Strength and microplasticity of biocarbons prepared by carbonization in the presence of a catalyst

The microdeformation has been investigated under uniaxial compression of beech-derived biocarbons partially graphitized during carbonization in the presence of a Ni- or Fe-containing catalyst. The strength and ultimate fracture strain have been determined at different temperatures of carbonization of the samples in the absence or in the presence of a catalyst. It has been shown using high-precision interferometry that the deformation of biocarbon samples under uniaxial loading occurs through jumps (in magnitude and rate of deformation) with axial displacements in the nanometer and micrometer ranges. The use of a catalyst leads to a decrease in the size of nanometer-scale jumps and in the number of micrometer-scale jumps. The standard deviations of the strain rate on loading steps from the smooth average dependence of the strain rate on the displacement have been calculated for micrometer-scale jumps. A similar characteristic for nanometer- scale jumps has been determined from the distortion of the shape of beats in the primary interferogram. It has been shown that the variation in the standard deviation of the strain rate with a change in the carbonization temperature is similar to the corresponding dependence of the ultimate fracture strain.     

Effects of CO2 activation on porous structures of coconut shell-based activated carbons

In this paper, textural characterization of an activated carbon derived from carbonized coconut shell char obtained at carbonization temperature of 600 °C for 2 h by CO₂ activation was investigated. The effects of activation temperature, activation time and flow rate of CO₂ on the BET surface area, total volume, micropore volume and yield of activated carbons prepared were evaluated systematically. The results showed that: (i) enhancing activation temperature was favorable to the formation of pores, widening of pores and an increase in mesopores; (ii) increasing activation time was favorable to the formation of micropores and mesopores, and longer activation time would result in collapsing of pores; (iii) increasing flow rate of CO₂ was favorable to the reactions of all active sites and formation of pores, further increasing flow rate of CO₂ would lead carbon to burn out and was unfavorable to the formation of pores. The degree of surface roughness of activated carbon prepared was measured by the fractal dimension which was calculated by FHH (Frenkel-Halsey-Hill) theory. The fractal dimensions of activated carbons prepared were greater than 2.6, indicating the activated carbon samples prepared had very irregular structures, and agreed well with those of average micropore size.     

Effect of carbonization temperature on the microplasticity of wood-derived biocarbon

The uniaxial compression strength under stepped loading and the 325-nm-stepped deformation rate of biocarbon samples obtained by carbonization of beech wood at different temperatures in the 600–1600°C range have been measured using high-precision interferometry. It has been shown that the strength depends on the content of nanocrystalline phase in biocarbon. The magnitude of deformation jumps at micro- and nanometer levels and their variation with a change in the structure of the material and loading time have been determined. For micro- and nanometer-scale jumps, standard deviations of the differences between the experimentally measured deformation rate at loading steps and its magnitude at the smoothed fitting curve have been calculated, and the correlation of the error with the deformation prior to destruction has been shown. The results obtained have been compared with the previously published data on measurements of the elastic properties and internal friction of these materials.     

基于简单碰撞理论煤粉燃烧动力学模型的研究-PART Ⅲ:氧气可达比表面积

根据不同温度下氧分子平均自由程的大小,比较了小孔、中孔和大孔中三种扩散速率与煤焦表面燃烧速度的大小.研究表明2000 K以内,颗粒表面分子扩散速率比氧化反应速率大1个数量级以上,过度扩散速率不小于氧化速率.温度小于1200K时,燃烧速率比Knudsen扩散速率小1～5个数量级,扩散孔径小于15～28 nm,反应主要在内外表面进行;1200～1600K时,燃烧速率与Knudsen扩散速率相当,扩散临界孔径28～38 nm,反应在外表面及浅层内表面进行;温度1600K以上时,Knudsen扩散速率比燃烧速率小1个数量级,孔径38～50 nm以下内表面上碳的氧化速度受扩散控制.煤焦的氧化主要发生在Knudsen扩散临界孔径10～50 nm以上的氧气可达表面上.     

Micro- and nanoscale instabilities of deformation in polymers

The rate and magnitude of the deformation in polymers under constant compressive stresses at room temperature have been measured. The use of laser interferometer has made it possible to perform measurements at small intervals of variations in the specimen length Δl = 0.325 μm, and the analysis of the form of beats has made it possible to estimate oscillations of the strain rate in nanoscale displacements. It has been shown that the average strain rate of polymers continuously varies and no creeping interval with a constant rate is observed. At all stages of smooth variations in the average rate, jumps of its current values corresponding to Δl from several nanometers to a hundred and more nanometers have been found. Changes in the structure with an increase in the deformation manifest themselves in an increase in the size of nanoscale jumps and in a complication of their shape.     

