Highly ordered TiO_2 nano-pore arrays fabricated from a novel polymethylmethacrylate/polydimethylsiloxane soft template

A novel soft polymer template containing a double-layer structure,which includes a thin layer of polymethylmethacrylate(PMMA)used as a pattern layer and a thicker layer of polydimethylsiloxane(PDMS)used as a back layer,was fabricated from a replica molding process.Anodic aluminum oxide(AAO)template was used as the replica mold to be replicated to the polymethylmethacrylate layer by a thermal infiltration process under a vacuum condition.Results indicate that PMMA/PDMS soft templates with different sizes could be easily fabricated from the as-prepared AAO replica mold.The PMMA/PDMS soft templates were then employed to imprint a TiO_2 gel for achieving TiO_2 nano-pore arrays.After the imprinting process,the PDMS layer was firstly peeled off and the PMMA layer was then removed into acetonitrile,which can avoid any demolding problems like damages or distortions.The TiO_2 nano-pore arrays with the crystalline of anatase could be obtained at a heat treatment temperature of 450°C.

Mineralogy and Thermal Analysis of Natural Pozzolana Opal Shale with Nano-pores

Thermodynamic stability, microvoid distribution and phases transformation of natural pozzolana opal shale（POS） were studied systematically in this work. XRD analysis showed that opal-CT, including microcrystal cristobalite and tridymite, is a major component of POS. DTA and FT-IR indicated that there were many hydroxyl groups and acid sites on the surface of amorphous SiO2 materials. FE-SEM analysis exhibited amorphous SiO2 particles（opal-A） covering over stacking sequences microcrystal cristobalite and tridymite. Meanwhile, MIP analysis demonstrated that porosity and pore size distribution of POS remained uniform below 600 ℃. Because stable porous microstructure is a key factor in improving photocatalyst activity, POS is suited to preparing highly active supported.

Low Temperature Synthesis of Nano Porous 12CaO?7Al_2O_3 Powder by Hydrothermal Method

Single-phase insulating 12CaO？7Al_2O_3（C12A7） powder was synthesized using an optimized hydrothermal method. Pure phase of C12A7 was got at a comparatively lower temperature（c.a. 300 ℃） than that has been previously reported. The crystallite size of the synthesized C12A7 powder was 7±2 nm. The surface area values calculated for all the samples at a synthesis temperature range of 250-800 ℃ for 5 h were in the range of about 19-24 m^2/g, with pore sizes of 12-20 nm. This low-temperature-based synthetic strategy along with nano porous structures and a high surface area value can facilitate catalyst application.

Porous Properties of Nano-fibriform Silica from Natural Chrysotile

With the TEM and physical gas adsorption techniques, porous properties of nano-ribriform silica （MLD： 92.73%） from natural chrysotile are studied in this paper. The results indicate that porous nano-fibriform silica results from brucite octahedral sheets of nature chrysotile dissolved completely and Si-O tetrahedral sheets collapsed by acid leaching. Its length is at a micron or nanometer scale. There are two types of pores： pores among neighboring fibers and pores in nanoriber. These pores （less than 6.5 nm in diameter, mostly 2.1 nm and 3.8 nm） all belong to mesopores. The pores in fibers consist of those among SiO2 particles, those among aggregates, remnant nanotubes and capillary tubes. Nanoribriform silica proves better than the traditional silica as a carrier of catalyzer and a filler for reinforce rubber and plastics.

Synchrotron radiation facility-based quantitative evaluation of pore structure heterogeneity and anisotropy in coal

In order to quantify coal pore structure heterogeneity and anisotropy,synchrotron radiation SAXS(Small Angle X-ray Scattering)was applied to obtain the SAXS images of two different rank coal samples.The surface fractal dimension(D1)and pore fractal dimension(D2)were obtained by processing the image data.The pore structure heterogeneity of two coal samples was quantified by pore fractal dimension(D2).Pore fractal dimension of Xinzhouyao coal is 2.74 and pore fractal dimension of Tangshan coal is 1.69.As a result,the pore structure heterogeneity of Xinzhouyao coal is stronger than that of Tangshan coal.3D pore structure imaging was achieved by synchrotron radiation nano-CT.The selected Region of Interest(ROI)of coal sample was divided into a certain number of subvolumes.Pore structure heterogeneity was quantified by calculating the limit of the relative standard deviation of each subvolume’s porosity.The heterogeneity value of Xinzhouyao coal pore structure is 3.21 and the heterogeneity value of Tangshan coal pore structure is 2.71.As a result,the pore structure heterogeneity of Xinzhouyao coal is also stronger than that of Tangshan coal,namely,pore structure heterogeneity from synchrotron radiation SAXS and synchrotron radiation nano-CT is consistent.Considering the corresponding relationship between the pore structure anisotropy and the permeability anisotropy,the quantification of pore structure anisotropy was realized by computing the permeability tensor of pore structure using the Lattice Boltzmann method(LBM),and the pore structure anisotropy was characterized by the eigenvalues and eigenvectors of the permeability tensor.The pore structure anisotropy obtained by the method proposed in this paper was validated by the pore structure geometrical morphology.

