纳米纤维状白炭黑的孔隙特征

在与传统白炭黑对比研究基础上,利用TEM、XRD、FT_IR和氮吸附法对纳米纤维状白炭黑(MLD为92.73%)进行研究,主要讨论了纳米纤维状白炭黑多孔结构的成因、孔径大小、孔分布及孔类型等特征。分析表明纤蛇纹石中氢氧镁石八面体层被酸溶蚀和硅氧四面体层的塌陷是导致这种白炭黑具有多孔纳米纤维结构的直接原因;有两种孔隙类型,即纤维上的孔隙和纤维的堆积孔隙;纤维上的孔隙包括SiO_2微粒间的孔隙、其聚结体间的孔隙、残余纳米管的管道和毛细管道;孔径2.1和3.8nm处的孔隙数量多,并且在纳米纤维(或管)上存在大量小于5nm左右的微孔。研究证明了在用于橡胶、塑料填充补强剂和催化剂载体等方面,纳米纤维状白炭黑更优于传统白炭黑。     

我国西北地区不同类型纤蛇纹石石棉的电镜研究

作者对西北地区不同类型温石棉矿床的石棉进行了扫描电镜和高分辩率透射电镜研究,拍摄到清晰的晶格象和电子显微象,发现茫崖型和小八宝型的温石棉纤维的晶格条纹、晶格缺陷及纤维形貌有明显差异。这种差异与成棉地质条件和温度有关。     

Hydrate phase equilibria in porous media: effect of pore size and salinity

ABSTRACT Considering the ever-increasing importance of marine gas hydrates, it is crucial to gain a better understanding of clathrate formation and decomposition in porous media. It is well established that, due to capillary effects, small-diameter pores – similar to those found in natural sediments – act to inhibit hydrate stability. However, accurate data constraining these effects are still lacking. Here, we present experimental methane clathrate dissociation data for 3.5 mass% methanol aqueous solutions in confined silica glass pores of narrow distribution (30.6, 15.8, and 9.2 nm mean diameters). These data have been used to validate a thermodynamic model for clathrate stability porous media. Experimental data show a marked improvement on literature data – which we attribute to the experimental and interpretative methods used – and are in good agreement with the model predictions. Results suggest that mass transfer of inhibitors (methanol) and dissolved gas during clathrate formation/dissociation within the porous network plays an important role in controlling gas hydrate equilibria.     

利用粉煤灰制备多孔氧化硅的实验

利用相分离原理,以粉煤灰经硅铝分离后所得的硅酸凝胶为原料,选用聚乙烯醇为造孔剂,硝酸为催化剂,成功地制备了多孔氧化硅。实验结果表明:制备的多孔氧化硅的孔道发育良好,含有三级孔道。扫描电镜分析显示:大孔孔径为1～2 μm,比表面积为12.03 m²/g,这与实际应用的硅藻土助滤剂制品大致相当。对实验制品在啤酒液中的稳定性实验结果显示:多孔氧化硅制品在浸泡于啤酒过程中几乎没有Ca²⁺、Fe³⁺离子溶出,浸泡后的啤酒液的pH值基本不变。上述结果表明:实验制备的多孔氧化硅制品作为硅藻土助滤剂的替代品具有良好的实际应用前景。     

四川石棉县蛇纹石猫眼的红外吸收光谱研究

采用Fourier变换红外吸收光谱和X射线粉晶衍射技术对四川石棉县蛇纹石猫眼进行了研究。红外吸收光谱结果表明:四川蛇纹石猫眼可分为纤蛇纹石和叶蛇纹石两种类型,两者在(960-1100)cm-1和(3600-3690)cm-1的范围内由Si-O伸缩振动的E1类振动和OH伸缩振动表现出的红外谱带分裂强度及谱带特征存在明显的差异。在(960- 1100)cm-1间:纤蛇蚊石的红外光谱分裂成三个明显的谱带,而叶蛇纹石在此区间只有两条谱带。在570cm-1附近的红外谱带以肩状出现;OH伸缩振动区:纤蛇蚊石出现两条红外谱带,而叶蛇蚊石只出现一条红外谱带。X射线粉晶衍射结果表明:叶蛇蚊石具有d202=0．2522nm(I/I0=19)和d203=0．2430nm(I／I0=18)的特征谱线,而纤蛇纹石则具有d202、006=0．2446nm(I／I0=29)的特征谱线,d020>0．245nm近0．249 nm的特征谱线缺失。     