Microplasticity of biomorphic SiC/Al composite under uniaxial compression

Inhomogeneity of the microplastic strain rate (deformation jumps) of a biomorphic SiC/Al composite under uniaxial compression has been studied by laser interferometry on the nanometer level. The value of strain rate jumps has been calculated from the deviation of the form of separate beats in the interferogram of a deformation from the standard form corresponding to a constant strain rate within one beat. In addition to strain rate oscillations extended by 100–180 nm along the displacement (the variation in the length of the specimen), peaks of small width and amplitude with a distance of 10–20 nm between them are observed, as well as peaks with a width of ∼ 50 nm. These peaks may be associated with the sizes of structural formations of an aluminum alloy (grains, subgrains, precipitates, etc.) or with the sizes of SiC nano- and microcrystals situated separately from large-grain crystals and surrounded by residual carbon. The results of this work offer hope to the possibility of enhancing plasticity and strength of biomorphic composites by increasing the fraction of fine-grain elements (< 1.5 μm) in their structure.     

Jumplike deformation of polymer materials on the micrometer and submicrometer structural levels

Jumplike creep is considered as a reflection of the structural heterogeneity of amorphous polymers on the mesoscopic and nanoscopic levels. The D-450 epoxy resin, poly(vinyl chloride), poly(vinyl butyral), and a composite consisting of the D-450 epoxy resin and diabase microparticles are studied at a temperature of 290 K. The creep rate of the specimens under compression is measured with a laser interferometer in submicrometer-scale deformation increments. Periodic variations of the creep rate with time or under deformation correspond to a jumplike (stepwise) behavior of the creep. It is shown that diabase particles (5–10 μm in size) are responsible for the appearance of micrometer-scale jumps in the creep of the composite and that the deformation jumps on the nanometer level are comparable to the sizes of the globules. The role of the resolution of the method employed in the evaluation of the scale of deformation jumps and structural units is considered.     

Size dependence of the activation energy of diffusion in multilayer Cu-Ni films

The results of studying the effect of the characteristic size on the rate of diffusion processes in nanometer Cu-Ni film systems have been reported. The film system has been prepared by sequential vacuum deposition of the components, and the activation energy of diffusion has been determined from a change in the electrical resistance of the film system in a heating-cooling cycle. It has been shown that the activation energy of grain-boundary diffusion decreases with decreasing characteristic size of the system and amounts to 0.25 eV for the film system with a characteristic size of 5 nm, which corresponds to an increase in the grain-boundary diffusion coefficient by 10 orders of magnitude with respect to massive samples.     

Surface precrystallization of normal C24 alkane in porous glass

The behavior of the enthalpy and specific heat of normal C24 alkane in the bulk and in porous glasses is investigated using an adiabatic scanning microcalorimeter. Enthalpy jumps, which precede a phase transition in the entire volume of the pores, are found in porous glass with characteristic pore size 1000 Å at a transition from the isotropic liquid into the rotator phase RII. The enthalpy jumps are interpreted as a layerwise growth of a crystal phase on the surface of porous glass. It is also found that porous glass substantially changes the phase behavior of alkanes.     

颗粒介质尺度效应的抗剪试验及物理机理分析

针对颗粒介质力学特性的颗粒尺度效应研究,选用土矿物颗粒制备不同颗粒尺度的抗剪试样,进行一系列直剪快剪和三轴抗剪试验,测得了不同颗粒粒径和体分比试样的变形曲线及剪应力强度;基于颗粒间微观作用力与重力比值和胞元体模型,首次从微观和细观角度解释颗粒尺度效应的物理机理.结果表明,随着介质中粗颗粒的比例增加和粒径减小,介质变形特性增强,剪应力强度也随之提高;体分比对变形和强度特性的影响比粒径的影响更加显著.基于介质特性尺度效应物理机理分析,提出衡量介质颗粒聚集和摩擦效应的微重比判别参数以及应变梯度和变形协调微裂纹引起颗粒尺度效应的细观机理解释;文中提出的胞元体模型大大减少了颗粒物质体系的计算自由度,为工业和工程设计的计算建模提供一种可行途径.     

