炸药爆轰法制备纳米石墨粉及其在高压合成金刚石中的应用

介绍了一种制备纳米石墨粉的新方法——负氧平衡炸药爆轰法. 对合成的黑粉产物进行x射线衍射分析，确认其为石墨结构，平均晶粒度为2.58 nm. 透射电子显微分析的结果表明，炸药爆轰法制备的黑粉为六方结构的纳米石墨粉，颗粒呈球形或椭球形. 用小角x射线散射法测定纳米石墨粉的粒度分布在1—50 nm，有92.6wt%的粉末粒度小于16 nm. 平均粒径为8.9 nm. 纳米石墨粉的比表面积约为500—650 m²/g. 在六面顶压机中用纳米石墨粉在Fe粉触媒的作用下进行金刚石的高压合成实验 关键词： 纳米石墨粉 爆轰 金刚石 合成     

爆轰裂解法制备纳米石墨粉的吸附性能研究

 在酸含量不同的原材料中,通过爆轰的方法制备纳米石墨粉,并利用BET方程以及BJH方法对所得纳米石墨粉进行比表面积和孔径分布分析。分析结果表明,所得爆轰产物中有的比表面积大致为天然鳞片石墨的5.3~9.2倍,而且随酸含量的增大逐渐增大,产物的等温线中存在吸附滞后现象。其中,增大的比表面积主要由分布在3 nm至7 nm之间的孔引起的,而且在爆轰后,孔径4 nm左右的孔,其数量达到最大值。通过对纳米石墨粉的研究,分析了酸在爆轰过程中的积极作用,并为纳米石墨粉的进一步应用提供了结构信息。     

炸药爆轰法制备的纳米石墨粉的拉曼光谱

负氧平衡炸药爆轰法合成的纳米石墨粉,是一种新型的具有良好实用前景的纳米粉体材料。采用负氧平衡炸药梯恩梯(TNT),在分别充有氮气、氩气、二氧化碳等保护性气体、压力为0.25～2 atm的密闭容器内爆轰制备了纳米石墨粉。用激光拉曼光谱对制备的样品进行了测试,结果表明样品为石墨结构。纳米石墨粉的Raman峰与块体石墨相比,其峰位向高波数方向偏移了约5 cm-1。纳米石墨粉Raman峰的半高宽约为22 cm-1,由此可计算出纳米石墨粉的颗粒大小为2.97～3.97 nm。与高纯石墨Raman峰相比,纳米石墨粉的Raman峰由于尺寸效应出现了蓝移现象, 并对此现象进行了讨论。用X射线衍射仪(XRD)和透射电子显微镜(TEM)测定了纳米石墨粉的物相,并对其颗粒粒径进行了估算,其结果为2.58 nm(酸处理前)和1.86 nm(酸处理后),与Raman光谱的结果基本吻合。     

爆轰裂解法制备纳米石墨粉的吸附性能研究(英文)

在酸含量不同的原材料中,通过爆轰的方法制备纳米石墨粉,并利用BET方程以及BJ H方法对所得纳米石墨粉进行比表面积和孔径分布分析。分析结果表明,所得爆轰产物中有的比表面积大致为天然鳞片石墨的5.3~9.2倍,而且随酸含量的增大逐渐增大,产物的等温线中存在吸附滞后现象。其中,增大的比表面积主要由分布在3 nm至7 nm之间的孔引起的,而且在爆轰后,孔径4 nm左右的孔,其数量达到最大值。通过对纳米石墨粉的研究,分析了酸在爆轰过程中的积极作用,并为纳米石墨粉的进一步应用提供了结构信息。     

凝聚炸药中超压爆轰的实验研究

 采用飞片碰撞技术，在TNT/RDX（40/60）炸药中获得了2.5倍于正常爆轰的最大超压值，得到了超压爆轰下爆轰产物物态方程p=Aρ^{k+A₁(p-p_J)}（p－爆压，单位GPa，ρ－密度，单位kg/m³，A=ρ_J/ρ^k_J，p_J=27.06 GPa，ρ_J=2.3×10³ kg/m³，k=2.77，A₁=2.7×10^-3 GPa^-1，下表J代表正常爆轰状态）。该方程还可以较好地描述超压爆轰产物的二次冲击状态。     

