Effects of GC temperature and carrier gas flow rate on on‐line oxygen isotope measurement as studied by on‐column CO injection

Although deemed important to δ¹⁸O measurement by on‐line high‐temperature conversion techniques, how the GC conditions affect δ¹⁸O measurement is rarely examined adequately. We therefore directly injected different volumes of CO or CO–N₂ mix onto the GC column by a six‐port valve and examined the CO yield, CO peak shape, CO–N₂ separation, and δ¹⁸O value under different GC temperatures and carrier gas flow rates. The results show the CO peak area decreases when the carrier gas flow rate increases. The GC temperature has no effect on peak area. The peak width increases with the increase of CO injection volume but decreases with the increase of GC temperature and carrier gas flow rate. The peak intensity increases with the increase of GC temperature and CO injection volume but decreases with the increase of carrier gas flow rate. The peak separation time between N₂ and CO decreases with an increase of GC temperature and carrier gas flow rate. δ¹⁸O value decreases with the increase of CO injection volume (when half m/z 28 intensity is <3 V) and GC temperature but is insensitive to carrier gas flow rate. On average, the δ¹⁸O value of the injected CO is about 1‰ higher than that of identical reference CO. The δ¹⁸O distribution pattern of the injected CO is probably a combined result of ion source nonlinearity and preferential loss of C¹⁶O or oxygen isotopic exchange between zeolite and CO. For practical application, a lower carrier gas flow rate is therefore recommended as it has the combined advantages of higher CO yield, better N₂–CO separation, lower He consumption, and insignificant effect on δ¹⁸O value, while a higher‐than‐60 °C GC temperature and a larger‐than‐100 µl CO volume is also recommended. When no N₂ peak is expected, a higher GC temperature is recommended, and vice versa. Copyright © 2015 John Wiley & Sons, Ltd.     

气基磁化焙烧回收包头稀土尾矿中铁的研究

试验采用磁化焙烧-磁选的方法来回收包头稀土尾矿中的Fe。考察了还原球团的粒径、焙烧温度、还原气体的成分、还原气气体流量、焙烧时间对于磁化焙烧回收Fe的影响。在焙烧温度为580℃,CO与CO2的浓度比为40∶60,还原气体气流量为1.2 L·min-1,焙烧时间为60 min的条件下对球团进行磁化焙烧,并将焙烧后的球团进行磨矿,使得-200目的物料占物料总重量的95%。将磨矿后的物料置于磁场强度为233 k A·m-1的磁选管中进行磁选,可以得到品位为60%左右的铁精矿,其铁回收率达到70%左右。     

运用系统动力学模型预测稀土战略储备规模

基于全球稀土资源的供需形势和中国稀土资源减少的趋势,运用系统动力学的模型来预测未来17年我国稀土资源储备量。选取了2000~2013的生产和消费数据,通过定量模拟计算中国稀土供需差波动系数,设计了稀土资源供需差波动范围分别为0%,20%的两个方案,模拟计算了两个方案的年储备量、累计储备量和储备量绝对值。方案一范围是(-0%,+0%),仿真预测出稀土未来17年累积储备量为720551 t,即战略储备规模达到720551 t,该方案下不论供需差发生如何波动,国家都会进行储备或释放调节;方案二范围是(-20%,+20%),预测出未来17年战略储备规模为461331 t,国家只需在这个范围外进行收储释放调节,从而调节市场供求,降低价格波动幅度。本文从不同供需差的波动系数来模拟计算储备量,目的是为国家相关部门在进行稀土储备决策时提供参考,可以根据我国经济景气状况和供需形势,以及稀土产业发展状况,进行不同规模的稀土储备。     

Modeling hydrate formation conditions in the presence of electrolytes and polar inhibitor solutions

In this paper, a new predictive model is proposed for prediction of gas hydrate formation conditions in the presence of single and mixed electrolytes and solutions containing both electrolyte and a polar inhibitor such as monoethylene glycol (MEG), diethylene glycol (DEG) and triethylene glycol (TEG). The proposed model is based on the γ–φ approach, which uses modified Patel–Teja equation of state (VPT EOS) for characterizing the vapor phase, the solid solution theory by van der Waals and Platteeuw for modeling the hydrate phase, the non-electrolyte NRTL-NRF local composition model and Pitzer–Debye–Huckel equation as short-range and long-range contributions to calculate water activity in single electrolyte solutions. Also, the Margules equation was used to determine the activity of water in solutions containing polar inhibitor (glycols). The model predictions are in acceptable agreement with experimental data. For single electrolyte solutions, the model predictions are similar to available models, while for mixtures of electrolytes and mixtures of electrolytes and inhibitors, the proposed model gives significantly better predictions. In addition, the absolute average deviation of hydrate formation pressures (AADP) for 144 experimental data in solutions containing single electrolyte is 5.86% and for 190 experimental data in mixed electrolytes solutions is 5.23%. Furthermore, the proposed model has an AADP of 14.13%, 5.82% and 5.28% in solutions containing (Electrolyte + MEG), (Electrolyte + DEG) and (Electrolyte + TEG), respectively.     

