腐蚀性能的检测分析了氮化硅薄膜对AZ31镁合金基底表面改性的作用。结果表明:中频孪生非平衡磁控溅射技术制备的薄膜为非晶态富N氮化硅。随着氮气流量比率的增加,薄膜的沉积速率降低,Si含量减少。在AZ31镁合金基底上制备氮化硅薄膜有效提高了基底的力学性能和抗腐蚀性能,显微硬度得到显著提高,腐蚀电流密度降低了3个数量级,并且薄膜与基底之间的结合力良好。     

Aerosol synthesis of titanium nitride nanoparticles by direct current arc discharge method

Arc discharge synthesis has industrial relevance due to its low cost and scale-up potential. The production of titanium nitride nanoparticles was achieved by direct current arc discharge in an atmospheric-pressured ambient composed of N₂ and Ar. We systematically investigated the effect of the synthesis parameters, including quench gas velocity, quench gas composition, and applied arc current, on the particle quality, yield, and size. It is found that increasing quench gas velocity enables to produce particles with a primary size of 10–15 nm, while titanium nitride particles of 20–50 nm are produced at low quench gas velocity based on scanning electron microscope (SEM) analysis. X-ray diffraction (XRD) results indicated that titanium nitride particles produced at various nitrogen compositions are almost stoichiometric, while the crystallite size increases almost 20 nm when increasing nitrogen contents in the quench gas. Quench gas composition also has a significant impact on the arc voltage as well as particle production rate. When increasing the nitrogen concentration from 20% to 100%, the production rate can be enhanced by a factor of three. Besides, raising the applied arc current from 12 A to 50 A leads to a yield enhancement of factor 10. According to the Brunauer-Emmett-Teller (BET) measurement, the increase of applied arc current has a limited impact on primary particle size. The enhancement in particle production rate is mainly reflected by the larger agglomerate sizes and agglomerate number concentration. Additionally, based on experimental observations and previous studies, a mechanism is presented to explain the growth of deposits on the cathode tip.     

电沉积氧化锌纳米柱的带隙和近带边发射蓝移

用电化学沉积方法制备了ZnO纳米柱阵列。在Zn(NO₃)₂基础电解液中加入新电解质并引入NH₄NO₃ 和Ga(NO₃)₃,实现了对ZnO纳米柱阵列的带隙、近带边发射、斯托克斯位移、直径、密度等物理性质的设计和裁剪。可在63~77 nm操控纳米柱的直径。增加电解液中的Ga(NO₃)₃浓度,阵列的密度可降低到7.0×10⁹ /cm²。新加入电解液中的盐类使ZnO纳米柱的带隙蓝移~50 meV并使光致发光图谱中的近带边发射蓝移53~73 meV以及斯托克斯位移蓝移23 meV,表明可对其非辐射复合进行抑制设计和裁剪。     

Kinetics of titanium nitride coatings deposited by thermo-reactive deposition technique

In this study, the growth kinetics of titanium nitride layer deposited on pre-nitrided AISI 1020 steel samples by thermo-reactive diffusion (TRD) techniques in a solid medium was reported. Steel was at first tufftrided and then titanium nitride coating treatment was performed in a powder mixture consisting of ferro-titanium, ammonium chloride and alumina at 1173, 1223 and 1273 K for 1-4 h. Titanium nitride layer thickness on the titanium nitride coated AISI 1020 steel ranged from 5.5 to 19.2 μm depending on treatment time and temperature. Layer growth kinetics was analyzed by measuring the depth of titanium nitride layer as a function of time and temperature. The kinetics equation of the reaction has also been determined with Arhenius equation K=K_oexp(−Q/(RT). The result showed that the diffusion coefficient (K) of the process increased with treatment temperature. Activation energy (Q) for TRD process was calculated as 187.09 kJ/mol. The diffusion coefficients (K) changed between 6.637×10⁻¹¹ and 2.097×10⁻¹⁰ cm²/s depending on the process temperature.