水在聚乙烯醇/水体系中的状态及氢键作用

水在聚乙烯醇(PVA)中的状态直接影响PVA的热塑加工.采用DSC和Raman光谱研究了水含量对其在PVA中的状态及氢键作用的影响.结果表明:水在PVA中以3种状态存在,随水含量增加,非冻结合水比例减小,可冻结合水和自由水比例增加.通过高斯分峰可将Raman光谱水的羟基伸缩振动峰分为5种羟基振动峰叠加,分别代表多氢键结合水分子的羟基对称与反对称伸缩振动,双氢键结合水分子羟基伸缩振动,单氢键结合水分子羟基伸缩振动,无氢键或弱氢键相互作用水分子的羟基伸缩振动.水含量增加,单氢键结合与多氢键结合水分子含量增加,而双氢键结合与无氢键结合水分子含量减少.     

温压条件下蒙脱石水化的分子动力学模拟

从深层页岩的黏土矿物特征出发,通过分子动力学模拟研究了含水量、温度和压力条件对蒙脱石水化中物质传导与力学弱化特征的影响规律。研究表明:随含水量的增加,层间距增大,但温压条件对蒙脱石晶体的层间距影响较小;含水量和温压条件对蒙脱石水化过程中水分子与钠离子的传导与分布和力学特征影响显著。随含水量增加、温度升高和压力降低,水分子和钠离子的扩散系数增加,侵入黏土晶层的能力增强,且钠离子配位数减少,使蒙脱石力学劣化效应更显著。     

水分子和离子在地聚合物胶凝材料中的分子动力学研究

地聚合物是一种具有三维网状结构的水泥基胶凝材料,其主要水化产物是水合硅酸铝钠凝胶(NASH).在工程应用中,氯盐侵蚀与硫酸盐侵蚀是影响耐久性的主要原因.运用分子动力学方法,研究NaCl溶液与Na2SO4溶液在NASH凝胶纳米孔道中的传输特性.结果表明,NaCl溶液与Na2SO4溶液在凝胶孔道的非饱和传输过程中,呈现出明显的毛细吸附现象,NASH凝胶界面呈现亲水性与电负性.Na2SO4溶液的侵入速率明显低于NaCl溶液,硫酸根离子对水分子侵入的抑制作用强于氯离子.     

钾基蒙脱石的分子力学和分子动力学模拟

利用分子力学(molecular mechanics,MM)和分子动力学(molecular dynamics,MD)模拟了K-蒙脱石层间阳离子和水的结构及动力学特征,并将模拟的X射线衍射结果与实验值进行比较.结果显示:在K-蒙脱石的最优构型中,层间距随着水含量的增加而增大;X射线衍射的模拟结果和实验结果一致;K+的位置和蒙脱石层间电荷位置有关,K+在1,2层水合物中依附于黏十的表面附近,而在3层水合物中K+则脱离表面开始向层中其它方向扩散.水分子在黏土层间分散于各个方向,而且存在水质子和K+竞争电荷位置的现象.水和K+在钾基蒙脱石中的活动性低于其在水中和溶液中的活动性.径向分布函数分析结果表明K+组织水分子的能力有限,说明K+对蒙脱石的水化膨胀起抑制作用.     

褐煤含氧官能团对褐煤中水分特性的影响

褐煤中的含氧官能团与褐煤中的水分具有较为明显的交互作用.利用不同浓度的氢氧化钠、盐酸及双氧水对褐煤进行化学改性,通过DSC(differential scanning calorimetry)分析改性褐煤样品中水分特性的变化,同时结合FTIR手段分析对改性前后的煤样化学官能团进行表征.结果表明,氢氧化钠改性后样品中自由水及结合水分的含量增加,盐酸溶液改性后样品水分冻结特性与原煤基本相同,双氧水溶液改性后的煤样中自由水含量减少,结合水基本消失.FTIR表征结果表明,—OH官能团增加是影响煤样中自由水及结合水分含量增加的主要原因.     

