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.     

Mössbauer and calorimetric studies of portland cement hydration in the presence of black gram pulse

Effect of different concentrations of naturally occurring admixture in the form of fine powder of black gram pulse (BGP) on the hydration of Portland cement was studied by isothermal calorimetry and ⁵⁷Fe Mössbauer spectroscopy. The spectra were recorded for anhydrous cement and the hydration products at room temperature and 77 K. In the presence of BGP, the spectra showed superparamagnetic doublets at room temperature and the sextet at 77 K, due to the presence of fine particles of iron containing component. Mössbauer studies of hydration products confirmed the formation of nanosize hydration products containing Fe^3?+?. The isomer shift (δ) and the quadrupole splitting (ΔE _Q) values of C₄AF in the cement confirmed iron in an octahedral and tetrahedral environment with +3 oxidation state. The high value of quadrupole splitting showed the high asymmetry of the electron environment around the iron atom. The overall mechanism of the hydration of cement in presence of BGP is discussed.     

Laser initiation of a mixture of PETN with NiC nanoparticles at elevated temperatures

The temperature dependence of the probability of the explosion of pentaerythritol tetranitrate (PETN) with an admixture of NiC particles (0.3 wt %) initiated by laser pulses (1064 nm, 20 ns) was studied over the temperature range 295–450 K. At 295–350 K, a weak temperature dependence was observed. The determining contribution to explosion initiation was made by the absorption of laser radiation by nanoparticles. The threshold of explosive decomposition at 295 K decreased by ∼40 times compared with samples free of NiC nanoparticles. Over the temperature range 400–450 K, the threshold of the explosive decomposition of samples containing NiC nanoparticles decreased with the activation energy ∼0.4 eV. A decrease in the threshold of explosive decomposition with a ∼0.4 eV activation energy over the temperature range 340–440 K was also observed for laser action on PETN samples not containing NiC. A hypothesis was suggested according to which the absorption of a light quantum caused the transfer of an electron from the valence band of the crystal to a level in the forbidden band with subsequent thermal positive ion dissociation to the carbocation and NO₃ radical.     

The Effect of Hydrolysis Temperature on Synthesis of Bimodally Nanostructured Porous Titania

Bimodally porous (2–4 and 20–100 nm) titania powders were prepared by hydrolysis of titanium tetraisopropoxide (TTIP), and the effect of hydrolysis temperature on the phase transformation and pore structure was investigated. The phase transformation was slightly retarded with increasing hydrolysis temperature, when the initial water concentration was small. The evolution of particle phase composition from amorphous to crystalline anatase and rutile was largely proportional to the calcination temperature and the initial water concentration. The pore size distribution was bimodal with fine intra-particle pores (2–4 nm in diameter) and larger inter-particle pores (20–100 nm). The intra-particle pores decreased in diameter at the hydrolysis temperature of 20°C. The specific surface area (SSA) of the dried powders ranged from 253 to 587 m²/g and the highest SSA was obtained at the hydrolysis temperature of 20°C.     

Phase transitions of fluids confined in porous silicon: A differential calorimetry investigation

The phase transitions of non-polar organic fluids and of water, confined in the pores of porous silicon samples, were investigated by Differential Scanning Calorimetry (DSC). Two types of PS samples (p^- and p⁺ type) with different pore size and morphology were used (with spherical pores with a radius of about 1.5 nm and cylindrical shape with a radius of about 4 nm respectively). The DSC results clearly show that the smaller the pores are, the larger is the decrease in the transition temperature. Moreover, a larger hysteresis between melting and freezing is observed for p⁺ type than for p^- type samples. A critical review of the thermodynamical properties of small particles and confined fluids is presented and used to interpret and discuss our DSC results. The effects of the chemical dissolution as well as the influence of anodization time are presented, showing that thick p⁺ type porous silicon layers are non-homogeneous. The DSC technique which was used for the first time to investigate fluids confined in porous silicon, enables us to deduce original information, such as the pore size distribution, the decrease in the freezing temperature of confined water, and the thickness of non-freezing liquid layer at the pore wall surface. Received: 11 May 1998 / Revised and Accepted: 29 July 1998     

Melting of Naphthalene Confined in Mesoporous Silica MCM-41

The ²H nuclear magnetic resonance (NMR) solid-echo spectra of naphthalene molecules as guests in the mesopores of neat MCM-41 with a pore width of 3.3 nm were measured in the temperature regime from 180 to 250 K. A strong reduction of the melting point of the naphthalene molecules by 152 K is observed. The line shape changes in the melting region were simulated with two different models, namely, the model of a narrow distribution of activation energies, which is typical for a crystal-like phase, and a two-phase model. Both models indicate a relatively narrow distribution of melting points of the naphthalene molecules inside the pores, indicative of a rather well-defined structure of the naphthalene molecules inside the pores. This finding supports the proposal of a plastic crystalline phase previously proposed by other groups.     