Ternary mutual diffusion coefficients of aqueous {l-dopa (1) + β-CD (2)} solutions at T = 298.15 K

Ternary mutual diffusion coefficients (D₁₁, D₂₂, D₁₂ and D₂₁) measured by the Taylor dispersion method are reported for aqueous solutions of {levodopa (l-dopa) + β-cyclodextrin (β-CD)} solutions at T = 298.15 K and concentrations up to 0.007 mol · dm⁻³. Significant effects on the diffusion were observed, suggesting interactions between this carbohydrate and l-dopa. Support for this came from ¹H NMR spectroscopy, which shows that these effects are due to formation of 1:1 (β-CD:l-dopa) complexes.     

Theoretical study on the degradation mechanism of methamidophos and chloramine phosphorus with OH radicals

Theoretical investigation on the gas‐phase degradation reaction mechanism of methamidophos (MAP) and chloramine phosphorus (CHP) with OH radicals is performed. The equilibrium geometries and the harmonic vibration frequencies of the stationary points are obtained at M06‐2x/6‐31+G(d,p) level, and the higher‐level energetic information is further refined at M06‐2x/6–311++G(3df,2p) level. The rate constants for the 14 reaction channels are calculated by the improved canonical variational transition state theory with small‐curvature tunneling correction over the temperature range 200–2000 K. The three‐parameter expressions of k₁(T) = 1.53 × 10^?19T^2.74exp(?1005.12/T), k₂(T) = 1.36 × 10^?20T^3.02exp(?1259.56/T) are given. The total rate constants of all reaction channels of MAP with OH radicals are in good agreement with the available experimental data. Our results indicate that the H‐abstraction reactions on methyl are the major channels for the reaction of MAP and CHP with OH radicals. © 2015 Wiley Periodicals, Inc.     

Dependency of dynamic interlaminar shear strength of composites on test technique used

Studies are presented on dependency of dynamic interlaminar shear (ILS) strength on the experimental technique used for a typical plain weave E-glass/epoxy composite. Dynamic ILS strength was determined based on two experimental techniques, namely torsional split Hopkinson bar (TSHB) apparatus using thin walled tubular specimens and compressive split Hopkinson pressure bar (SHPB) apparatus using single lap specimens. The results obtained from these techniques are compared. In general, it is observed that dynamic ILS strength for composites obtained by TSHB testing using thin walled tubular specimens is lower than the dynamic ILS strength obtained using single lap specimens in compressive SHPB. The issues involved in TSHB testing of thin walled tubular specimens made of composites are discussed and the reasons for reduced dynamic ILS strength using thin walled tubular specimens are highlighted. Finite element analysis (FEA) of thin walled tubular specimens made of composite and resin subjected to quasi-static torsional loading is presented. Using FEA results, the reasons for lower ILS strength of composite thin walled tubular specimens are substantiated.     

Synergistic effect of maleimido phenyl urea derivatives mixed with some commercial stabilizers on the efficiency of thermal stabilization of PVC

Four novel antimicrobial maleimido phenyl urea stabilizers 1–4 were synthesized from N-[4-(chlorocarbonyl) phenyl] maleimide with phenyl urea and its derivatives (p-methyl, o-chloro and p-carboxy). The effect of mixing maleimido phenyl urea stabilizer 2 with each of the reference stabilizers, dibasic lead carbonate (DBLC), cadmium-barium-zinc stearate (Cd-Ba-Zn stearate) or n-octyltin mercaptide (n-OTM), on the stabilization efficiency in thermal degradation of rigid PVC at 180 °C in air, has been investigated. Mixing was effected in the range of 0–100 wt% of stabilizer 2 relative to each of the reference stabilizers. The stabilizing efficiency was evaluated by measuring the length of the thermal stability period (Ts), the period during which no detectable amount of hydrogen chloride gas could be observed, and also from the rate of dehydrochlorination as measured by continuous potentiometric determination, and by the extent of discoloration of the degraded polymer samples. The results show a true synergistic effect from the combination of stabilizer 2 with any of the reference stabilizers. Mixing of the stabilizers improves the Ts values, decreases the rate of dehydrochlorination and lowers the extent of discoloration of the polymer. The maximum synergism was attained when stabilizer 2 is mixed with either of the three reference stabilizers in equivalent weight ratio (50%/50%). The observed synergism may be attributed to the different mechanisms by which the investigated and the reference stabilizers work.     

The free retraction of natural rubber: A momentum-based model

The free retraction of vulcanised strips of natural rubber released from simple uniaxial deformation is studied using high speed cinematography in the context of a simple momentum theory. Good agreement between the theory and experiment is observed when vulcanisates are released from stresses below 1 MPa, which corresponds to tensile strains rates below 1 × 10³ s⁻¹. Above this critical stress and corresponding strain rate value, an increasing dispersion is observed in the form of slowing down of the characteristic retraction pulse, and also by a relaxation of strain ahead of the pulse front (a dispersion of the pulse). Holding samples at high strains for an extended period of time prior to releasing results in a further, significant retardation of the retraction pulse velocity. These effects are related to the increasing non-linearity of high strain rate retraction stress–strain behaviour. Energy balance arguments show that the dispersion of the retraction pulse is a prerequisite for pulse propagation, and that its magnitude underpins the deviation from the momentum model outlined in this paper.