Tween20/40的CMC测定及NaCl的影响

以高浓度碘的水溶液作为显色剂,用紫外吸收分光光谱法测定非离子表面活性剂Tween20和Tween40的临界胶束浓度（CMC）分别为519×10-5 mol/L和190×10-5 mol/L,再采用黏度法测定这2种表面活性的CMC分别为500×10-5 mol/L和193×10-5 mol/L,并研究了不同浓度的NaCl溶液对临界胶束浓度和黏度的影响。结果表明黏度法的测定结果与文献基本接近。当体系中存在NaCl溶液时,CMC值基本无变化,而溶液的相对黏度随着盐的浓度增大呈下降趋势。当NaCl为定值时,体系的相对黏度呈现先增加,在CMC之后,体系黏度基本保持不变。 关键词：分光光度法;黏度;临界胶束浓度     

水泥基材料中自由氯离子浓缩的影响因素

研究了NaCl浸泡液浓度、浸泡时间、养护时间、浸泡温度和压滤压力对水泥基材料孔溶液中氯离子浓缩的影响。结果表明:在NaCl溶液中浸泡56 d后,水泥基材料试件孔溶液中自由氯离子浓度与浸泡液的氯离子浓度有很好的线性关系。当浸泡液浓度≤0.3 mol/L时,自由氯离子浓度比浸泡液的氯离子浓度至少高40%;当浸泡液浓度>0.3mol/L,自由氯离子浓度只稍微高出浸泡液的氯离子浓度。浸泡后的前63d,自由氯离子浓度随浸泡时间增加逐渐增加,随后,自由氯离子浓度开始随浸泡时间增加而降低。孔溶液中氯离子浓度随养护时间增加而减少。浸泡温度和压滤压力对自由氯离子浓缩没有太大的影响。双电层和试样孔结构压滤前后变化是水泥基材料孔溶液中的自由氯离子浓度升高的主要原因。     

三甲基壳聚糖季铵盐水凝胶的制备及性能

采用反应活性强和交联条件温和的二乙烯基砜为交联剂,制备了N,N,N-三甲基壳聚糖季铵盐水凝胶（TMCG）并研究了TMCG的溶胀行为、水的状态和分布以及力学性能等。结果表明,TMCG在水中溶胀迅速,平衡溶胀度达40倍,并且具有离子响应性;水分子在TMCG中以自由水、可冻结的结合水和非冻结的结合水三种形式存在,其非冻结的结合水含量随交联剂浓度的增加而增大。TMCG具有良好的力学性能,拉伸强度达13.8 MPa,断裂伸长率达135.3%。     

小角激光光散射法测定纤维素硫酸钠的分子量

采用小角激光散射法测定了纤维素硫酸钠(NaCS)的分子量,考察了盐离子及其浓度对分子量测定的影响. 结果表明,取代度分别为0.28, 0.40, 0.73的3个样品的分子量分别为879.8, 593.5和226.9 kDa,盐离子浓度为0.05~0.075 mol/L时测定较准确,盐离子浓度为0~0.05 mol/L时光散射强度精密度较低,不利于分子量测定,粘度变化较大,表明此时NaCS分子处于膨胀伸展状态,不利于光散射法测定分子量.     

甲基硅酸钾页岩抑制剂抑制蒙脱石水化机理的分子模拟

有机硅页岩抑制剂相较于传统的KCl抑制剂具有不会腐蚀钻具、更加环保等优点,因此有机硅钻井液体系得到广泛应用。利用分子模拟方法,选择甲基硅酸钾、甲基硅酸钠、KCl和NaCl作为研究对象,构建了四种抑制剂的分子模型和钠蒙脱石晶体模型。通过分子动力学方法模拟发现,甲基硅酸钾能够抑制蒙脱石层间Na~+的水化作用,限制水分子和Na~+的自扩散运动,并提高钠蒙脱石晶体的力学性能。对比四种页岩抑制剂的各项模拟结果发现,甲基硅酸钾的抑制效果最佳,其次是甲基硅酸钠和KCl,NaCl的抑制效果最差。从离子的角度看,K~+的抑制效果优于Na~+,甲基硅酸根的抑制效果优于Cl~-,这是由于K~+能镶嵌于钠蒙脱石晶层表面的硅氧六元环中,而甲基硅酸根能够通过氢键吸附于硅氧六元环上,它们均能使蒙脱石晶层发生不完全水化从而抑制蒙脱石的水化膨胀。     

含盐蒙脱石中甲烷水合物的生成/分解特性及离子分布研究

目前,天然气水合物成藏和开采是新能源开发应用的热点,但海域沉积物中天然气水合物的形成/分解特性,及盐离子对水合物稳定性的影响等关键问题亟待解决。利用天然气水合物原位取样技术对甲烷水合物在含盐多孔介质中生成和分解过程进行原位扫描电镜(Scanning Electron Microscopy, SEM)测试和能谱分析(Energy Dispersive Spectrometry, EDS),系统研究了含0.5 mol/L NaCl溶液的蒙脱石中甲烷水合物生成、分解过程中形貌的变化及离子分布特征。研究发现水合物生成和分解过程元素分布发生明显改变,水合物生成的排盐效应使得NaCl在水合物颗粒与颗粒交结处以水合盐离子的形成存在,并且Na+和Cl-在蒙脱石表面分层排布。水合物生成后蒙脱石表面呈独立颗粒状,水合物分解后蒙脱石表面凹陷并形成微小的气体通道,并且水合物分解后蒙脱石的骨架堆积结构发生改变。研究得出水合物成核、生长、分解过程均在特定基元颗粒间是独立进行的,并且生长与分解过程与水合物晶胞结构有关。     