Relaxation of radiation-induced defects in CuO

The relaxation of radiation-induced defects in the CuO polycrystal and nanoceramic with the particle size d = 15 nm irradiated by an electron dose of F = 5 × 10¹⁸ cm^?2 has been studied. In the irradiated samples, a strong susceptibility increase with decreasing temperature T < 150 K is observed. This increase is due to the formation of ferromagnetic polarons in the antiferromagnetic matrix near the defects. The structural symmetry distortion makes the samples unstable. The time variations of the magnetic properties in the CuO samples prepared by different methods are compared.     

退火对He注入及随后208Pb27+辐照的Al2O3单晶PL谱的影响

利用高能离子研究了110 keV 的He⁺注入Al₂O₃单晶及随后230 MeV的²⁰⁸Pb²⁷⁺辐照并在不同温度条件下退火样品的光致发光的特性. 从测试结果可以清楚地看到在375 nm，390 nm，413 nm 和450 nm 出现了强烈的发光峰. 经过600 K退火2 h后测试结果显示，390 nm发光峰增强剧烈，而别的发光峰显示不明显. 在900 K退火条件下，390 nm的发光峰开始减弱相反在510 nm出现了较强的发光峰，到1100 K退火完毕后390 nm的发光峰完全消失，而510 nm的发光峰相对增强. 从辐照样品的FTIR谱中看到，波数在460—510 cm^-1间的吸收是振动模式，经过离子辐照后，吸收带展宽，随着辐照量的增大，Al₂O₃振动吸收峰消失，说明Al₂O₃振动模式被完全破坏. 1000—1300 cm^-1之间为Al-O-Al桥氧的伸缩振动模式，辐照后吸收带向高波数方向移动. 退火后的FTIR谱变化不大.     

Temperature dependent luminescence of Dy3+ doped BaYF5 nanoparticles for optical thermometry

Dy³⁺ doped BaYF₅ nanoparticles with tetragonal structure were synthesized by hydrothermal method and solvothermal method. The structural and the luminescent properties of the samples were characterized by X-ray diffraction pattern, TEM and photoluminescence spectra. Emission of Dy³⁺ originated from ⁴I_15/2 located at 450 nm and ⁴F_9/2 located at 478 nm, 573 nm and 660 nm were observed under excitation of 355 nm laser. Behavior of fluorescence intensity ratio with temperature increasing from room temperature to approximately 800 K was investigated. And the optimum temperature range for thermometry is obtained to be 550–800 K according to its sensitivity-temperature relation, indicating the potential application of BaYF₅:Dy³⁺ as a luminescent temperature sensor.     

基于准弹性中子散射谱分析水化硅酸钙(C-S-H)中受限水的动态

研究水化硅酸钙(C-S-H)中受限水动态的一种重要手段是准弹性中子散射(quasi-elastic neutron scattering, QENS)实验. C-S-H样品的QENS谱数据可通过跳跃扩散和转动扩散模型进行分析拟合, 进而导出C-S-H样品微纳孔中水动态的相关物理参数: 不动水指数C、转动扩散系数D_r、均方位移< u² >、自扩散系数D_t及平均停留时间τ₀. 本文对水与水泥质量比为30%的C-S-H样品, 测量温度为230-280 K的QENS谱进行了分析, 得到的拟合参数可定量描述C-S-H样品内不同尺度的微纳孔中受限水随温度变化的动态过程. 转动扩散系数D_r随散射矢量Q的变化可知, Q值较大时, 水分子的转动对QENS谱影响较大. 均方位移 < u² > 随Q值的不同而变化, 其拟合值可区分C-S-H样品中的不动水、强受限水和受限水. 在Q较小时, D_t 和τ₀ 的拟合值随温度而变化, 并分别在230和240 K突然增大, 由此揭示温度为230-240 K 时, C-S-H 样品中受限水分子的动态特性发生了转变.     

