New Insights into Keggin‐Type 12‐Tungstophosphoric Acid from 31P MAS NMR Analysis of Absorbed Trimethylphosphine Oxide and DFT Calculations

The acid and transport properties of the anhydrous Keggin‐type 12‐tungstophosphoric acid (H₃PW₁₂O₄₀; HPW) have been studied by solid‐state ³¹P magic‐angle spinning NMR of absorbed trimethylphosphine oxide (TMPO) in conjunction with DFT calculations. Accordingly, ³¹P NMR resonances arising from various protonated complexes, such as TMPOH⁺ and (TMPO)₂H⁺ adducts, could be unambiguously identified. It was found that thermal pretreatment of the sample at elevated temperatures (≥423 K) is a prerequisite for ensuring complete penetration of the TMPO guest probe molecule into HPW particles. Transport of the TMPO absorbate into the matrix of the HPW adsorbent was found to invoke a desorption/absorption process associated with the (TMPO)₂H⁺ adducts. Consequently, three types of protonic acid sites with distinct superacid strengths, which correspond to ³¹P chemical shifts of 92.1, 89.4, and 87.7 ppm, were observed for HPW samples loaded with less than three molecules of TMPO per Keggin unit. Together with detailed DFT calculations, these results support the scenario that the TMPOH⁺ complexes are associated with protons located at three different terminal oxygen (O_d) sites of the PW₁₂O₄₀³⁻ polyanions. Upon increasing the TMPO loading to >3.0 molecules per Keggin unit, abrupt decreases in acid strength and the corresponding structural variations were attributed to the change in secondary structure of the pseudoliquid phase of HPW in the presence of excessive guest absorbate.     

7A04铝合金的本构关系和失效模型

使用万能材料试验机、扭转试验机和Taylor撞击实验研究了高强铝合金7A04在常温至250 ℃的 准静态、动态本构关系和失效模型。基于实验结果,修改了Johnson-Cook强度模型中的应变强化项以及 Johnson-Cook失效模型中的温度软化项,并结合数值模拟标定了模型参数。实验结果表明,7A04铝合金的 应变和应变率强化效应不显著,失效应变随温度的增加、应力三轴度的减小和应变率的减小而增加。     

一种新型SPH-FEM耦合算法及其在冲击动力学问题中的应用

为了充分发挥光滑粒子流体动力学方法(smoothed particle hydrodynamics,SPH)在处理大变形和有限元(finite element method,FEM)问题时计算精度高的优势,提出了一种新型SPH-FEM耦合算法.该耦合算法在大变形区域使用SPH粒子离散,其余区域使用有限元离散.在耦合界面...