纳米二氧化钛粉体的气相爆轰制备

 介绍了利用氢氧混合气体为原料、以四氯化钛为前驱体、气相爆轰制备纳米二氧化钛粉体的方法。利用XRD衍射结果分析证明,产物为金红石相和锐钛矿相的二氧化钛混晶,其晶粒尺度为纳米量级。通过XRD、SEM、TEM分析可以得出,粒子基本为球形,大部分粒子粒径为10~20 nm,也有少量的100 nm左右的粒子产生。分析后发现,反应发生在爆燃转爆轰的过程中和爆轰管中的湍流现象是导致大粒子产生的主要原因。在对在氢过量和氧过量两种状况下,对爆轰所产生的产物的形貌进行了对比,分析发现两种状况产生纳米二氧化钛粉末粒径分布和形貌并没有太大变化。     

乳化炸药爆轰合成纳米氧化铈及表征

为通过爆轰法合成纳米氧化铈,设计并制备了以Ce(NO3)3·6H2O为主要氧化剂的5种乳化炸药。综合考虑Ce(NO3)3含量对乳化炸药爆速的影响和纳米氧化铈的得率,筛选出适用于爆轰法制备纳米氧化铈的乳化炸药配方。通过在爆炸罐中起爆乳化炸药,制备得到了纳米氧化铈。利用X射线衍射仪(XRD)和透射电镜(TEM)对样品进行表征。XRD测试结果表明,乳化炸药爆轰法合成的纳米氧化铈属于立方晶系,理论粒径为74nm。TEM测试结果表明,合成的纳米氧化铈外观呈球形,具有较好的分散性和粒度均一性,平均粒径为70nm。     

气相/凝聚炸药爆轰合成的碳包铜纳米颗粒特征

采用凝聚炸药爆轰和气相爆轰分别制备碳包铜纳米颗粒,并利用XRD,Raman和TEM等方法对合成纳米产物进行对比分析。其中凝聚炸药爆轰法以柠檬酸铜干凝胶、油酸和黑索金为原料按照一定比例配成爆炸源,在氮气的保护氛围中引爆;而气相爆轰法以乙酰丙酮铜为原料,分别以H2和O2,H2和空气为爆炸源,在负氧条件下引爆。通过XRD,Raman和TEM分析结果表明,两类爆轰法均可得到分散性良好的碳包覆铜纳米颗粒,碳壳石墨化程度较高。气相爆轰可以合成10 nm以下的纳米晶粒,而凝聚炸药爆轰合成的晶粒尺寸在20~40 nm,且存在较多空壳结构;气相爆轰产物其碳壳尺寸在2~3 nm,凝聚炸药爆轰产物其碳壳尺寸在2~5 nm。     

气相/凝聚炸药爆轰合成的碳包铜纳米颗粒特征

采用凝聚炸药爆轰和气相爆轰分别制备碳包铜纳米颗粒,并利用XRD,Raman和TEM等方法对合成纳米产物进行对比分析。其中凝聚炸药爆轰法以柠檬酸铜干凝胶、油酸和黑索金为原料按照一定比例配成爆炸源,在氮气的保护氛围中引爆;而气相爆轰法以乙酰丙酮铜为原料,分别以H2和O2,H2和空气为爆炸源,在负氧条件下引爆。通过XRD,Raman和TEM分析结果表明,两类爆轰法均可得到分散性良好的碳包覆铜纳米颗粒,碳壳石墨化程度较高。气相爆轰可以合成10 nm以下的纳米晶粒,而凝聚炸药爆轰合成的晶粒尺寸在20~40 nm,且存在较多空壳结构;气相爆轰产物其碳壳尺寸在2~3 nm,凝聚炸药爆轰产物其碳壳尺寸在2~5 nm。     

利用棱镜谱仪研究氢燃烧转变为爆轰的过程

本文利用Polaroid高速感光底片在一次实验中成功地拍摄到氢燃烧转变为爆轰(DDT)的光谱;利用光电技术研究了氢燃烧转变为爆轰过程中OH基(0.3064μm,0.3428μm)的变化过程.研究表明:在氢燃烧转变为爆轰过程中OH基是逐渐增大的,出现爆轰时OH基出现明显增长;OH(0,0)辐射早于O_2(0,14)辐射,它说明O_2在链式反应中能量比较低,它只有和自由原子和自由基相互碰撞获取高的能量而被激发.     