Intense blue luminescence of anodic aluminum oxide

The luminescence spectra of aluminum oxide with an ordered system of through pores have been studied. The diameter and density of pores were ≈ 50 nm and 1.2 × 10¹⁰ cm^?2, respectively. Amorphous aluminum oxide formed by anodization of aluminum foil in an oxalic acid electrolyte shows intense luminescence in the blue spectral region. Processing of spectra with the use of an oxalic acid approximation by Gaussian curves gives three bands peaking at ～ 382 (3.2 eV), 461 (2.7 eV), and 500 nm (2.5 eV), which correspond to different types of defects. The bands at 382 and 461 nm can be assigned to optical transitions involving F⁺ and F centers (vacancies of oxygen with one or two electrons), respectively. The lower-energy band near 500 nm can be presumably assigned to luminescence from F⁺⁺ centers (vacancy of oxygen without an electron). Analysis of the luminescence excitation spectra has revealed an inhomogeneous character of the distribution of the corresponding luminescence centers in the Al₂O₃ matrix.     

Synthesis of single-crystal Sm-Co nanoparticles by cluster beam deposition

Single-crystal Sm-Co nanoparticles have been successfully produced by a cluster beam deposition technique. Particles have been deposited by DC magnetron sputtering using high Ar pressures on both single-crystal Si substrates and Au grids for the magnetic and structural/microstructural properties, respectively. Oxidation of the particles is prevented by using carbon buffer and cover layers. Nanoparticles have a uniform size distribution with an average size of 4.2, 6 and 7 nm at 1, 1.5 and 2 Torr of Ar pressure, respectively. At 1 Torr, the particles have the disordered 1:7 structure and a high coercivity of 19 kOe at 10 K. These particles show a superparamagnetic behavior with a blocking temperature of T_B = 145 K. From this value of T_B and the particle volume, the value of anisotropy constant K is estimated to be around 2.2 × 10⁷ ergs/cc. Heat is introduced to the particles during their flight to the substrate to increase the particle size. Nanoparticles of SmCo₅ with an average size of 15 nm and high room temperature coercivity have been produced. No change in magnetic and structural properties of the samples has been observed even after 10 months. Cluster beam deposition could play a key role for the production of rare earth nanoparticles for many applications.     

The1HT 1 study of the influence of clay addition on Portland cement hydration

Effects of addition of three standard clay minerals, Na-montmorillonite, illite and kaolinite, on Portland cement hydration properties were studied. The¹H spin-lattice relaxation of exchangeable water was monitored during hydration time and the data were processed by spin-grouping analysis. The values and evolution dynamics of both resolvedT ₁ components and corresponding magnetization fractions show that each day mineral lowers the fluidity of Portland cement paste and accelerates its hydration in dormant. In advanced stages of hydration, the Na-montmorillonite provides the accelerating influence, while the kaolinite exhibits the retarding effect. The final values of gel pores to capillaries percentage fractions ratio indicate a slightly lower porosity of samples with Namontmorillonite and a higher porosity of pastes with the same percentage of illite or kaolinite, regarding to the pure hardened Portland cement.     

Effects of ordering quality of the pores on the photoluminescence of porous anodic alumina prepared in oxalic acid

Photoluminescence (PL) of the anodic alumina has been studied and related with quality of hexagonal ordering of the pores. The photoluminescence excitation (PLE) spectra have been successfully de-convoluted into primarily two sub-bands with peak positions at about 355 and 395 nm and maximum emission at about 450 and 500 nm, respectively; the former being assigned to F⁺ centers and the latter to the F-centers. A red shift in the PLE takes place, at a given anodizing voltage, when the quality of the hexagonal pore ordering deteriorates with an increase in number density of defects, i.e., pentagons and hexagons with missing pores. The metallic hills at these defects change the curvatures of the metal-oxide and the oxide-electrolyte interfaces that could affect the field distribution and hence the stress-state and other characteristics of the oxide at the defects. This allows a comparatively larger concentration of F centers (395 nm band), causing a red shift in the PLE with increase in defect density.     

超临界CO_2在岩石孔隙内流动状态的分子模拟

本文采用分子模拟的方法研究了地质封存条件下超临界CO_2在镁橄榄石孔隙内的流动,分析了孔隙尺寸、温度、压强对超临界CO_2的密度分布和流动速度的影响.研究结果表明,只有当孔隙尺寸大于5.0 nm时,超临界CO_2分子在岩石孔隙内的流动才符合Poiseuille流动;同时,超临界CO_2分子在岩石近壁面存在1.5 nm的密度震荡,当孔隙尺寸小于15 nm时,密度振荡现象会影响CO_2分子在岩石孔隙内的平均密度;升高温度、降低压强的方法可以减小密度震荡的第一峰值,减弱岩石壁面与CO_2的相互作用,使得CO_2的流动速度增加.     

