水化硅酸钙纳米压痕分子动力学模拟方法优化

针对水化硅酸钙纳米压痕模型忽视了压头与基底之间相互作用的问题，由尺寸差异引起的金刚石压头难以计算的问题，以及Wittmann模型无法得到实际接触面积的问题，提出了新的模型与计算方法．结合分子动力学方法，采用金刚石压头-Wittmann模型基底的组合方式构建无定形态水化硅酸钙纳米压痕试验模型．在建模阶段，考虑到压头模型与基底模型粒子间尺寸差异，提出了等比例替换模型，通过公式推导并就不同尺寸模拟结果验证了等比例替换模型的可行性．在计算阶段，提出了局部前处理的弛豫方法进行模拟．确定最大荷载位置处的接触面积为546 nm2，进而求出水化硅酸钙模型硬度H为0.84 GPa、折合模量Er为30.52 GPa．并通过纳米压痕试验，验证了模拟结果的准确性，证明了模型的科学性，对今后水化硅酸钙(C-S-H)纳米层面的模拟具有重要借鉴意义．     

含水合物沉积物多相渗流特性研究进展

天然气水合物作为一种储量大、无污染的清洁能源近些年受到了广泛关注. 近20年来,中国进行了较大范围的陆海域天然气水合物储层勘探与储量预测.2017年,中国地质调查局牵头对南海神狐海域的天然气水合物进行了基于降压渗流原理的试验性开采.国内外已进行的水合物试采工程面临着气体产量低、出砂较多等问题,其最主要的原因之一是开发过程中沉积物内复杂多相渗流机理尚不明晰.本文综述了平行毛细管模型、Kozeny模型等广泛应用于天然气水合物开发渗流分析的理论模型,对比分析了水合物开发多尺度渗流过程模拟方法,简述了国内外含水合物沉积物渗透率测试、渗流过程中沉积物物性演变以及水合物开采室内模拟等方面的渗流实验进展,总结了矿场尺度的天然气水合物储层开采过程中产气数值模拟手段,展望了多相渗流模型、储层原位含水合物样品室内测试及结构与物性演化、矿场尺度数值模拟与水平井压裂技术等应用研究的未来方向与挑战.      

pH/temperature double responsive behaviors and mechanical strength of laponite‐crosslinked poly(DEA‐co‐DMAEMA) nanocomposite hydrogels

A nanocomposite (NC) hydrogel crosslinked by inorganic Laponite XLG was successfully synthesized via in situ free radical polymerization of monomers N,N‐diethylacrylamide and (2‐dimethylamino) ethyl methacrylate (DMAEMA). Polymerization was carried out at room temperature due to the accelerating effect of DMAEMA. The as‐prepared hydrogels displayed controlled transformation in optical transmittance and volume in response to small diversification of environmental factors, such as temperature and pH. The compressive strength of swollen D_6:1G₆ hydrogels was as high as 2219 kPa while compressive strain was 95%. Cyclic compression measurement exhibited good elastic properties of NC hydrogels. This work provides a facile method for fabricating stimuli‐responsive hydrogels with superior mechanical property. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 876–884     

Attapulgite grafted with polystyrene via a simultaneous reverse and normal initiation atom transfer radical polymerization

The surface grafting of attapulgite (ATP) with polystyrene (PS) was established via a simultaneous reverse and normal initiation atom transfer radical polymerization (SR&NIATRP). 4‐(chloromethyl)phenyltrimethoxysilane (CMPTMS) chemical bounded on the surface of ATP (ATP‐Cl, Cl‐I) was prepared via one‐step self‐assembly. SR&NI ATRP of styrene was conducted using CuCl₂ complex tris(2‐(dimethylamino)ethyl)amine (Me₆‐TREN) as the catalytic system, initiated by 2,2‐azobis(isobutyronitrile) (AIBN) and ATP‐Cl. FT‐IR, XRD, XPS, TGA and TEM data were consistent with the grafting of benzyl chloride groups and PS chains on ATP surface. The controllability of polymerization was investigated by the kinetics behavior under different molar ratio of AIBN and CuCl₂. The obtained polymer possessed a uniform distribution of molecular weights with a lower polydispersity index of 1.2～1.4. The relationship between polymerization on the surface of ATP and in solution was discussed in detail based on TGA data of hybrid particles and GPC trace of free polymer in solution. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1508–1516     

西北太平洋表层沉积物地球化学特征及其物源指示意义

为深入了解西北太平洋表层沉积物地球化学特征及物质来源，对大洋40航次在西北太平洋马尔库斯-威克海山区采集的表层沉积物进行了全岩地球化学和黏土矿物测试分析。结果表明，研究区表层沉积物稀土元素（REE)平均质量分数为302.87×10^-6，北美页岩标准化稀土配分模式与黄土相似，并具Ce轻微负异常和Eu无异常特征。稀土配分模式、判别函数（discriminant functions,DF）、M/I（蒙脱石/伊利石）及涂片鉴定等结果指示沉积物物源具有多源性，主要为陆源风尘物质，并受海洋自生物质的强烈影响，海山玄武岩及其蚀变产物和硅质生物也有一定的贡献。研究区沉积物稀土特征既不同于边缘海沉积物，也有别于远洋沉积物，而与弧后盆地沉积物类似。结合1/δCe-LREE/HREE和LREE/HREE-Y/Ho判别图解结果，研究区沉积物物源结构属性应介于边缘海沉积物与远洋沉积物之间，为洋陆过渡区沉积。     