Theoretical study of molecular hydrogen and spiltover hydrogen storage on two-dimensional covalent-organic frameworks

Molecular hydrogen and spiltover hydrogen storages on five two-dimensional （2D） covalent-organic frameworks （COFs） （PPy-COF, TP-COF, BTP-COF, COF-18 A, and HHTP-DPB COF） are investigated using the grand canonical Monte Carlo （GCMC） simulations and the density functional theory （DFT）, respectively. The GCMC simulated results show that HHTP-DPB COF has the best performance for hydrogen storage, followed by BTP-COF, TP-COF, COF-18 A, and PPy-COE However, their adsorption amounts at room temperature are all too low to meet the uptake target set by US Department of Energy （US-DOE） and enable practical applications. The effects of pore size, surface area, and isosteric heat of hydrogen on adsorption amount are considered, which indicate that these three factors are all the important factors for determining the H2 adsorption amount. The chemisorptions of spiltover hydrogen atoms on these five COFs represented by the cluster models are investigated using the DFT method. The saturation cluster models are constructed by considering all possible adsorption sites for these cluster models. The average binding energy of a hydrogen atom and the saturation hydrogen storage density are calculated. The large average binding energy indicates that the spillover process may pro- ceed smoothly and reversibly. The saturation hydrogen storage density is much larger than the physisorption uptake of H2 molecules at 298 K and 100 bar （1 bar = 105 Pa）, and is close to or exceeds the 2010 US-DOE target of 6 wt% for hydrogen storage. This suggests that the hydrogen storage capacities of these COFs by spillover may be significantly enhanced. Thus 2D COFs studied in this paper are suitable hydrogen storage media by spillover.     

Experimental study of the influence of annular nozzle on acoustic characteristics of detonation sound wave generated by pulse detonation engine

Acoustic characteristics of the detonation sound wave generated by a pulse detonation engine with an annular nozzle, including peak sound pressure, directivity, and A duration, are experimentally investigated while utilizing gasoline as fuel and oxygen-enriched air as oxidizer. Three annular nozzle geometries are evaluated by varying the ratio of inner cone diameter to detonation tube exit diameter from 0.36 to 0.68. The experimental results show that the annular nozzles have a significant effect on the acoustic characteristics of the detonation sound wave. The annular nozzles can amplify the peak sound pressure of the detonation sound wave at 90° while reducing it at 0° and 30°. The directivity angle of the detonation sound wave is changed by annular nozzles from 30° to 90°. The A duration of the detonation sound wave at 90° is also increased by the annular nozzles. These changes indicate that the annular nozzles have an important influence on the acoustic energy distribution of the detonation sound wave, which amplify the acoustic energy in a direction perpendicular to the tube axis and weaken it along the direction of the tube axis.     

Sonochemical synthesized BaMoO4/ZnO nanocomposites as electrode materials: A comparative study on GO and GQD employed in hydrogen storage

Due to poor rate proficiency and electrochemical capacity of transition metal oxides, production electrode materials as operative way to develop the electrochemical performance is a crucial strategy to make sure the great electroactive sites and fast electron/ion diffusion route. In order to solve this problem, carbon-based nanocomposites as conductive substrates are applied. The nanostructured BaMoO₄/ZnO was produced by sonochemical method in the presence of tween 20 as stabilizing agent. Effect of graphene quantum dots (GQDs) and graphene oxide (GO) for developing hydrogen capacity of BaMoO₄/ZnO was studied by providing representative composites of BaMoO₄/ZnO-GQDs and BaMoO₄/ZnO-GO. For this purpose, GQDs was synthesized using green source of Spiraea crenata and the GO provided by commercial company. The structural analysis shows preparation of scales-like morphology of BaMoO₄/ZnO without any impurities through SEM, TEM, XRD, EDS and FT-IR characterization data. Also, the specific surface area for BaMoO₄/ZnO-GQDs (11 m²/g) and BaMoO₄/ZnO-GO (124 m²/g) nanocomposites increased by comparing to BaMoO₄/ZnO (9.1 m²/g). The resultant nanocomposites used as new active compounds for applying in hydrogen storage strategies using cyclic voltammetry and chronopotentiometry tests. Comprehensively, the hydrogen capacitance after 15 cycles was demonstrated on the nanostructured BaMoO₄/ZnO about 129 mAhg⁻¹. It demanded the maximum capacitance for BaMoO₄/ZnO-GQDs and BaMoO₄/ZnO-GO nanocomposites were 284 and 213 mAhg⁻¹ respectively, which was higher than the initial nanostructured BaMoO₄/ZnO. It was exposed from the carbon based structured that; the endorsed electrochemical hydrogen storage (EHS) performance is ascribed to the reaction of the redox pair of Mo⁶⁺ /Mo⁵⁺ at the active sites throughout the EHS procedure. This study delivers a novel plan and potential sorption electrode materials to progress the intrinsic action of conductive compounds.     