Regularities of Microstrain of Ultrahigh-Molecular-Weight Polyethylene Modified with Halloysite Additives

The effect of additives of 1 and 3 wt % of halloysite on the rate and small jumps of deformation under uniaxial compression of ultrahigh-molecular-weight polyethylene was investigated. A procedure for precision interference measurement with a resolution of 325 nm for displacement and 1 kHz for frequency enabled the detection of several levels of deformation in the micro- and nanometer ranges. The addition of halloysite results in a decrease in the strain rate under the same loading conditions and a change in the characteristics of the strain jumps. Calorimetric measurements showed that melting of polyethylene with a different concentration of halloysite causes a change in the transition energy and the degree of crystallinity.     

纳米TiO2的表面能态及光生电子-空穴对复合过程的研究

以液相法制备了水溶态纳米TiO2,并通过X射线衍射(XRD)、X射线光电子能谱(XPS)和傅里叶红外光谱仪(FTIR)对纳米TiO2的结构和组成作了细致分析.并对其紫外-可见光谱(UY-Vis spectrum)和荧光发光光谱(PL spectrum)进行了分析.结果发现纳米TiO2呈现较好的锐钛矿型,平均粒径为5 nm.水溶态纳米TiO2由于吸附而在表面形成了Ti-OH和Ti-H2O的表面态,其能级位于其价带以上约0.6和0.54eV;500℃热处理后样品的表面吸附水基本消失,但OH-仍然存在,同时在纳米TiO2晶格中出现了氧空位,其能级位于价带以上3.13 eV.对于水溶态纳米TiO2,表面复合是电子-空穴对的主要复合过程;热处理后的样品,由于表面态遭到破坏,粒子半径变大,直接复合成为电子-空穴对的主要复合过程,同时还伴随有通过氧空位的间接复合和通过Ti-OH的表面复合.     

Nanofractal surface structure under laser sintering of titanium and nitinol for bone tissue engineering

Comparative microanalysis and histological studies of porous titanium and nitinol (NiTi) implants fabricated by selective laser sintering are carried out. Sintered Ti and NiTi nanoporous structures are developed with grain sizes ranging from dozens to several hundreds nanometer and their formation is discussed. Dependence of the surface morphology of the implant on laser processing parameters (laser power, scanning velocity and beam diameter) is observed by analyzing the fractal-type nanostructure and its self-organization from the nano- to the macro-passing through the microlevel.It is shown that functional characteristics of the synthesized medical implants depend on the pores size distribution and their relative location as well as on the nanostructural morphology of the sintered surface.     

Effect of the magnetic field on nanometer-scale deformation jumps in polymers

The effect of a constant magnetic field on the rate of jumplike creep under compression is investigated for vitreous polymers with a globular structure. The interferometric method used for recording the creep makes it possible to measure deformation jumps from 300 nm and larger. It is demonstrated that the sizes of deformation jumps in polyester and epoxy resins decrease in the magnetic field (B = 0.2 T). Taking into account that the deformation jump size corresponds to the size of structural inhomogeneities, it is assumed that macroglobules under the action of a constant magnetic field are separated into smaller structural units on the nanometer level.     

Surface effect on the size evolution of surface plasmon resonances of Ag and Au nanoparticles dispersed within mesoporous silica

The optical absorption has been investigated for silver and gold nanoparticles dispersed within the pores of monolithic mesoporous silica after annealing at different temperatures. It has been shown that with reduction of the particle size, the surface plasmon resonance position blue-shifts first and then red-shifts for silver/silica samples, but only red-shifts for gold/silica samples. This size evolution of the resonance is completely different from that previously reported for fully embedded particles. Based on the interaction of the particle surface with ambient air and the porosity at the particle/matrix interface, we present a multi-layer core/shell model and assume that the chemical adsorption of gas molecules from the air on the free surface of nanoparticles within the pores is mainly responsible for the observed size evolution of the resonance.     

Non-stationary heat conduction of a porous medium

The thermal diffusion process is examined for a porous sample with idealized arrangement and form of the pores, when its surface is illuminated by a modulated light. A formula for the frequency dependence of the average surface temperature is derived. It is shown that it depends on the porosity, the form of the pores, and the ratio between a characteristic pore size and the thermal wavelength. In the limiting cases of low frequency of modulation and low porosity the results agree well with those quoted in the literature. The frequency dependence of the surface temperature of a microporous rubber sample, glass filtering crucibles, and leather samples have been measured by a PA cell and compared with the analytical results. The influence of various processes on the heat diffusion in porous media is discussed.     