High Alumina Fiber Composite SiO_2 Based Nanoporous Insulation Boards

The specimens were prepared with high alumina fiber accounting for 0. 5% , 10% or 15% by mass of the total amount of amorphous silica and high alumina fiber, using phenolic resin as binder, and extra-adding 0 or 0. 5% ZnO as sunscreen to cut the cost of SiO2 nanoporous insulation board. The hot volume stability and thermal conductivity （flat plate method ） of the specimens were tested and multi-Jimetion simulation equipment was used to study the thermal insulation performante. The results show that： （1） with high alumina fiber addition increasing, the linear shrinkage rate decreases, but thermal eonductivity changes a little; （2） adding ZnO can decrease thermal conductivity obviously; （3）for the specimen with ZnO and 15% of high alumina fiber, its cold face temperature hardly rises during the simulation experiment at 1 000 ℃ for 2 h, and the cold face temperature of the specimen with the smallest thickness of 2 cm doesn＇t exceed 180 ℃.

Effect of Nano Silica on Hydration and Microstructure Characteristics of Cement High Volume Fly Ash System Under Steam Curing

The influences of nano silica (NS) on the hydration and microstructure development of steam cured cement high volume fly ash (40 wt%, CHVFA) system were investigated. The compressive strength of mortars was tested with different NS dosage from 0 to 4%. Results show that the compressive strength is dramatically improved with the increase of NS content up to 3%, and decreases with further increase of NS content (e g, at 4%). Then X?ray diffraction (XRD), differential scanning calorimetry-thermogravimetry (DSCTG), scanning electron microscope (SEM), energy disperse spectroscopy (EDS), mercury intrusion porosimeter (MIP) and nuclear magnetic resonance (NMR) were used to analyze the mechanism. The results reveal that the addition of NS accelerates the hydration of cement and fly ash, decreases the porosity and the content of calcium hydroxide (CH) and increases the polymerization degree of C-S-H thus enhancing the compressive strength of mortars. The interfacial transition zone (ITZ) of CHVFA mortars is also significantly improved by the addition ofNS, embodying in the decrease of Ca/Si ratio and CH enrichment of ITZ.

纳米C-S-H/PCE对蒸养UHPC力学性能增强机理研究

目前超高性能混凝土(UHPC)制品的力学性能有待进一步提升,采用纳米C-S-H/PCE对UHPC进行增强在理论上是一种可行的技术途径。本文研究了蒸养条件下掺入以聚羧酸(PCE)为分散剂的纳米水化硅酸钙(C-S-H/PCE)对UHPC力学性能的影响,通过测试水化热、水化产物、微观形貌和孔结构等对其机理进行了分析。结果表明,掺入3.0%(质量分数)纳米C-S-H/PCE可以显著提高蒸养UHPC的抗压强度和抗折强度。掺入纳米C-S-H/PCE可以促进UHPC的早期水化,生成更多的水化硅酸钙(C-S-H)凝胶,使水化放热温峰增高,并缩短达到水化温峰的时间。掺入纳米C-S-H/PCE可有效改善蒸养UHPC的孔结构,在掺量为3.0%(质量分数)时总孔隙率最小,有害孔比例最低。该研究可为纳米C-S-H/PCE在蒸养UHPC中的应用提供参考。