石英砂粒径对水合物沉积物力学性质的影响

利用自主研发的水合物沉积物原位合成与力学性质测试的高压低温三轴仪,通过多级加荷的试验方法,以不同粒径的砂粒作为沉积物骨架进行三轴压缩试验,得到了剪切过程的应力-应变关系曲线,以及不同粒径尺寸沉积物的强度,还有剪切过程中的体积变化关系。结果表明:含水合物沉积物强度随着沉积物粒径尺寸的增大而增强;在降压剪切过程中,所有粒径的水合物沉积物式样均有明显的剪缩现象。     

Accurate Geometry and Non-Covalent Interactions in 1-Phenylethanol and its Monohydrate: A Rotational Study

The pure rotational spectra of 1-phenylethanol and its monohydrate were measured by using a pulsed jet Fourier transform microwave spectrometer. One conformer of the 1-phenylethanol monomer with the trans form was observed in the pulsed jet. The experimental values of rotational constants of ten isotopologues, including eight mono-substituted ¹³C and one D isotopologues, allow an accurate structure determination of the skeleton of 1-phenylethanol. For its monohydrate, only one isomer has been observed, of which 1-phenylethanol adopts the trans form and binds with water through an O−H⋅⋅⋅O_w and an O_w−H⋅⋅⋅π hydrogen bond. Each rotational transition displays a doublet with a relative intensity ratio of 1 : 3, due to a hindered internal rotation of water around its C₂ axis. This study provides the information on accurate geometry of 1-phenylethanol (PE) and large amplitude motion of water in the PE monohydrate.     

Antibacterial and antifungal LDPE films for active packaging

Active antimicrobial packaging is a promising form of active packaging that can kill or inhibit microorganism growth in order to maintain product quality and safety. One of the most common approaches is based on the release of volatile antimicrobial agents from the packaging material such as essential oils. Due to their highly volatile nature, the challenge is to preserve the essential oils during the high‐temperature melt processing of the polymer, while maintaining high antimicrobial activity for a desired shelf life. This study suggests a new approach in order to achieve this goal. Antimicrobial active films are developed based on low‐density polyethylene (LDPE), organo‐modified montmorillonite clays (MMT) and carvacrol (used as an essential oil model). In order to minimize carvacrol loss throughout the polymer compounding, a pre‐compounding step is developed in which clay/carvacrol hybrids are produced. The hybrids exhibit a significant increase in the d‐spacing of clay and enhanced thermal stability. The resulting LDPE/(clay/carvacrol) films exhibit superior and prolonged antibacterial activity against Escherichia coli and Listeria innocua, while polymer compounded with pure carvacrol loses the antibacterial properties within days. The films also present an excellent antifungal activity against Alternaria alternata, used as a model plant pathogenic fungus. Furthermore, infrared spectroscopy analysis of the LDPE/(clay/carvacrol) system displayed significantly higher carvacrol content in the film as well as a slower out‐diffusion of the carvacrol molecules in comparison to LDPE/carvacrol films. Thus, these new films have a high potential for antimicrobial food packaging applications due to their long‐lasting and broad‐spectrum antimicrobial efficacy. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Experimental investigation on the dissociation conditions of methane hydrate in the presence of imidazolium-based ionic liquids

In this work, the performance of nine ionic liquids (ILs) as thermodynamic hydrate inhibitors is investigated. The dissociation temperature is determined for methane gas hydrates using a high pressure micro deferential scanning calorimeter between (3.6 and 11.2) MPa. All the aqueous IL solutions are studied at a mass fraction of 0.10. The performance of the two best ILs is further investigated at various concentrations. Electrical conductivity and pH of these aqueous IL solutions (0.10 mass fraction) are also measured. The enthalpy of gas hydrate dissociation is calculated by the Clausius–Clapeyron equation. It is found that the ILs shift the methane hydrate (liquid + vapour) equilibrium curve (HLVE) to lower temperature and higher pressure. Our results indicate 1-(2-hydroxyethyl) 3-methylimidazolium chloride is the best among the ILs studied as a thermodynamic hydrate inhibitor. A statistical analysis reveals there is a moderate correlation between electrical conductivity and the efficiency of the IL as a gas hydrate inhibitor. The average enthalpies of methane hydrate dissociation in the presence of these ILs are found to be in the range of (57.0 to 59.1) kJ ⋅ mol⁻¹. There is no significant difference between the dissociation enthalpy of methane hydrate either in the presence or in absence of ILs.