Measuring nanopore size from the spin-lattice relaxation of CF4 gas

The NMR 19F spin-lattice relaxation time constant T1 for CF4 gas is dominated by spin-rotation interaction, which is mediated by the molecular collision frequency. When confined to pores of approximately the same size or smaller than the bulk gas mean free path, additional collisions of molecules with the pore walls should substantially change T1. To develop a method for measuring the surface/volume ratio S/V by measuring how T1 changes with confinement, we prepared samples of known S/V from fumed silica of known mass-specific surface area and compressed to varying degrees into cylinders of known volume. We then measured T1 for CF4 in these samples at varying pressures, and developed mathematical models for the change in T1 to fit the data. Even though CF4 has a critical temperature below room temperature, we found that its density in pores was greater than that of the bulk gas and that it was necessary to take this absorption into account. We modeled adsorption in two ways, by assuming that the gas condenses on the pore walls, and by assuming that gas in a region near the wall is denser than the bulk gas because of a simplified attractive potential. Both models suggested the same two-parameter formula, to which we added a third parameter to successfully fit the data and thus achieved a rapid, precise way to measure S/V from the increase in T1 due to confinement in pores.     

Evolution of morphologic properties on the preparation of Ir/Al2O3 catalysts with high metallic contents

Ir/Al₂O₃ catalysts with high metallic contents are applied on satellite thruster to decompose hydrazine. The present work has as principal aim the study of the morphologic evolution of Ir/Al₂O₃ catalysts with metallic contents from 12 to 30 wt.%. The catalysts were prepared through consecutive impregnations from the H₂IrCl₆ precursor, using three different types of aluminas. The specific surface area, volume and distribution of pore size, specific metallic area and metallic particles average diameter, as well as the mechanical resistance were determined. Results show that the Ir addition leads to a decrease of the specific surface area and the pores volumes, while increases the mechanical resistance. Values for average diameter of metallic particles are comprised between 1.4 and 2.4 nm when the metallic content increases from 12 to 30 wt.%. Catalysts containing 30 wt.% of Ir presents specific metallic areas around 30 m²/g, although pores volumes and distributions of pore size were considerably different for the three supports. Their metallic particles dispersion and size values are very close to those of a commercial catalyst Shell 405, even though the preparation methods were different. These results show that there is a strong interaction between the alumina and the iridium precursor.     

Effect of γ-radiation on the strain characteristics of a high-filled wood-plastic composite

The strain rate and the characteristics of the jumps at micro- and nanolevels were measured by the high-precision interferometric method for a wood-plastic composite irradiated to doses of 0–100 kGy. Radiation was shown to strengthen the material and change the characteristics of strain rate and value jumps. Strain jumps and mean-square deviations of the measured strain rate from its smoothened time dependence were determined for micro- and nanosized jumps. The change of these characteristics depending on the radiation dose of specimens was traced. A relation between the characteristics of micrometer jumps and the macroscopic strain was revealed.

     

Studies of intrawall porosity in the hexagonally ordered mesostructures of SBA-15 by small angle X-ray scattering and nitrogen adsorption

Ordered mesoporous silicas (OMSs) such as SBA-15 (p6mm symmetry group) synthesized in the presence of block copolymers containing poly(ethylene oxide) blocks possess irregular complementary pores in the walls of ordered mesopores. The X-ray scattering caused by this complementary porosity contributes to the background of the SAXS patterns. This work shows the possibility of using the SAXS data for the study of intrawall channels interconnecting ordered cylinders in SBA-15. The proposed SAXS analysis was tested by using a series of SBA-15 samples obtained at different temperatures of hydrothermal treatment (from 60 to 180 °C). The structural modelling of the SAXS patterns recorded for a series of SBA-15 samples was performed by using the continuous density function (CDF) technique in combination with the derivative difference minimization (DDM) method of full-profile refinement. This method is well suited for extraction of the background curves from the SAXS patterns. The resulting smooth background curves were analyzed by the well-known method in the SAXS theory used for evaluation of heterogeneity distributions, which in this case characterize the intrawall complementary porosity. A relatively good agreement has been observed between the data obtained by SAXS and nitrogen adsorption analysis. The SAXS analysis is sufficiently sensitive for examination of heterogeneous microporosity in SBA-15 materials. The average diameter of intrawall pores for the SBA-15 sample obtained at 60 °C was only about 1.4 nm. However, this diameter increased with the increasing temperature of hydrothermal treatment; namely, it was 1.5, 1.8, 2.6, 2.6, 3.5 and 5.2 nm for the SBA-15 samples hydrothermally treated at 80, 100, 120, 140, 160 and 180 °C, respectively.