The effect of lattice constant on the storage capacity of hydrogen hydrates: a Monte Carlo study

ABSTRACT

We use grand canonical Monte Carlo simulations to examine the effect of the size of hydrate cavities (as reflected through the lattice constant of the hydrate unit cell) on the efficiency of clathrate hydrates in storing hydrogen gas. With this approach, the hydrate lattice is treated as a solid substrate where gas absorption takes place. Of practical interests are cases, where the lattice-size parameters are changed in such a way that they can promote/enhance multiple cavity occupancy, namely the presence of more than one guest-gas molecule in the same hydrate cavity. This phenomenon is commonly observed in the case of hydrogen hydrates and could increase their storage capacity. A parametric analysis is also carried out to quantify the correlation between the change in the lattice constant and the storage capacity since small changes in the size of the crystal unit cell may induce significant changes in the storage capacity especially in cases where multiple cavity occupancy occurs.     

Numerical studies on autoignition and detonation development from a hot spot in hydrogen/air mixtures

Detonation development inside spark ignition engines can result in the so called super-knock with extremely high pressure oscillation above 200?atm. In this study, numerical simulations of autoignitive reaction front propagation in hydrogen/air mixtures are conducted and the detonation development regime is investigated. A hot spot with linear temperature distribution is used to induce autoignitive reaction front propagation. With the change of temperature gradient or hot spot size, three typical autoignition reaction front modes are identified: supersonic reaction front; detonation development and subsonic reaction front. The effects of initial pressure, initial temperature, fuel type and equivalence ratio on detonation development regime are examined. It is found that the detonation development regime strongly depends on mixture composition (fuel and equivalence ratio) and thermal conditions (initial pressure and temperature). Therefore, to achieve the quantitative prediction of super-knock in engines, we need use the detonation development regime for specific fuel at specific initial temperature, initial pressure, and equivalence ratio.     

Substitution effects on the hydrogen storage behavior of AB2 alloys by first principles

The hydrogen storage behavior of the TiCr₂ and ZrCr₂ alloys substituted with the third components (Zr, V, Fe, Ni) have been studied using first-principles calculations. The change of the hydrogen absorption energies caused by metal doping is arising from the charge transfer among the doped alloys interior. Zr and V atoms devoted abundant electrons, leading to a great enhancement of the H absorption energy, while Fe and Ni atoms always accepted electrons, yielding a remarkable decrease of the H absorption energy. The hydrogen diffusion energy barrier is closely correlated with the geometry effect rather than the electronic structure.     

钒基固溶体储氢材料弹性性质第一性原理研究

采用基于密度泛函理论的第一性原理赝势平面波方法,计算了（59Cr-41Ti）_100－xV_x（x=5,15,30,60,80,100）六种钒基储氢合金的晶格常数、弹性性质和电子态密度,计算结果与实验值符合较好.发现当x=60时的钒基合金具有较好弹性性质,杨氏模量为14930 GPa,切变模量为5442 GPa及体弹模量为19396 GPa.结合实验循环性能分析认为在吸放氢过程中合金已经发生塑性变形,弹性 关键词： 钒基固溶体 储氢合金材料 密度泛函理论 弹性性质     

碱金属掺杂碳纳米管储氢量差异的理论分析

采用巨正则蒙特卡罗方法模拟锂掺杂单壁碳纳米管阵列（SWCNTA－Single Walled Carbon Nanotube Array）和钾掺杂SWCNTA的物理吸附储氢。重点研究了碱金属原子的种类和掺杂位置对SWCNTA储氢的影响。通过分析碱金属掺杂SWCNTA与氢分子间相互作用的差异及其变化的原因,给出了碱金属掺杂SWCNTA储氢量差异的理论解释,并对今后的研究工作提出了新的建议。     

元素替代对LiNH2储氢材料释氢能力影响的第一性原理研究

采用第一性原理赝势平面波方法,研究了元素替代对 LiNH₂释氢能力影响及作用机理.计算给出了结合能、电子态密度、电荷布居,分析了结构的稳定性和原子间的成键情况.结果表明：金属Ca,Na,Al替代LiNH₂部分Li时,可以使N—H键有所减弱.Mg,Al同时替代Li时,效果最好.在Li（Mg）NH₂中,非金属元素B,C,P替代N时,C的效果最好.预测Mg,Al,C共同替代时,会得到的一种较低释氢温度的储氢材料. 关键词： 2储氢材料')" href="#">LiNH₂储氢材料 密度泛函理论 元素替代行为 释氢能力