利用X射线衍射研究冲击波合成纤锌矿型氮化硼

 用X射线衍射法，对不同结晶度的石墨型氮化硼（gBN）在冲击波作用下转变成的纤锌矿型氮化硼（wBN）产物进行了研究，对wBN中的杂质含量等进行了分析。结果表明：gBN的石墨化指数G.I值对wBN的产率有明显的影响。     

纤锌矿型氮化硼及其应用的研究（Ⅰ）——纤锌矿氮化硼的冲击波合成

 用hBN（Ⅰ、Ⅱ型层状结构的六角氮化硼）作原料，在斜冲击波的高温高压作用下，实现了hBN向wBN（纤锌矿型氮化硼）的转变。X光结构分析表明，生成的超硬氮化硼全部为wBN，没有发现zBN（闪锌矿型氮化硼）生成的任何证据。X光荧光光谱分析结果，得到的wBN的纯度接近99%。差热分析显示，在空气中温度为1 127 K时，开始吸热反应，吸热峰位于1 260 K。这表明wBN的热稳定性介于zBN和金刚石之间。     

冲击波合成氮化硼的形貌及热稳定性

 报告了冲击波合成的纤锌矿型氮化硼（wBN）微粉颗粒的细观特征，包括形貌、比表面积、微密度、晶粒度及硼、氮原子数之比等的测量结果，反映wBN晶体中存在很高的微观缺陷密度。并对在大气、氮气及氩气氛中wBN微粉的热稳定性进行了分析。     

一种间接测量圆柱形管内样品冲击波压力的方法

 描述了一种联合使用锰铜计和康铜计间接测量柱对称滑移爆轰条件下，金属管内样品中冲击波压力的方法。给出了冲击压缩方法合成纤锌矿型氮化硼（wBN）时的测量结果。结果表明：管内样品中压力范围大致在11.5~22 GPa范围内，满足冲击波合成wBN所需的压力条件；管内样品压力的发展变化具有不连续性。证明了这种间接测量管内压力的方法是可行的。     

多次冲击石墨合成聚晶金刚石的实验研究

 利用高能炸药爆轰产物驱动金属飞片，碰撞“硬”回收包套以输入平面冲击波，在24~37 GPa的压力范围内，对纯石墨进行1~4次的冲击压缩实验，合成出了纯度很高、形貌良好的立方型聚晶金刚石。随着冲击次数的增加，金刚石的转化率和粒度有增大的趋势。但是，当金刚石粒度较大时（约100 μm以上），如果冲击温度较低（约1 000 K以下），同时冲击压力又较高（约20 GPa以上），金刚石颗粒就容易被冲击波破碎。     

MgO在Mg-hBN体系中对合成cBN晶体的影响

 以金属镁粉为触媒，以六角氮化硼为原料，其中加入适量比例的氧化镁，在国产六面顶压机上，在约5.0 GPa压力、1 500～1 800 K温度条件下，合成出了颜色均匀、晶形完整的黄色立方氮化硼单晶体。实验结果表明，在Mg-hBN体系中，氧化镁对合成cBN晶体的颜色及合成温度有很大的影响。     

在触媒生长cBN区观察到wBN晶粒

 用高分辨率（0.2 nm）电子显微镜，对hBN-触媒体系经高温高压处理后的产物观察中，看到尺寸约为30 nm的微小颗粒，经电子衍射方法判定其具有纤锌矿结构，为wBN的雏形晶粒。     

高温高压合成立方氮化硼的热力学分析

 从热力学角度计算出了以六角氮化硼为原料、用高压触媒法合成立方氮化硼时所形成稳定的临界晶粒半径r_k的大小,当p=6.0 GPa、T=1 600 ℃时,r_k≈15 nm。分析了r_k的大小与合成温度、压力的关系,以及在给定压力下立方氮化硼晶粒转化率与温度的关系。结果表明：在立方氮化硼稳定区,在相同压力下,r_k随温度的升高而增大;在相同温度下,r_k随压力的升高而减小,r_k越小立方氮化硼晶粒的转化率越高。计算结果与实际合成实验所得结果完全一致。     

高压合成立方氮化硼用的新触媒材料的研究

 本文研究了合成立方氮化硼用新触媒材料Mg₃B₂N₄及Ca₃B₂N₄的制备方法，并对它们的稳定性及其催化作用进行了讨论。氮化硼原料的结晶状态及合成温度、合成时间、气流量等对新触媒的合成有着重要的影响。本文还在高温高压下利用新触媒进行了立方氮化硼的合成实验，结果表明，与碱土金属触媒相比新触媒具有合成压力低、转化率高、合成温度和压力范围宽、产物杂志含量低、破碎强度高等优点，是一种应用前景很大的触媒材料。     

纤锌矿氮化硼及其应用的研究（Ⅱ）——纤锌矿型氮化硼的等温状态方程

 使用两种不同的高压在位X光衍射法，研究了用爆炸法合成的纤锌矿型氮化硼（wBN）在室温下的等温状态方程。一种方法是用转靶X光角色散粉末衍射法，研究了它在0~40 GPa压力范围内的等温压缩行为。结果表明，wBN在0~40 GPa的压力范围内是稳定的，没有发生结构相变。通过p-V数据对Murnaghan方程拟合，得到wBN在p=0时的等温体模量B₀=(335±34) GPa及其对压力的一阶导数B₀'=4.21；另一种是用同步辐射X光能量色散衍射法，研究了它在0~25 GPa压力范围内的等温状态方程。实验中，使用了改进的自动加压的DAC高压装置，此装置保证了实验中衍射角θ₀固定不变。将获得的p-V数据仍用Murnaghan方程拟合，得到wBN在p=0时等温体模量B₀=(280±56) GPa，及其B₀'=4.39。     

