煤层顶板砂岩在高温下的力学特性及破坏机理

采用偏光显微镜、扫描电镜及岩石力学试验系统等仪器设备研究了煤层顶板砂岩在常温到1200℃范围内的力学特性和破坏机理.结果表明,煤层项板砂岩在加热过程中强度急剧降低的温度与岩石内部裂隙形成和晶体形态变化的温度基本一致,说明岩石微观结构在高温下的变化对其力学特性有显著影响;煤层顶板砂岩中有机物在高温下的分解和析出,对砂岩中裂隙形成与发展具有一定的影响,该砂岩在高温作用下的破坏是晶体晶型转变和膨胀等产生的热应力及有机物析出共同作用的结果.     

Effect of Li2O Addition on the Preparation of (Y2‐yLiy)Ti2O7‐y

A new series of (Y_2‐yLi_y)Ti₂O_7‐y having an ordered pyrochlore phase was prepared by a solid state reaction method with a solid solution range of 0.05 ≥ y ≥ 0.10. Unit cell parameters obtained by the Rietveld refinement method shows that the a‐axis decreases linearly with increasing the amount of Li ion addition, indicating the successful incorporation of the Li ion into unit cell. The average x‐fractional coordinate of the O(1) site depends on the ionic radius ratio of r(A³+)/r(Ti⁴⁺) in the A₂Ti₂O₇ with a pyrochlore phase. The Ti K‐edge XANES spectra of the (Y_2‐yLi_y)Ti₂O_7‐y show that the valence of the Ti ions is slightly less than 4 so that Ti is in the mixed valence state. Average particle size increases with increasing the amount of extra Li ion addition, which acts as a flux to lower the melting point of the materials.     

Gold nanoparticles-induced enhancement of the analytical response of an electrochemical biosensor based on an organic-inorganic hybrid composite material

The design and characterization of a new organic-inorganic hybrid composite material for glucose electrochemical sensing are described. This material is based on the entrapment of both gold nanoparticles (AuNPs) and glucose oxidase, which was chosen as a model, into a sol-gel matrix. The addition of spectroscopic grade graphite to this system, which confers conductivity, leads to the development of a material particularly attractive for electrochemical biosensor fabrication. The characterization of the hybrid composite material was performed using atomic force microscopy and scanning electron microscopy techniques. This composite material was applied to the determination of glucose in presence of hydroxymethylferrocene as a redox mediator. The system exhibits a clear electrocatalytic activity towards glucose, allowing its determination at 250 mV vs Ag/AgCl. The performance of the resulting enzyme biosensor was evaluated in terms of sensitivity, detection limit, linear response range, stability and accuracy. Finally, the enhancement of the analytical response of the resulting biosensor induced by the presence of gold nanoparticles was evaluated by comparison with a similar organic-inorganic hybrid composite material without AuNPs.     

Experimental and theoretical investigation of stress corrosion crack (SCC) growth of polyethylene pipes

Degradation of polymers is usually manifested in a reduction of molecular weight, increase of crystallinity in semicrystalline polymers, increase of material density, a subtle increase in yield strength, and a dramatic reduction in toughness. Stress corrosion cracking (SCC) results from strongly coupled thermo-mechano-chemical processes, and is sensitive to material composition and morphology. The individual crack propagation stage is critical in determining the lifetime of pipe. Based on author's previous works, crack layer (CL) theory model is adopted in this study to describe the individual stress corrosion (SC) crack propagation kinetics and the time interval from crack initiation to instability and break through. The effect of localized chemical degradation at the crack tip on SC crack growth kinetics is addressed. Typical SC crack growth is presented and discussed as a step-wise manner based on the proposed model. In addition, scanning electron microscopy (SEM) observation and Fourier transform Infrared spectroscopy (FTIR) analysis of failed samples obtained by accelerated SCC tests are applied to validate the proposed model. SEM is useful to identify the change of fracture mechanisms from chemically driven crack to mechanically driven crack by the formation of visible striations. FTIR analysis enables tracking of the accumulation of chemical degradation by detecting the amount of carbonyls on the crack surface. Carbonyl index is defined to compare the amount of chemical degradation quantitatively. The purpose of this paper is to continue to develop the technical theory and understanding behind SCC phenomena to facilitate all polymer pipe industries and in particular the polyethylene pipe industry to design better resins and piping systems.     