松辽盆地古龙页岩纳米孔喉体系中页岩油组分及成熟度分异效应

陆相页岩油储层中石油的微运移效应会导致微观孔隙空间中赋存的页岩油性质发生分异,然而页岩储层孔隙半径较小,孔喉结构复杂,很难通过常规手段对其进行精细刻画,导致对页岩油的微观富集机理认识不清。通过对松辽盆地古龙凹陷青山口组页岩岩心样品进行分步-接力抽提、低温氮气吸附实验,并开展全烃气相色谱、族组分定量、饱和烃气相色谱质谱和金刚烷双质谱等地球化学分析,揭示出页岩储层纳米孔喉体系内的石油组分和成熟度分异效应。结果表明,古龙页岩孔隙以介孔为主,随着页岩样品粒径的逐级减小,更多初始连通性较差的孔隙会被释放出来,同时微观纳米孔喉中烃类的重质组分相对增加,极性更强,页岩油的成熟度也相对更高,这与不同连通性孔隙空间中页岩油的排烃和微运移效应具有一定的相关性。研究成果可为精细表征页岩油的微观赋存特征,阐明页岩油储层烃类微观差异富集机理提供有效的技术手段,同时也为页岩油的可动性评价和甜点优选提供可靠的理论依据。

过热水蒸气作用下碳质页岩纳米孔隙结构演变规律研究

对流加热方式下碳质页岩纳米孔隙结构的演变是探明煤系烃源岩原位热解油气产出机理的关键。为此,基于烃源岩过热水蒸气热解平台,联合低温N2吸附技术,研究了不同过热水蒸气温度下页岩纳米孔隙结构的演变规律。结果表明:随着过热水蒸气温度的升高,碳质页岩纳米孔隙体积和比表面积呈现先降后升的变化规律,而平均孔径呈相反的变化趋势,300℃时孔体积和比表面积最低,550℃两者最高,小于10 nm孔隙数量的增多是高温段页岩比表面积和孔体积提高的主要原因。过热水蒸气热解作用下碳质页岩纳米孔隙的演变可划分为5个阶段。有机质热解生烃、无机矿物的溶蚀和分解、黏土矿物转化的综合作用控制了每个阶段纳米孔隙的演变特征。

纳米二氧化硅强化再生骨料混凝土微观结构研究

利用纳米二氧化硅增强的再生骨料(RAs)制备再生骨料混凝土(RAC)并研究其微观结构。试验中选取5种浓度(0%、1.0%、1.5%、2%、2.5%)的纳米二氧化硅溶液,分别在两种不同条件下(常压和1bar的真空加压)浸泡RAs。测试了纳米二氧化硅增强RAs和RAC的化学组分、孔隙率和孔隙结构并表征了其微观形貌。结果表明,单独使用真空加压条件时,2%为二氧化硅溶液的最佳浓度。该处理条件使CH含量降低了40%以上,总孔隙率下降,平均孔径缩小,以及少害孔(小于50nm)的体积分数降低。该结果经环境扫描电镜(ESEM)验证,归因于二次水化使水化产物增多和纳米颗粒的填充作用。微观层面的研究解释了纳米二氧化硅对再生骨料混凝土的强化作用,为建筑与拆除废弃物的高质利用奠定了理论基础。

正渗透离子截留性能的分子动力学模拟

正渗透离子截留性能的分子动力学模拟可为纳米孔材料的优化设计提供理论依据和技术指导。文章采用正渗透膜纳米通道模型,运用分子动力学模拟方法,模拟了不同孔径和亲水性纳米通道对离子的截留行为,分析了通道内离子截留率与离子水化数、离子水化半径及平均力势间的关系。结果表明:离子进入纳米通道需克服的能量势垒是由离子水化物的脱水引起,随纳米通道孔径的增大,离子水化物需脱去的水分子数减少;Na+和Cl-的截留率随孔径的增大而降低,当孔径≥1.356 nm时,二者均可通过膜纳米通道;离子进入纳米通道需克服的能量势垒、膜纳米通道对离子的截留率均随亲水性的增强而降低。