我国四大矿区温石棉粉尘诱导A549细胞凋亡和周期阻滞的对比研究

通过FT-IR和XRD对四川新康、陕西陕南、甘肃阿克塞和青海茫崖四大矿区温石棉的物相成分、谱学特征进行测试分析,利用MTT法、流式细胞术检测了4种温石棉纤维粉尘染毒A549细胞后的细胞存活率、凋亡率和细胞周期分布,比较和探讨了四大矿区温石棉纤维粉尘抑制细胞增殖能力的大小及其对细胞凋亡和周期阻滞的影响。研究结果显示,四大矿区温石棉的主要物相是斜纤蛇纹石,新康温石棉成分比其他3种温石棉的复杂,阿克塞和茫崖温石棉的成分相似;四大矿区的温石棉化学基团基本相同,阿克塞和茫崖温石棉纤维的表面结构较陕南和新康温石棉的完善。4种温石棉均能不同程度地抑制A549细胞增殖,诱导细胞凋亡和周期阻滞:茫崖组凋亡率最大(22. 56±2. 56)%,陕南组凋亡率最小(19. 57±3. 07)%;细胞周期阻滞均以G2/M期阻滞为主,新康、陕南、阿克塞和茫崖组处于G2/M期细胞比例分别增加8. 90%、8. 58%、9. 13%和10. 44%。4种温石棉导致细胞凋亡和周期阻滞的能力:茫崖新康阿克塞陕南。     

纤蛇纹石石棉的纳米效应与生物活性

本文首次从纳米材料与纳米效应角度出发讨论了纤蛇纹石石棉的形态、表面结构、表面性质与生物活性的关系。结果表明,纤蛇纹石石棉属自然界产出的一种特殊的一维纳米丝状矿物,在形态、结构和表现性质等方面表现出纳米材料所具有一般特性,其中,形态上一寸及高表面化学活性构成了它的生物活性特征。纤蛇纹石石棉纤维对动物的危害,既具有一般纤维的危害性,又具有非晶质ＳｉＯ２的危害性。由于纤维的小尺寸效应和高表面活性而使生物     

The zeta-potentials of natural and synthetic chrysotiles

Different specimens of the asbestos mineral chrysotile show widely different zeta-potentials. Strongly positive values are found with samples containing an excess of magnesia in the form of brucite, Mg(OH)₂. Synthetic chrysotile and natural samples containing little or no brucite give moderately positive ζ-values over the pH range 3–11. Feebly positive or weakly negative natural chrysotiles are materials which have suffered weathering; and deliberate acid-leaching of any chrysotile ultimately leaves a strongly negative pseudomorph of silica gel.Since the pH and the ambient concentration of Mg²⁺ ions near the surface are the main factors controlling ζ, and since chrysotile is readily susceptible to leaching in practically all aqueous media and does not come to a true ionic equilibrium in any practical time, the zeta-potential of an ideal chrysotile surface is a hypothetical concept.The results also explain the temporary colloidal stability of very dilute suspensions of chrysotile in weakly acidic media and the mutual coagulation of chrysotile and amosite slurries.     