Facile strategies for the synthesis and crystallization of linear trinuclear nickel(II)-Schiff base complexes with carboxylate bridges: Tuning of coordination geometry and magnetic properties

Three new linear trinuclear nickel(II) complexes, [Ni₃(salpen)₂(OAc)₂(H₂O)₂]·4H₂O (1) (OAc = acetate, CH₃COO⁻), [Ni₃(salpen)₂(OBz)₂] (2) (OBz = benzoate, PhCOO⁻) and [Ni₃(salpen)₂(OCn)₂(CH₃CN)₂] (4) (OCn = cinnamate, PhCHCHCOO⁻), H₂salpen = tetradentate ligand, N,N′-bis(salicylidene)-1,3-pentanediamine have been synthesized and characterized structurally and magnetically. The choice of solvent for growing single crystal was made by inspecting the morphology of the initially obtained solids with the help of SEM study. The magnetic properties of a closely related complex, [Ni₃(salpen)₂(OPh)₂(EtOH)] (3) (OPh = phenyl acetate, PhCH₂COO⁻) whose structure and solution properties have been reported recently, has also been studied here. The structural analyses reveal that both phenoxo and carboxylate bridging are present in all the complexes and the three Ni(II) atoms remain in linear disposition. Although the Schiff base ligand and the syn–syn bridging bidentate mode of the carboxylate group remain the same in complexes 1–4, the change of alkyl/aryl group of the carboxylates brings about systematic variations between six- and five-coordination in the geometry of the terminal Ni(II) centres of the trinuclear units. The steric demand as well as hydrophobic nature of the alkyl/aryl group of the carboxylate is found to play a crucial role in the tuning of the geometry. Variable-temperature (2–300 K) magnetic susceptibility measurements show that complexes 1–4 are antiferromagnetically coupled (J = −3.2(1), −4.6(1), −3.2(1) and −2.8(1) cm⁻¹ in 1–4, respectively). Calculations of the zero-field splitting parameter indicate that the values of D for complexes 1–4 are in the high range (D = +9.1(2), +14.2(2), +9.8(2) and +8.6(1) cm⁻¹ for 1–4, respectively). The highest D value of +14.2(2) and +9.8(2) cm⁻¹ for complexes 2 and 3, respectively, are consistent with the pentacoordinated geometry of the two terminal nickel(II) ions in 2 and one terminal nickel(II) ion in 3.     

从郎之万方程出发建立多孔介质微观模型

岩土类多孔介质宏观物理力学性质是岩土工程界关注的焦点,其关键是岩土类多孔介质本身的复杂的微观结构。综述了当前多孔介质建模的研究现状,简要分析了各种模型建立方法的优势和劣势。针对多孔介质建模的复杂性,从随机动力学相分离过程的朗之万方程出发,将多孔介质的形成过程看作是固相粒子和孔隙相粒子相互作用演化的结果,建立了构造随机多孔介质的微观生长模型。通过不断向空间播撒固相粒子和孔隙相粒子控制多孔介质的演化过程,同时计算了不同参数条件下演化过程中多孔介质孔隙率、欧拉数以及分形维数的变化趋势。由于考虑了固体相和空隙相粒子之间的相互作用力,本模型生成的多孔介质与自然界真实的多孔介质更为接近,存在连通和不连通的孔隙结构,孔道迂回曲折。通过与真实样品的微观结构的比对,验证了本模型的实用性,可行性。     