纳米碳酸钙对水泥石氯离子结合量的影响

混凝土孔溶液中的自由氯离子转化为结合氯离子可有效降低沿海、盐湖地区钢筋混凝土结构中的钢筋的腐蚀程度。以纳米碳酸钙掺量和氯离子浓度为变量,研究了纳米碳酸钙对水泥石氯离子结合量的影响,采用电位滴定法测定结合氯离子含量,根据氯离子等温吸附理论绘制结合氯离子与自由氯离子的拟合关系曲线来分析水泥石的氯离子结合能力,通过XRD和热重分析研究水泥石的氯离子结合机理。结果表明:纳米碳酸钙的掺入提高了水泥石的氯离子结合量,当其掺量达3%(质量分数)时,水泥石的氯离子总结合量最大;随着氯离子浓度的提高,掺纳米碳酸钙的水泥石氯离子结合量会相应增加;纳米碳酸钙的掺入可以加快水泥水化,促进C-S-H凝胶和Friedel's盐的生成,有利于水泥石的氯离子物理吸附和化学结合。     

Experimental investigation and modeling on the dissociation conditions of methane hydrate in clayey silt cores

As the majority of global natural gas hydrate reserve, the dissociation conditions of hydrate in clayey silts are of great significance for its efficient production. In this work, the dissociation conditions of methane hydrate in clayey silt cores were experimentally measured by step-heating method at the temperature range of 280.76–289.55 K and pressure range of 8.11–15.03 MPa, respectively. Various cores including quartz powder, montmorillonite, and South China Sea sediments at the water content range of 20%–33% were used for investigation. The results showed that the dissociation temperatures of methane hydrate in clayey silt cores depressed compared to bulk hydrate. The grain size, salinity, and lithology of clayey silt cores significantly affect the dissociation conditions of hydrate. In comparison to grain size, salinity, and lithology had a more significant influence on the equilibrium temperature depression. The dissociation temperature depression of methane hydrate was considered as a consequence of the water activity depression which is caused by the effect of capillary, salt, or clay. A water activity meter was used to measure the water activity in clayey silt cores. The influence of salt component and mineral characteristics on the water activity was investigated. By combining the measured water activity data with the Chen-Guo model, a novel water activity measurement (WAM) method for the hydrate dissociation conditions prediction was proposed. With the maximum deviation less than 12%, the predicted results are in good agreement with the experimental data. It demonstrated that the WAM method could effectively predict the dissociation conditions of methane hydrate in clayey silts with convenience and accuracy.     

游离氧化钙对水泥浆体体积膨胀的影响机制

硬化水泥桨体由于水泥中游高氧化钙水化会导致体积膨胀。研究发现,浆体的体积膨胀除与ｆＣａＯ的含量和活性有关外,还与浆体的结构和性能密切ｆＣａＯ水化形成Ｃａ（ＯＨ）２时,不仅固相体积增加,而且空隙体积亦增加,而且空隙体积亦增加。ｆＣａＯ在浆体硬化结构形成之后水化,且其水化产物成堆聚集时才会导致浆体体积膨胀。     

Rheological properties of sodium montmorillonite dispersions

The rheological behaviour of dispersions of montmorillonite in water is highly pH- and salt-dependent. This is exemplified for 4% (wt/wt) dispersions of montmorillonite from Wyoming and its homoionic sodium form in water, 0.01 M NaCl and 0.1 M NaCl solutions, at different pH and at temperatures from 20°C to 60°C. Generally, the shear stress (for instance, at shear rates of about 100 s⁻¹) decreases sharply in an acidic medium to a minimum around pH 6 (pH 7.5 for the homoionic sodium form) and then increases again very strongly. Thixotropic and antithixotropic behaviour depend on pH, salt concentration and temperature.The presence of Ca²⁺ ions (molar ratio Na/Ca about 6.5/1) in the “pristine” montmorillonite affects the type of flow very sensitively. Ca²⁺ ions convert diffuse ionic layers into quasicrystalline structures with a central layer of gegen ions. Attractive potentials are then created in the contact regions between the particles, even in diluted salt solutions. Formation of band-like structures (as in the “Bändermodell” of A. Weiss) is promoted.Further, results are reported on the influence of particle size (fractions < 0.06 μm to 2 μm) on the flow behaviour at different concentrations of homoionic sodium montmorillonites from Amory and Cameron.     

