物理化学还原法处理-电感耦合等离子体发射光谱(ICP-OES)法测定污染土壤中的六价铬

定量分析土壤中六价铬Cr(Ⅵ)含量对于生态环境的恢复治理具有重大意义。使用机械球磨-多硫化钙(CPS)物理-化学相结合的处理方法,以电感耦合等离子体光谱仪(ICP-OES)为测试手段,测定污染土壤中的Cr(Ⅵ),同时还探讨了球磨转速、球磨时间和球料比等球磨工艺条件以及还原剂添加量对六价铬浸出浓度的影响。结果表明,当球磨速度500 r/min、球磨时间2 h、球料比12、还原剂添加量为3%时,Cr(Ⅵ)的浸出浓度可显著降低至3.0 mg/kg以下(GB 36600—2018,第一类用地筛选值),大大减少了还原剂的使用量。通过研究碱消解提取过程中的化学反应,控制pH值的条件范围,确保Cr(Ⅵ)的准确测定。同时,碳酸钠、磷酸缓冲溶液、氯化镁在提取过程中的重要作用也不容忽视;在碱消解提取过程中,计算出盐分在提取液中的理论含量,并通过稀释达到降低盐分浓度、拓宽线性范围,减小基体影响的目的。与传统化学还原法相比,物理化学法可以更快、更有效地减少和固化土壤中的Cr(Ⅵ)。     

Plastic analysis of thin plates with anisotropic hardening

In this paper we discuss the adoption of the anisotropic hardening model due to the existence of Bauschinger effect when thin plate is applied by repeated loading. The loading condition of thin plates for linear kinematic hardening has been deduced in terms of generalized forces and generalized plastic deformation. And it can be extended to nonlinear kinematic hardening and mixed hardening. Finally as an example the numerical results are obtained for a circular plate.     

Sn-Co合金作为锂离子二次电池负极材料的研究

在机械球磨过程中通过固相还原反应制备了不同原子配比（2：1，4：1，8：1）的Sn-Co合金，采用X射线衍射（XRD）和电子扫描电镜（SEM）分析了其结构和形貌，并通过组装模拟电池考察了该合金作为锂离子电池负极材料的电化学性能．实验结果表明：具有非晶纳米结构的CoSn4合金具有较高的初始放电容量（430mAh／g）和良好的循环性能，15周后仍能放出360mAh／g的容量，容量保持率为84％．     

联系概率的由来及其在风险决策中的应用

观察一简单随机摸球实验:当盒子中只有白球时,事件A="任抽一球是白球"是必然事件;当盒子中有白球黑球时,事件A是随机事件,这一实验表明事件A的随机性是2个事物(白、黑球)相互联系的一种属性,借此实验说明概率用联系数表述的原理以及联系概率的来由,同时还介绍了引出联系概率时用到的一些新概念,举例说明联系概率在风险决策中的应用.     

FTIR显微镜/ATR物镜法检测圆珠笔迹的研究

纸面上的圆珠笔迹,因其颜色深、纸面反射率低等诸多原因,在FTIR显微镜上用反射方式直接对其检测效果很差。在FTIR显微镜上加用ATR物镜,利用物镜与纸面笔迹接触的ATR检测原理,得到了圆珠笔迹和纸纤维的混合红外光谱,扣除纸纤维的红外光谱,使用差谱法得到圆珠笔迹的红外光谱,谱图中的３个强吸收峰分别是1 581,1 361和1 172 cm-1,这些峰都来源于三苯甲烷类染料,另外1 724 cm-1的羰基吸收来自于圆珠笔油墨中油剂类的醇酸树脂,使用3D-Mapping软件显示了1 581 cm-1在纸面上的强度分布。这种检测方式既得到了清晰的红外光谱图,提供了丰富的笔迹信息,又保护了被检样品的原始性。     

Optimization,Nature, and Mechanism Investigations for the Adsorption of Ciprofloxacin and Malachite Green onto Carbon Nanoparticles Derived from Low-Cost Precursor via a Green Route