pH值对于表面硼改性纳米二氧化钛交联剂交联性能的影响

传统有机硼交联羟丙基瓜胶 （HPG）冻胶压裂液体系具有稠化剂用量大,压裂施工成本高,压裂残渣多,裂缝导流能力差等诸多缺点。为了达到降低压裂液稠化剂用量、提高压裂施工效果的目的, 采用“两步法”制备了一种表面硼改性的纳米二氧化钛颗粒 （NCC）作为HPG压裂液交联剂。研究了pH值对于NCC交联HPG冻胶耐温性能的影响,结果表明随着pH值的增加,NCC冻胶压裂液的耐温性能先增大后减小。所形成的冻胶压裂液在pH=12时耐温性能最佳。与传统有机硼交联剂相比,NCC可大大减小稠化剂用量,NCC交联的0.3 wt.% HPG冻胶在pH值为8~14的范围内均能保持良好的耐温性能。利用扫描电镜表征了NCC冻胶在不同pH值条件下的交联形貌及交联结构,结果表明,在pH值为12时,NCC冻胶微观形貌最致密。     

EFFECT OF MONTMORILLONITE ADDITION ON MECHANICAL CHARACTERIZATIONS OF POLYIMIDE NANOCOMPOSITE FILMS

Tensile deformation and fracture characteristics of polyimide/montmorillonite nanocomposite films are investigated to enhance the particular mechanical properties and understand the effective factors in dominating the mechanical properties of nanocomposites, such as the nanolayer, matrix and nanolayer/matrix interface. How to contribute to the mechanical properties of nanocomposite film is a very complex problem. In this paper, these factors are analyzed based on the addition amount and fracture mechanics. The results indicate that the specimen at 20 wt% MMT breaks prematurely with a fracture strength （σb = 78 MPa） much lower than that （σb = 128 MPa） at the 1 wt% MMT. However, the Young＇s modulus （3.2 GPa） of the former is higher than that （1.9 GPa） of the latter. Fractography also indicates that the brittle cracking formed in high content addition is the main cause of failure but microscopically ductile fracture morphology still exists locally. And for the trace element addition, the smaller threading slipping veins are evenly distributed on the entire fracture section of these films. Therefore, these characteristics would presumably be associated with both the concentration effects of size of nanocomposite sheets and the increasing deformation harmony in nanolayers.     

混合物理化学气相沉积法(HPCVD)制备的MgB2超导厚膜样品的成分分析

本介绍了基于混合物理化学气相沉积法(HPCVD),以B2H6为硼源,在(000l)取向的Al2O3单晶衬底上,制备了MgB2超导体厚膜样品．该样品平均厚度约为40μm．其Tc(onset)=39K,Tc(0)=37．2K．X光衍射图显示该膜沿(101)方向生长,具有少量Mg和MgO杂相．SEM图像、X射线能量损失谱以及背散射电子衍射图证实了这两种杂相的存在,并显示该样品成分富镁．样品表面的镁与空气接触形成MgO膜,在一定程度上阻止了MgB2样品进一步被氧化．对于MgB2厚膜成膜过程及反应机理,我们提出了一种新的推断．     

纳米ZSM-5分子筛的合成与表征

水热法合成常规微米 ZSM- 5分子筛并使用其作为基准物 ,以中孔碳纳米管为惰性基体 ,限定空间尺寸法合成了 Si O2 /Al2 O3 =1 0 0的纳米 ZSM- 5分子筛。 X射线粉末衍射测定结果表明该合成产品具有典型的 ZSM- 5骨架结构和纳米尺寸。红外光谱显示所合成产品具有典型的 ZSM- 5型沸石分子筛的骨架振动 ,但与基准物相比较同时出现了蓝移和红移现象。透射电镜显示纯化后的碳纳米管具有 2 0— 30 nm的内径并已多处开口 ,晶粒度在 30— 6 0 nm之间。扫描电镜表明纳米沸石的存在 ,同时由于小尺寸效应该样品呈球形聚集态。该方法可用于合成不同晶粒大小的产品 ,且沸石的分离较容易。