鄂尔多斯盆地延长探区延长组页岩气储层孔隙结构特征

为了评价陆相页岩气储层的储集空间和储气能力,以鄂尔多斯盆地延长探区上三叠统延长组长7段、长9段页岩为研究对象,运用电子扫描显微镜、高压压汞、低温CO2和N2气体吸附等实验方法,对陆相页岩气储层孔隙类型特征、孔隙结构及其影响因素进行研究。结果表明：(1)延长探区上三叠统延长组陆相页岩发育多种类型微观孔隙,以粒间孔和粒内孔为主,少量晶间孔和溶蚀孔,有机质孔发育较少,为陆相页岩气赋存提供了储集空间;(2)延长组页岩中介孔(2～50 nm)贡献了其主要的孔容和比表面积,占总孔容的7437%,占总比表面积的6440%,且长9段页岩的总孔容和总比表面积均大于长7段页岩;(3)延长组页岩孔隙结构以狭缝型孔和板状孔为主,孔径主要分布在04～09 nm、3～25 nm和5～200 μm区间段内,延长组页岩平均孔径为853 nm,且长7段页岩平均孔径大于长9段页岩;(4)页岩有机碳含量、有机质成熟度及矿物成分含量共同影响着延长组页岩孔隙的发育,其中矿物成分含量是以介孔孔隙为主的延长组页岩孔隙发育的主控因素,有机碳含量及成熟度的增加主要对页岩中微孔孔隙的发育起到积极作用。     

四川盆地五峰组—龙马溪组重点井含气页岩孔隙类型与孔径分布

针对四川盆地五峰组—龙马溪组过成熟海相页岩,开展普通薄片观察、SEM成像、X-衍射全岩组分和黏土矿物分析、TOC含量测定、N₂-CO₂联合吸附实验和RG测定。结果表明,海相页岩发育有机孔、无机孔和微裂缝。有机孔多呈气孔状或海绵孔状,大、小混杂;无机孔多呈三角状、棱角状或长方形状;微裂缝多呈条带状,能有效沟通有机孔和无机孔。过成熟海相中,有机孔数量个数>97%,无机孔和微裂缝数量<3%。孔隙以孔径<10 nm的微孔和介孔为主,孔隙数量和体积占比均大于80%,孔径>10 nm的孔隙数量和体积不足20%。在大于10 nm的介孔和宏孔中,有机孔数量超过97%,面孔率超过50%,无机孔和微裂缝数量不足3%,面孔率低于50%。介孔孔径以5~400 nm为主,孔径<20 nm的数量占比>70%。有机孔面孔率随着孔径增大而增大,孔径为100~400 nm的孔隙面孔率占比普遍超过50%。无机孔主要为石英晶间孔和碳酸盐溶蚀孔及少量长石溶蚀孔,孔径为100~400 nm的孔隙面孔率贡献最大,多数页岩均接近100%。随着TOC含量增高,有机孔孔径减小,其面孔率则先增大后减小,TOC为5.5%时常出现拐点。龙马溪和龙一段页岩孔隙由下至上,面孔率逐渐降低。平面上,龙一_1¹小层不同地区面孔率大小及孔隙组成也存在差异,泸州地区面孔率最大,渝西地区最低。渝西地区无机孔含量最高,长宁地区无机孔含量最低。石英晶间孔隙度与石英含量呈正相关,溶蚀孔隙度与碳酸盐矿物含量呈正相关,这可能与石英抗压实能力强、碳酸盐矿物易于溶蚀有关。     

4种天然温石棉致大鼠肺损伤及对HO-1和HSP-70的影响

探讨了我国四大矿区天然温石棉致大鼠肺部损伤作用及肺组织中HO-1和HSP-70的表达差异。从我国四大天然矿区采集4种天然温石棉,用扫描电镜、红外光谱和X射线荧光光谱分析其粉尘形貌、表面活性基团和化学组分。将90只初断乳SPF级Wistar大鼠,随机分为5组(甘肃阿克塞、青海茫崖、四川新康、陕西陕南温石棉组和生理氯化钠溶液阴性对照组),用2. 0 mg/m L温石棉粉尘悬液0. 5 m L(1次/月)对大鼠非暴露式气管内滴注染毒。于1、6、12个月分批处死大鼠6只,测定支气管肺泡灌洗液(BALF)中的乳酸脱氢酶(LDH)、碱性磷酸酶(AKP)和总蛋白(TP)含量,采用qRT-PCR检测肺组织中血红素氧化合酶1(HO-1)和热休克蛋白70(HSP-70) mRNA表达水平,采用western blot检测肺组织中HO-1和HSP-70蛋白表达水平。结果显示,阿克塞、茫崖和新康温石棉组LDH及各温石棉组AKP和TP在各时间点均比阴性对照组高(P 0. 05),且随染毒时间延长呈上升趋势(P 0. 05)。染毒1月时,各染毒组HO-1、HSP-70 mRNA和HO-1、HSP-70蛋白表达量比阴性对照组高(P 0. 05);染毒6月时,各染毒组比阴性对照组高,阿克塞和陕南温石棉组低于茫崖和新康温石棉组(P 0. 05);染毒12月时,阿克塞和陕南温石棉组高于茫崖和新康温石棉组(P 0. 05),茫崖和新康温石棉组低于阴性对照组。     