The spread of organic pollutants in water spoils the environment, and among the best-known sorbents for removing organic compounds are carbonaceous materials. Sunflower seed waste (SFSW) was employed as a green and low-cost precursor to prepare carbon nanoparticles (CNPs) via pyrolysis, followed by a ball-milling process. The CNPs were treated with a nitric–sulfuric acid mixture (1:1) at 100 °C. The scanning electron microscopy (SEM) showed a particle size range of 38 to 45 nm, and the Brunauer–Emmett–Teller (BET) surface area was 162.9 m² g⁻¹. The elemental analysis was performed using energy-dispersive X-ray spectroscopy, and the functional groups on the CNPs were examined with Fourier transform infrared spectroscopy. Additionally, an X-ray diffractometer was employed to test the phase crystallinity of the prepared CNPs. The fabricated CNPs were used to adsorb ciprofloxacin (CFXN) and malachite green (MLG) from water. The experimentally obtained adsorption capacities for CFXN and MLG were 103.6 and 182.4 mg g⁻¹, respectively. The kinetic investigation implied that the adsorption of both pollutants fitted the pseudo-first-order model, and the intraparticle diffusion step controlled the process. The equilibrium findings for CFXN and MLG sorption on the CNPs followed the Langmuir and the Fredulich isotherm models, respectively. It was concluded that both pollutants spontaneously adsorbed on the CNPs, with physisorption being the likely mechanism. Additionally, the FTIR analysis of the adsorbed CFXN showed the disappearance of some functional groups, suggesting a chemisorption contribution. The CNPs showed an excellent performance in removing CFXN and MLG from groundwater and seawater samples and possessed consistent efficiency during the recycle–reuse study. The application of CNPs to treat synthetically contaminated natural water samples indicated the complete remediation of polluted water using the ball-mill-fabricated CNPs.     

L-苏氨酸手性分子印迹硅胶分离固定相的制备及分离性能研究

本文使用堆砌硅珠法以硅溶胶为原料、苏氨酸(L-Thr)为手性源构造手性环境,制备具有手性分离能力的全无机介孔手性硅胶球,对其进行元素分析、红外光谱法分析、透射电镜、扫描电镜和氮气吸附等表征,采用HPLC法探究无机介孔硅胶球制备的固定相对手性异构体和苯系位置异构体的拆分性能,成功分离了9对外消旋化合物和8种苯系位置异构体...     

Manipulating Reaction Energy Coordinate Landscape of Mechanochemical Diaza-Cope Rearrangement

Chiral vicinal diamines, a unique class of optically-active building blocks, play a crucial role in material design, pharmaceutical, and catalysis. Traditionally, their syntheses are all solvent-based approaches, which make organic solvent an indispensable part of their production. As part of our program aiming to develop chemical processes with reduced carbon footprints, we recently reported a highly practical and environmentally-friendly synthetic route to chiral vicinal diamines by solvent-free mechanochemical diaza-Cope rearrangement. We herein showed that a new protocol by co-milling with common laboratory solid additives, such as silica gel, can significantly enhance the efficiency of the reaction, compared to reactions in the absence of additives. One possible explanation is the Lewis acidic nature of additives that accelerates a key Schiff base formation step. Reaction monitoring experiments tracing all the reaction species, including reactants, intermediates, and product, suggested that the reaction profile is distinctly different from ball-milling reactions without additives. Collectively, this work demonstrated that additive effect is a powerful tool to manipulate a reaction pathway in mechanochemical diazo-Cope rearrangement pathway, and this is expected to find broad interest in organic synthesis using mechanical force as an energy input.     

基于重球触地实验的空区塌落振动分析及治理

根据相似理论,以重球落地实验模拟采空区坍塌进而指导采空区治理为出发点,在振动波动特性分析的基础上,分别开展了质量为4 kg和10 kg的重球从1.0、1.5和2.0 m的高度落地的峰值振动速度测试实验;首次提出了累计振动速度衰减率和相对能量比概念;以普氏拱理论为基础,分析了采空区坍塌振动速度。研究表明:振动速度与重球质量和落地高度成正相关,且前者对累计衰减率的影响大于后者;随着测点距离的增大,振动速度整体表现为衰减趋势;重球质量为4 kg和10 kg时,在水平距离重球落地点3.0 m处的累计衰减率分别为79.79%~81.61%和79.95%~83.52%。不同介质交界面的反射和折射可引起振动速度的小幅度“跃增”。重球质量对振动能量衰减影响明显;质量越大,近区能量衰减越慢。采空区冒落体582.5~5 926.5 t,引起的振动速度远大于边坡安全允许值。采用“采空区顶板崩落+边坡削坡”方案进行治理后,边坡安全系数可达到1.26,消除采空区安全隐患。     

Simulation of ball motion and energy transfer in a planetary ball mill

A kinetic model is proposed for simulating the trajectory of a single milling ball in a planetary ball mill, and a model is also proposed for simulating the local energy transfer during the ball milling process under no-slip conditions. Based on the kinematics of ball motion, the collision frequency and power are described, and the normal impact forces and effective power are derived from analyses of collision geometry. The Hertzian impact theory is applied to formulate these models after having established some relationships among the geometric, dynamic, and thermophysical parameters. Simulation is carried out based on two models, and the effects of the rotation velocity of the planetary disk and the vial-to-disk speed ratio ω/Ω on other kinetic parameters is investigated. As a result, the optimal ratio ω/Ω to obtain high impact energy in the standard operating condition at = 800 rpm is estimated, and is equal to 1.15.