松辽盆地北部葡萄花油田泉四段扶余油层致密油成岩特征及成岩相

为明确葡萄花油田扶余油层致密油相对优质储层分布,综合铸体薄片、扫描电镜、核磁和微米CT等测试,在致密油储层特征和成岩作用分析基础上,开展成岩相定量划分。结果表明:①扶余油层以残余粒间孔、晶间微孔为主,次为粒内溶孔、粒间溶孔,孔隙、喉道半径分别为0.82~39.42μm和0.02~1.28μm,平均为4.96μm和0.68μm,为微纳米孔隙+纳米喉道。②扶余油层视压实率和视胶结率高达56%和35%,强烈的机械压实、早期方解石和伊利石充填堵塞粒间孔隙和喉道,是导致储层致密化的重要原因。③绿泥石包壳减缓压实强度、保留了部分原生孔,长石和火山岩岩屑的酸性溶蚀形成各类次生孔隙,是形成相对优质储层的关键。④通过多种成岩强度参数的Q型聚类将扶余油层分为4种成岩相,弱胶结强溶蚀次生溶孔相和弱压实强溶蚀残余粒间孔相物性好、试油产能高,是扶余油层有利储层类型。

橡胶-再生骨料保温混凝土热传输机理及微观结构分析

采用橡胶颗粒(RP)、再生骨料(RA)作为保温轻骨料,纳米SiO_(2)(NS)作为辅助胶凝材料,制备橡胶保温混凝土(IRC)。通过自然光照和模拟光照下的环境模拟试验,并结合材料密度、吸水率、导热系数、微观孔结构等指标,研究IRC的热工性能及热传输机理.结果表明:RP的掺加引入了大量孔隙,密度、吸水率和孔容逐渐增大,形成了多孔结构,提高了IRC的保温性能,RP掺量为20%时,导热系数为1.01 W(m·K)^(-1);NS的掺加细化了IRC的孔径,破坏了连通的热流通道,进一步提高了IRC的保温性能,掺入3%的NS后,导热系数进一步降低7.8%~9.4%。

NS-VAE泡沫混凝土微观分析与宏观性能研究

首先分别探究了VAE乳液(Ethylene-vinylacetatecopolymer,乙烯-醋酸乙烯共聚物)和纳米二氧化硅(NS)对泡沫混凝土干密度和抗压强度等宏观性能的影响,然后对VAE与NS复合改性泡沫混凝土的改性机理进行了微观分析。研究证明当NS掺入比例在0%~1%,VAE掺入比例在2%时,NS-VAE泡沫混凝土较普通泡沫混凝土改善了孔隙率和平均孔径,提高了3 d和28 d抗压强度,减小了0~7 d干缩值。微观分析表明NS形成的晶核附着在水化产物表面,并在水化产物表面与VAE一同形成致密的凝胶网膜结构,这些致密的凝胶网膜结构减小了泡沫混凝土内部的孔隙孔径,提高了复合改性泡沫混凝土的干密度与抗压强度。总体来看,NS-VAE泡沫混凝土同时具备VAE泡沫混凝土和NS泡沫混凝土的优点,早期干缩值小,不易开裂,早期抗压强度高,具备更优秀的力学性能。

中国油气储层中纳米孔首次发现及其科学价值

油气储层孔隙可分为毫米级孔、微米级孔、纳米级孔3种类型,常规储层孔隙直径一般大于1μm。北美地区页岩气储层纳米级孔径范围为5～160nm,主体为80～100nm。在对中国非常规油气储层研究中,应用场发射扫锚电子显微镜与纳米CT重构技术,首次发现了小于1μm的油气纳米孔。其中,致密砂岩油气储层中纳米级孔隙以颗粒内孔、自生矿物晶间孔及微裂缝为主,喉道呈席状、弯曲片状,孔隙直径范围10～1000nm,主体为300～900nm;页岩气储层纳米级孔隙以有机质内孔、颗粒内孔及自生矿物晶间孔为主,孔隙直径范围5～300nm,主体为80～200nm。纳米级孔是致密储层连通性储集空间的主体。纳米级孔隙系统的发现,改变了微米级孔隙是油气储层唯一微观孔隙的传统认识,为认识常规油气局部富集,非常规油气连续聚集的地质特征、研究连续型油气聚集机理、增加资源潜力具有重要的科学意义。

核磁共振与高压压汞实验联合表征致密油储层微观孔喉分布特征

通过设计算法程序,利用压汞实验得到的致密储层孔喉分布数据,校正优化了核磁共振实验T2弛豫时间与孔喉半径的换算系数,提高了核磁共振表征孔喉分布的精度,建立了表征致密储层微观孔隙分布特征的核磁实验方法。该方法应用于松辽盆地南部白垩系致密油样品孔喉分布表征,不同含油饱和度样品孔喉分布数据表明,含油饱和度小于10%的样品孔喉集中在10-300 nm;含油饱和度介于10%~40%的样品孔喉集中在20-1 000 nm;含油饱和度大于40%的样品孔喉集中在20-3 000 nm。致密储层中不同级别微纳米级孔隙系统的发育控制了致密油含油性。