Sectors in polygonal serpentine. A model based on dislocations

Based on coexisting rolled chrysotile and polygonal serpentine fibers with 15 or 30 sectors each, a crystallographic model for polygonization of chrysotile is proposed. It is based on an assumed chrysotile-to-lizardite transition. Polygonization of chrysotile requires more likely 15 partial dislocations per turn, as required by polytype translational operators for serpentines. The observed number of sectors corresponds to the two most elastically stable arrays of dislocations. Homogeneous shear of the layer stacking arising from intersector kinking results in a cyclic distribution of twins and/or different polytypes. This makes the fiber axis a fivefold symmetry axis and consequently polygonal serpentine and chrysotile to be both forms of serpentine with local fivefold symmetry. This model is alternative to the recent crystallograpic model by Chisholm (1991, 1992).     

Dehydration reactions and micro/nanostructures in experimentally-deformed serpentinites

High-T torsion experiments on lizardite + chrysotile serpentinites produced mineralogical and micro/nanostructural changes, with important implications in rheological properties. High-resolution TEM showed that specimens underwent ductile [by microkinking and (001) interlayer glide] and brittle deformation (by microfracturing), together with dehydration and break-down reactions. Lizardite is affected by polytypic disorder and microkinking [kink axial planes at high angle with respect to (001) planes], that were not present in the initial ordered 1T-lizardite. Chrysotile fibres are deformed, resulting in elliptical cross-sections, with strong loss of interlayer cohesion. Both lizardite and chrysotile break down to a fine intergrowth of olivine (up to 200 nm), talc (up to 30 nm) and poorly-crystalline material. Lizardite-out reaction preferentially occurs at kink axial planes, representing sites of preferential strain and enhanced reactivity; conversely, chrysotile break-down is a bulk process, resulting in large healed olivine aggregates, up to micrometric in size. Overall observations suggest that dehydration and break-down reactions are more advanced in chrysotile than in lizardite.     

Asbestos in lake and reservoir waters of Staten Island,New York: Source,concentration, mineralogy,and size distribution

There is strong evidence indicating that the six commonly recognized varieties of asbestos are cancer-producing agents Epidemiological and experimental data indicate that, although response to inhalation exposure is most marked, exposure by ingestion probably also entails a risk of excess tumor incidence. The toxicity of mineral fibers can be related to fiber dimensions, mineralogy, chemistry, and surface-active properties. In the Silver Lake Reservoir in Staten Island, New York, where chrysotile from serpentinite bedrock exposures is a potential source of contamination, chrysotile asbestos levels of 15 to 86 million fibers per liter (MFL) were measured, with an average of 53 MFL Much lower levels (average 0 3 MFL) were observed in small lakes and ponds with clayey bottoms on the Staten Island Serpentinite.     