Vacancy effects on one-dimensional migration of interstitial clusters in iron under electron irradiation at low temperatures

We performed in situ observation of one-dimensional (1D) migration of self-interstitial atom (SIA) clusters in iron under electron irradiation at 110–300 K using high-voltage electron microscopy. Most 1D migration was stepwise positional changes of SIA clusters at irregular time intervals at all temperatures. The frequency of 1D migration did not depend on the irradiation temperature. It was directly proportional to the damage rate, suggesting that 1D migration was induced by electron irradiation. In contrast, the 1D migration distance depended on the temperature: distribution of the distance ranged over 100 nm above 250 K, decreased steeply between 250 and 150 K and was less than 20 nm below 150 K. The distance was independent of the damage rate at all temperatures. Next, we examined fluctuation in the interaction energy between an SIA cluster and vacancies of random distribution at concentrations 10^?4–10^?2, using molecular statics simulations. The fluctuation was found to trap SIA clusters of 4 nm diameter at vacancy concentrations higher than 10^?3. We proposed that 1D migration was interrupted by impurity atoms at temperatures higher than 250 K, and by vacancies accumulated at high concentration under electron irradiation at low temperatures where vacancies are not thermally mobile.     

Analysis of bolometer operation near the superconducting transition edge using microwave readout

The results of pioneering experiments on using a new method of microwave recording the bolometric response from a metal film near its superconducting transition edge are analyzed. Experiments are carried out at 4.5 K using a thin-film niobium absorber with a critical temperature of 6.7 K. The validity of the adopted electrodynamic model is confirmed. The chip contains a miniature antenna tuned to approximately 600 GHz and integrated into a planar resonator with a frequency of 6 GHz, which is weakly coupled with a pump line. Based on the experimental and model data, the presence of electrothermal feedback is shown, stability criteria are found, and I–V characteristics at microwaves are obtained. Bulk experimental samples with an absorber measuring 5 μm × 2.5 μm × 15 nm are fabricated with optical photolithography. At an amplifier channel noise of 3 K, the optical sensitivity of a prototype receiver can be expected at a level of 10^?15 W/Hz^1/2.     

低温下Er3+/Yb3+共掺碲酸盐玻璃的发光特性研究

研究了在8—300K温度范围中, Er³⁺/Yb³⁺共掺碲酸盐玻璃的15μm荧光光谱、上转换光谱与温度的关系. Er³⁺:⁴I_13/2→⁴I_15/2跃迁发射光谱通过高斯拟合和简单的四能级系统估计了Er³⁺离子⁴I_13/2和⁴ 关键词： 碲酸盐玻璃 上转换发光 低温 荧光特性     

High sensitivity of palladium on porous silicon MSM photodetector

In this work, the nanocrystalline porous silicon (PS) is prepared through the simple electrochemical etching of n-type Si (1 0 0) under the illumination of a 100 W incandescent white light. SEM, AFM, Raman and PL have been used to characterize the morphological and optical properties of the PS. SEM shows uniformed circular pores with estimated sizes, which range between 100 and 500 nm. AFM shows an increase in its surface roughness (about 6 times compared to c-Si). Raman spectra of the PS show a stronger peak with FWHM=4.3 cm⁻¹ and slight blueshift of 0.5 cm⁻¹ compared to Si. The room temperature photoluminescence (PL) peak corresponding to red emission is observed at 639.5 nm, which is due to the nano-scaled size of silicon through the quantum confinement effect. The size of the Si nanostructures is estimated to be around 7.8 nm from a quantized state effective mass theory. Thermally untreated palladium (Pd) finger contact was deposited on the PS to form MSM photodetector. Pd/PS MSM photodetector shows lower dark (two orders of magnitude) and higher photocurrent compared to a conventional Si device. Interestingly, Pd/PS MSM photodetector exhibits 158 times higher gain compared to the conventional Si device at 2.5 V.     

注入Ar+的蓝宝石晶体退火前后光致发光谱的分析

对注入Ar⁺后不同晶面取向的蓝宝石晶体在不同退火条件下的光致发光谱进行了分析.分析结果表明:三种晶面取向的蓝宝石样品经Ar⁺注入后,其光致发光谱中均出现了新的位于506nm处的发光峰;真空和空气气氛下的退火均对样品在506nm处的发光有增强作用,不同晶面取向的样品发光增强程度不同,且发光增强至最大时的退火温度也不同,空气气氛下的退火使样品发光增强程度更为显著.由此可以看出,退火气氛、退火温度和晶面取向均对样品发光峰强度有影响. 关键词： 2O₃')" href="#">Al₂O₃ 离子注入 退火 光致发光谱