基于格子Boltzmann方法的页岩气微观流动模拟

页岩中的主要孔隙类型是纳米孔隙,气体在纳米孔隙中的流动不同于在常规孔隙中的流动,其存在微尺度效应,因此基于连续介质假设的达西方程不再适用。由于页岩气藏一般处于高压环境,气体比较稠密,理想气体状态方程也不再适用。而格子Boltzmann方法是一种介观流动模拟方法,其不基于连续介质假设,适用于从滑移区到过渡区的气体流动模拟,并且能够考虑气体稠密性和非理想气体状态方程的影响。基于考虑努森层影响和微尺度效应的非理想气体格子Boltzmann方法,结合镜面反射格式与反弹格式组合的滑移边界条件,采用二维平板模型,研究了孔隙尺寸、压力和温度等因素对微尺度效应的影响,并对影响机理进行了分析。结果表明:努森数是微尺度气体流动的控制参数;在滑移区和自由分子流区,各因素对微尺度效应的影响较小,而在过渡区,各因素对微尺度效应的影响较大;通过表观渗透率与固有渗透率比值随努森数的变化关系,并与常用的页岩气藏表观渗透率计算模型进行对比,验证了目前常用页岩气藏表观渗透率计算模型的准确性。

鄂尔多斯盆地延长组长7致密油储层微观孔隙特征研究

利用场发射扫描电镜、微米CT、自动矿物识别系统(QEMSCAN)、微图像拼接(MAPS)等测试新技术结合常规分析方法对鄂尔多斯盆地延长组长7致密油储层孔隙特征进行综合研究。结果表明:致密油储层具有微米—纳米级多尺度孔隙连续分布的特征,大于2μm的微米级孔隙构成主要的储集空间;颗粒间充填胶结物质剩余的各尺度残余粒间孔及溶蚀形成的各尺度溶蚀孔隙是最重要的孔隙类型;致密油储层各尺度孔隙连通性较好,可以作为有效的储集空间及渗流通道;深湖细粒沉积及后期强压实、强胶结及强溶蚀为主的成岩作用是现今长7致密油储层微孔隙发育的主要控制因素;由于具备源储近邻或互层配置及异常高压驱动优势条件,致密油储层微孔隙中形成了富集石油的特征。

龙马溪组页岩黄铁矿微观赋孔特征及地质意义

随着页岩气地质理论的不断完善,页岩气储层研究也更加精细、量化,黄铁矿作为页岩气储层普遍发育的物质成分,其矿物学特征、赋孔特征与地质意义引起了关注。为细化、量化对页岩储层黄铁矿的地质认识,通过氩离子抛光—场发射扫描电镜(FE-SEM)、能谱(EDS)、X射线衍射(XRD)等实验手段结合图像处理技术(Image Processing),以渝东南地区龙马溪组中下部优质页岩储层样品为例,探究页岩储层黄铁矿的发育类型和特征,量化表征评价页岩基质莓状黄铁矿在纳米尺度下的孔隙发育特征,并在此基础上讨论黄铁矿的页岩气地质意义,尤其是其储层意义。实验结果表明,莓状黄铁矿是龙马溪组页岩基质中最主要的黄铁矿类型,集合体直径介于3~10μm之间;莓状黄铁矿集合体内部晶体间有机质纳米孔发育,孔隙直径主要分布在100 nm以下,在页岩储层孔隙分类中莓状黄铁矿孔隙应归入有机成因孔隙类型;莓状黄铁矿集合体及其控制的有机质可以为页岩储层贡献0.7%~7%的孔隙比例,是对储集空间具有正贡献的、不应忽视的孔隙类型;基于图像处理技术(Image Processing)的孔隙分类表征与评价技术可以为储层孔隙研究提供新思路,是实现不同类型孔隙量化研究的可行方法。龙马溪组基质黄铁矿既可以贡献一定储集空间,也与有机质具有成因联系,可以为优质储层发育机理研究与优质储层勘探预测提供依据,在页岩气储层研究与勘探开发中具有重要地质意义。