鄂尔多斯盆地延长组泥页岩储层SiO2赋存状态研究

鄂尔多斯盆地泥页岩储层纯页岩段黏土矿物含量高,储集空间体积小。因此,黏土矿物转化释放的二氧化硅缺乏足够的空间,不能生长成自生石英,只能以非晶态存在于黏土矿物之间;而其粉砂质泥岩夹层中常见微米级孔洞。孔洞由长石溶蚀和黏土矿物转化形成,内部则发育晶形完好的自生石英、绿泥石及含铁方解石。此外,粉砂质泥岩的碎屑颗粒间常发育结块状非晶态二氧化硅,碎屑石英颗粒周围则以次生加大边的形式发育粒状和席状(或片状)非晶态二氧化硅。二氧化硅主要来源于黏土矿物转化与石英碎屑颗粒溶蚀。     

阳泉新景矿高煤级煤的孔隙结构分形特征

分形理论是宏观上定量评价储层非均质性的有效手段。以阳泉新景矿高煤级煤样品压汞数据为基础,建立分形几何模型,定量描述了孔隙结构。实验结果表明:样品孔隙以纳米孔为主,孔径、比表面积及孔容也集中分布在纳米孔段。煤样孔径65 nm以上的孔隙具有显著的分形特征,分维值分布范围为2.89~2.99,体积增量呈现阶段式的变化,孔隙结构复杂;孔径65 nm以下孔隙几乎无分形特征,比表面积增量与孔径在对数坐标中呈线性关系;基于分形特征及分子运动规律,将储层孔隙以孔径65 nm为界划分为扩散孔和渗透孔2个大类6个小类。分维值与体积孔隙中值半径、总孔隙体积呈负相关,与孔径65 nm以上的孔隙体积、比表面积呈正相关,与孔隙度无相关性。分形分维值对储层结构具有较全面的表征能力,可以作为综合指标在煤储层孔隙研究中加以应用。      

干酪根对页岩基质中甲烷运移规律的影响

微/纳米孔隙内甲烷的运移研究是进行页岩气藏开发预测及评价的前提和基础.页岩中分布大量的微/纳米孔隙,其中干酪根中的纳米级孔隙分布广泛.由于气体在不同尺度孔隙中的运移机理大不相同,且在有机孔中存在明显的吸附/解吸现象.因而,甲烷在页岩中的运移机理仍需完善.本研究综合物理模拟及数学分析方法,对甲烷渗流规律进行研究.研究结果表明:（1）温度升高,单位质量页岩的产量减少,达到平衡的时间缩短,总体体现在甲烷在高温下的吸附/解吸-扩散速率大.（2）相同生产压力下,随入口压力升高,甲烷运移速率增大,达到产量平衡的时间增长.（3）数学模型充分考虑干酪根中甲烷扩散对气体运移过程的影响,并与实验结果及不考虑干酪根影响的模型进行对比分析,结果显示,本文建立的数学模型能更准确地描述甲烷在页岩基质中的运移动态.      

多重分形在海积软土微观结构研究中的应用

本文将多重分形谱引入到土微观结构分形研究中,对天津市滨海新区三个不同地点海积软土原状样及不同固结压力后土中孔隙的多重分形特征进行研究,从多重分形的角度对孔隙的不均匀性进行定量描述,并建立孔隙多重分形谱各特征参数与荷载之间的关系.结果表明三个地点的海积软土孔隙多重分形特征存在差异.     

The surface of labradorite feldspar after acid hydrolysis

After reaction with a pH < 4, the surface of labradorite is extensively enriched in Si and H, and depleted in Al, Ca and Na relative to an unreacted crystal. However, the amount of hydrogen measured in the reacted surface is less than that predicted on the basis of exchange of hydrogen (or hydronium) ions for cations in the feldspar. By analogy with studies of silicate glass, this low concentration of hydrogen suggests that some silanol groups in the reacted surface repolymerize subsequent to ion-exchange and depolymerization reactions. The net result is a relatively porous, Si-rich leached layer which is amorphous to electron diffraction, and which allows rapid diffusion of unreactive solutes.

Both the surface area of the reacted feldspar and the porosity increase with acid hydrolysis. Modeling of nitrogen sorption onto the surface suggests that the pores have a nominal radius of 20–80 Å or less. This distribution of pore sizes resembles other acid-reacted silicate materials, such as glass, chrysotile and kaolinite. Although the mineral surface clearly becomes more porous during acid hydrolysis, the increase in powder area also does not coincide with an increase in the flux of dissolved Si from the powder. We thus attribute most of this increase in area to spallation of the silica-rich surface from the feldspar upon drying.