Crystallographic aspects related to the high pressure–high temperature phase transformation of boron nitride

Crystallographic relations between different forms of boron nitride (BN) appearing at the high pressure–high temperature structural phase transformation have been revealed by high-resolution transmission electron microscopy (HRTEM). As starting materials, crystalline hexagonal BN (hBN) with different degrees of crystallinity, or with defects intentionally introduced, were used. Cubic BN (cBN) is formed only as a minor component, the rest consisting of different forms of sp ² bonded BN: hBN, compressed, monoclinic deformed hBN, or turbostratic BN (tBN). The small cBN crystallites (300–400?nm) contain many defects such as twins, stacking faults and nanoinclusions of other BN forms: tBN, rhombohedral BN (rBN) and wurtzite BN (wBN). The cBN phase grows epitaxially on the basal plane of hBN. The nucleation sites for cBN are revealed by HRTEM. They consist of nanoarches (sp ³ hybridized, highly curved nanostructures), frequently observed at the edges of the hBN crystallites in the starting materials. Based on HRTEM observations of specimens not fully transformed, a nucleation and growth model for cBN is proposed which is consistent with existing theoretical and experimental models.     

Thermal phase stability of rhombohedral boron nitride

Abstract

Thermal phase stability of rhombohedra] boron nitride has been studied between 0 and 8 GPa from 300 to 2700 K. Analysis of the data obtained points to the decisive role of kinetic factors in the rBN phase transformations, the structure and dispersity of the samples under study being of great importance. rBN phase transformations in the cBN thermodynamic stability region of the equilibrium p,T phase diagram for boron nitride occur according to Ostwald stepwise principle by the rBN→hBN→(wBN)→cBN scheme.     

Electronic band structure and x-ray spectra of boron nitride polytypes

The electronic band structures of boron nitride crystal modifications of the graphite (h-BN), wurtzite (w-BN), and sphalerite (c-BN) types are calculated using the local coherent potential method in the cluster muffin-tin approximation within the framework of the multiple scattering theory. The specific features of the electronic band structure of 2H, 4H, and 3C boron nitride polytypes are compared with those of experimental x-ray photoelectron, x-ray emission, and K x-ray absorption spectra of boron and nitrogen. The features of the experimental x-ray spectra of boron nitride in different crystal modifications are interpreted. It is demonstrated that the short-wavelength peak revealed in the total densities of states (TDOS) in the boron nitride polytypes under consideration can be assigned to the so-called outer collective band formed by 2p electrons of boron and nitrogen atoms. The inference is made that the decrease observed in the band gap when changing over from wurtzite and sphalerite to hexagonal boron nitride is associated with the change in the coordination number of the components, which, in turn, leads to a change in the energy location of the conduction band bottom in the crystal.     

Temperature dependence of angular characteristics of boron nitride sputtering

The angular dependence of the sputtering yield and the spatial distribution of particles ejecting from a boron nitride polycrystal with a wurtzite structure in the temperature range from 0 to 2800°C under bombardment with 300 eV xenon ions are calculated by the molecular dynamics method. A reduction of steepness of the curves of angular dependence of boron nitride sputtering with increasing temperature is revealed. Features of the obtained distributions are analyzed on the basis of mechanisms of interaction of slow heavy ions with surface target atoms.     

一种新的氮化碳相的冲击波合成

 为了合成理论预测存在的高密度氮化碳相,以富氮的C-N-O非晶材料和晶态的双氰胺为前体,在低于50 GPa的冲击压力范围内进行了一系列冲击回收实验。回收产物的XRD衍射表明,形成了由β-C₃N₄和一种新的氮化碳相组成的复合相。该新相的衍射峰可以完全指标化为一个单斜晶胞,晶胞常数为a=0.981 nm,b=0.723 nm,c=0.561 nm,β=95.2°,晶胞体积V_cell=0.396 6 nm³。根据实验结果可以认为,氮化碳复合相的形成是前体有机分子在瞬态的冲击波化学反应后,经历了极高速的冲击淬火过程（约10⁹ K/s）,作为一种高压亚稳相而被保存下来。冲击压缩富氮的有机物前体,是合成氮化碳相的一种新方法。     

High Temperature Thermal Insulation System for Millimeter Wave Sintering of B4C

Boron carbide (B₄C) is one of advanced materials and is being used in a wide rage of applications. The unique feature of this material is its large neutron-absorbing cross-section. Some of its most prominent applications are controlling rods in nuclear reactors and radiation protection. 24 GHz microwave processing for B₄C ceramics were performed under flowing argon gas using the sintering system. Sintering at the high temperature (up to 2200°C) was achieved using thermal insulation system consists of fiber-board, boron nitride powder, and boron nitride case. The sintered samples were achieved 90 % of theoretical.