PAN纤维共聚单体作用机理的光电离质谱研究

本工作以丙烯腈/衣康酸（IA）二元共聚原丝以及丙烯腈/IA/丙烯酸甲酯（MA）三元共聚原丝为研究对象，利用热重分析仪（TG）和热解-同步辐射真空紫外光电离质谱（Py-SVUV-PIMS）对其热稳定化过程进行研究。TG结果表明，氮气气氛下，二元共聚原丝（PAN/IA）和三元共聚原丝（PAN/IA/MA）分别呈现三阶段和两阶段的热分解过程，其中PAN/IA的第一和第二阶段均对应PAN线型分子链的断裂，但前者是由自由基环化反应放热引发的，后者则是由正常温度下的热分解所致，而单体MA的加入显著抑制了自由基环化反应，使得PAN原丝的热稳定化能够以单体IA诱导的离子型环化反应为主较平缓地进行，相应的热失重过程也由两阶段转变为了单阶段。Py-SVUV-MS的实验结果表明，两种共聚PAN原丝在程序升温过程中会生成包括含氮小分子、丙烯腈单体及低聚物、成环化合物在内的三类主要热解产物，对比各类产物的生成趋势和产量，推断单体MA通过降低PAN结构的规整度，使其无定形化，从而增加环化反应的引发点，促进PAN原丝向稳定的预氧丝转变，同时由典型热解产物——甲基丙烯腈的生成路径可知，MA本身并不参与PAN大分子的环化反应，属于中性共聚单体。空气气氛下，CO₂的产量差异也间接证明了MA单体能够有效提升PAN纤维的固碳能力，采用三元共聚方法制得的PAN纤维热稳定性能更佳。     

Systematic convergence of nonlinear stochastic estimators on the Special Orthogonal Group SO(3)

This paper introduces two novel nonlinear stochastic attitude estimators developed on the Special Orthogonal Group with the tracking error of the normalized Euclidean distance meeting predefined transient and steady‐state characteristics. The tracking error is confined to initially start within a predetermined large set such that the transient performance is guaranteed to obey dynamically reducing boundaries and decrease smoothly and asymptotically to the origin in probability from almost any initial condition. The proposed estimators produce accurate attitude estimates with remarkable convergence properties using measurements obtained from low‐cost inertial measurement units. The estimators proposed in continuous form are complemented by their discrete versions for the implementation purposes. The simulation results illustrate the effectiveness and robustness of the proposed estimators against uncertain measurements and large initialization error, whether in continuous or discrete form.     

Development of mobile miniature natural gas liquefiers

With increasing consumption of natural gas (NG), small NG reservoirs, such as coalbed methane and oil field associated gas, have recently drawn significant attention. Owing to their special characteristics (e.g., scattered distribution and small output), small-scale NG liquefiers are highly required. Similarly, the mixed refrigerant cycle (MRC) is suitable for small-scale liquefaction systems due to its moderate complexity and power consumption. In consideration of the above, this paper reviews the development of mobile miniature NG liquefiers in Technical Institute of Physics and Chemistry (TIPC), China. To effectively liquefy the scattered NG and overcome the drawbacks of existing technologies, three main improvements, i.e., low-pressure MRC process driven by oil-lubricated screw compressor, compact cold box with the new designed heat exchangers, and standardized equipment manufacturing and integrated process technology have been made. The development pattern of “rapid cluster application and flexible liquefaction center” has been eventually proposed. The small-scale NG liquefier developed by TIPC has reached a minimum liquefaction power consumption of about 0.35 kW·h/Nm³. It is suitable to exploit small remote gas reserves which can also be used in boil-off gas reliquefaction and distributed peak-shaving of pipe networks.     

Reasons for breaking of chemical bonds of gas molecules during movement of explosion products in cracks formed in rock mass

The purpose of this study was to develop a physico-mathematical model and technique for estimation of chemical bond stability depending on electric field intensity of an external point charge. A hypothesis for a possible physico-chemical mechanism of the formation of additional harmful gases in the rock destruction by blasting was proposed. The theoretical basis of the hypothesis is the method of theretical evaluation of bond energy depending on the distance to a point charge, the third Coulomb centre. The quantum-mechanical model for calculating the electronic terms of molecules makes it possible to solve problems associated with the determination of parameters of molecules under the action of various physical fields on the system under consideration. The model was approved for some diatomic molecules. The discrepancy between the experimental data and calculated data did not exceed 14%, which proves accuracy of the obtained results. The model can be used in the field of research into the causes of gas-dynamic phenomena in underground coal mines, in studies of the degree of stability of nanostructured components of coal under physical influences, and in the theoretical design of new compounds and structures in the field of nanomaterial science and nanotechnology.     

Selective Analysis of Sulfur-Containing Species in a Heavy Crude Oil by Deuterium Labeling Reactions and Ultrahigh Resolution Mass Spectrometry

A heavy crude oil has been treated with deuterated alkylating reagents (CD₃I and C₂D₅I) and directly analyzed without any prior fractionation and chromatographic separation by high-field Orbitrap Fourier Transform Mass Spectrometry (FTMS) and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) using electrospray ionization (ESI). The reaction of a polycyclic aromatic sulfur heterocycles (PASHs) dibenzothiophene (DBT), in the presence of silver tetrafluoroborate (AgBF₄) with ethyl iodide (C₂H₅I) in anhydrous dichloroethane (DCE) was optimized as a sample reaction to study heavy crude oil mixtures, and the reaction yield was monitored and determined by proton nuclear magnetic resonance spectroscopy (¹H-NMR). The obtained conditions were then applied to a mixture of standard aromatic CH-, N-, O- and S-containing compounds and then a heavy crude oil, and only sulfur-containing compounds were selectively alkylated. The deuterium labeled alkylating reagents, iodomethane-d₃ (CD₃I) and iodoethane-d₅ (C₂D₅I), were employed to the alkylation of heavy crude oil to selectively differentiate the tagged sulfur species from the original crude oil.     