海底沉积物层CO2封存中水合物研究进展

海底沉积物层内CO2封存被认为是缓解全球气候变暖的有效途径,本文介绍了CO2封存时水合物自封机理、水合物形成条件和水合物稳定带范围,描述了水合物生成动力学研究现状,包括成核动力学、生长动力学以及水合物结晶过程驱动力,水合物的成核模型有成簇成核模型、成簇成核扩展模型、界面成核模型、Chen-Guo模型,水合物生长动力学模型有Englezos、Kvamme生长模型、指数增长模型、流体流动模型以及LB模型,水合驱动力有化学势差、温差、吉布斯自由能差、浓度差、压差或逸度差。总结了多孔介质渗透率和孔隙度随水合物成核和生长的演化关系,有KC模型、NR模型、平行毛细管束模型、渗透率下降模型和Morisdis相对渗透率模型,最后介绍了CO2水合实验情况,展望了CO2海底沉积物层内封存与水合物相关的科学问题。     

Influence of the Salt Concentration on the Properties of Salt‐Free Polyelectrolyte Complex Membranes

Polyelectrolyte complexes (PECs) prepared by solution mixing of cationic poly(diallyldimethylammonium chloride) and anionic poly(sodium 4‐styrene sulfonate) with various NaCl content are processed into films. Salt‐free (SF‐PEC) membranes are produced by rinsing the PEC in water overnight. The main finding of this paper is that SF‐PEC films have different properties depending on the NaCl concentration used during the processing step. Dynamic mechanical analysis measurement confirms that hydrated SF‐PEC film processed from higher salt content has a higher modulus than when processed without salt and the glass transition temperature appears to shift to higher values. Processing the PECs films in the presence of salt also has an interesting effect on their shape memory characteristics. SF‐PEC films prepared with high‐salt concentration are shown to maintain a programmed temporary shape better than materials prepared with low salt, while recovery is possible within a short period of time when immersed in hot water.     

Size Control Mechanism for Bio-Nanoparticle Fabricated by Electrospray Deposition

The present work employed a molecular dynamics method to investigate the effect of NaCl concentration on the deformation, breakup, and evaporation characteristics of bio-nanodroplets under a strong electric field. It aims to reveal the size control mechanism for a nanoparticle produced by electrospray deposition. The results show that when the droplet dissolves NaCl, it is elongated to be a longer “spindle” by the electric field force, compared to the droplet without NaCl, and several small clusters are ejected from two tips of the spindle due to the hydration effect of Na⁺ and Cl^?. In addition, the formation of ion pairs is observed when the droplet dissolves NaCl. The NaCl concentration affects the hydration degree and the formation of ion pairs significantly, which leads to different spindle lengths and number of clusters. The longer spindle and the larger cluster number could enlarge the free surface area and remarkably accelerate evaporation. Fabrication of smaller bio-nanoparticle requires both a faster evaporation rate and larger cluster number, which can be achieved by selecting an appropriate NaCl concentration.     

Concentration of sodium chloride in aqueous solution by chlorodifluoromethane gas hydrate

The decomposition temperature and pressure (quadruple point) of chlorodifluoromethane (R22) gas hydrate in aqueous sodium chloride (NaCl) solution was measured at different NaCl concentrations in the solution as a phase diagram. The operative concentration curve of NaCl was obtained as a function of temperature. The maximum decomposition temperature of R22 hydrate was about 290 K at 0.9 MPa pressure, and it decreased as the NaCl concentration increased in the solution. R22 hydrate caused supercooling, and the supercooling occurrence temperature was much lower than the decomposition temperature. The ultrasonic charge reduced the supercooling of hydration effectively even though the ultrasonic charge did not change the decomposition temperature at all. The concentration experimental results from the several NaCl solutions having different NaCl concentrations were in good agreement with the theoretical operative concentration curve for NaCl.     

十二烷基苯磺酸钠表面张力的研究

通过表面张力的测定,研究了浓度、温度对溶液表面张力的影响,同时考察无机盐浓度对溶液表面张力的影响.结果表明:十二烷基苯磺酸钠溶液表面张力随浓度的增加、温度的升高和无机盐浓度逐渐的增大而降低,最终确定其CMC值为1.47×10-3mol/L,由于键能和水合离子半径的原因,NaCl对十二烷基苯磺酸钠表面张力的影响明显于KCl.