Simultaneous determination of mycotoxin in commercial coffee

Mycotoxins are secondary metabolites produced by filamentous fungi that usually contaminate food products. Coffee is a natural product susceptible to mycotoxin contamination. The present study evaluates the presence of nivalenol, deoxynivalenol, T-2 and HT-2 Toxin, diacetoxyscirpenol, aflatoxin B₁, aflatoxin B₂, aflatoxin G₁, aflatoxin G₂, fumonisin B₁, fumonisin B₂, ochratoxin A, zearalenone, enniatin A, enniatin A₁, enniatin B, enniatin B₁, and beauvericin in coffee samples, using liquid chromatography tandem mass spectrometry (LC-MS/MS). The results show that zearalenone was not present in any sample. In the positive samples the contents of fumonisins ranged from 58.62 to 537.45 μg/kg, emerging mycotoxins ranged from 0.10 to 3569.92 μg/kg, aflatoxins ranged from 0.25 to 13.12 μg/kg, and trichothecenes, excepting nivalenol, ranged from 5.70 to 325.68 μg/kg. Nivalenol presented the highest concentrations, from 0.40 to 25.86 mg/kg. Ochratoxin A ranged from 1.56 to 32.40 μg/kg, and five samples exceeded the maximum limit established by the European Commission.     

机加工孔套管抗挤压强度有限元分析

套管屈服强度直接影响套管抗挤压性能，套管在加工孔过程中可能诱发孔眼附近材料发生金属相变，导致套管屈服强度不再均匀分布，进而影响套管抗挤压强度。在相同工况下，对比了P110完整套管和机加工孔套管的抗挤压强度，以此为参照组分析了相变区域面积和相变区域屈服强度对机加工孔套管抗挤压强度的影响。结果表明，机加工孔会改变材料屈服强度，进而影响套管抗挤压性能。随金属相变区域屈服强度减小，机加工孔套管抗挤压强度减弱；当金属相变区域屈服强度增大时，机加工孔套管抗挤压强度增强。且机加工孔套管相变区域面积对机加工孔套管抗挤压强度的影响随相变区域屈服强度增加而逐渐削弱。     

基于旋翼负压混合吸附的爬壁清洗机器人系统动力学性能研究

针对爬壁清洗机器人越障时,负压装置的吸附力下降导致吸附不稳定的问题,设计了一种旋翼负压混合吸附工作的多边形履带清洗机器人,并对爬行稳定性及越障性能进行了动力学分析。首先根据机器人爬壁的运动原理,建立机器人沿玻璃幕墙上的动力学模型,计算出电机理论驱动力矩;其次分析机器人在跨越障碍过程中的运动模型,结合与壁面接触的实际受力状态,对越障过程中关键阶段的本体倾翻、滑移两种失效形式进行运动学和动力学分析;然后根据玻璃幕墙实际的障碍高度,确定多边形履带的参数和理论驱动力矩的大小,并研制了实验样机进行爬行和越障试验,结果表明所设计的机器人具有良好的越障性能。     

不同制样方法对直流辉光放电质谱法测定氮化硼中27种杂质元素的影响

讨论了3种制样方法对直流辉光放电质谱法(dc-GDMS)检测氮化硼中的Na、Mg、Al、Si等27种杂质元素的影响。3种制样方法分别如下所示:方法1,直接把氮化硼压在铟薄片上;方法2,把氮化硼压在铟薄片上后,再盖上一层铟罩;方法3,把压碎后的氮化硼放在针状钽勺上。在优化的辉光放电参数下对比了3种不同制样方法对基体信号强度的影响。试验表明:在方法1中,当氮化硼尺寸约为3mm×3mm,厚度小于1mm时,基体¹¹B的信号可达1.8×10⁷ cps;在方法2中,选择铟孔大小合适的铟罩,基体¹¹B的信号可达1.0×10⁷ cps;方法3获得基体信号强度比方法1、方法2高一个数量级。大部分元素在中分辨率下可获得较好的结果,而对于在高分辨率下也较难分离的元素,可选择丰度较低的同位素在中分辨率下进行测定,如Ge选择⁷⁰Ge⁺,Se选择⁸²Se⁺,Cd选择¹¹¹Cd⁺,Sn选择¹¹⁹Sn⁺,Ag选择¹⁰⁹Ag⁺,Pt选择¹⁹⁴Pt⁺。氮化硼中的杂质元素含量可通过样品片中待测元素含量减去来自于铟薄片或钽勺中该元素贡献的含量来计算获得。将样品平行测定5次,相对标准偏差均在20%以内。对于Al、Si、Ti等元素的测定,3种制样方法的测定结果基本一致;方法1、方法2中检测到的In含量较大,使得铟中的Ni、Cu对氮化硼的测定值影响较大;方法3由于钽中Fe、Cu的贡献导致氮化硼中Fe、Cu的检测值较大,但方法3获得的基体信号强度大,可降低部分元素的检出限,如Cr、Mn、Ga、Ge等。综上所述,方法3为优选方法。