基于TG-FTIR的落叶松木材热失重与热解气相演变规律研究

采用热重红外光谱联用分析法考察了落叶松木材在不同升温速率下的热失重特性及气相演变规律,并与其组分模混物的热解特性进行了对比分析。结果表明,落叶松的主要失重区域相对于模混物较宽,落叶松残炭率(18.97%)相对于模混物(29.83%)较低;在低温段,模混物的活化能高于落叶松木材,而在高温段二者差别不大;落叶松木材热解过程经历了水分析出、主成分热分解、后期炭化等阶段,气体析出主要集中在375℃左右;落叶松在热解反应过程中,主要气体产物生成量顺序为CO2>H2O>CH4>CO,随着升温速率的增加,上述气体产物的生成量明显增多;模混物与落叶松木材热解生成气体规律基本相似,但模混物中各气体析出强度均相对较高。     

Polarized neutron imaging: A spin-echo approach

Polarized neutron imaging has recently been introduced as an efficient method to three-dimensionally visualize and measure magnetic fields even in the bulk of massive objects. Here we introduce a spin-echo approach for polarized neutron imaging, which has the potential to overcome some drawbacks of the first attempts, namely to deal with strong fields, arbitrary field directions and quantification. Furthermore our novel approach increases the efficiency of quantitative studies due to relaxed monochromatisation requirements for spin-echo neutron imaging and with respect to additional information available in the recorded images, which allows for straightforward quantification in many cases.     

中子半影成像的数值模拟

 半影成像具有灵敏度高的特点,该技术是未来惯性约束聚变（ICF）中子成像的主要技术路线。基于中子半影成像的基本要求,利用蒙特卡罗方法,采用偏移抽样法和面通量的体通量替代技巧,模拟中子在半影成像系统中的输运,得到2维图像,并通过图像重建程序得到重建的源区图像。利用模拟结果,对编码孔屏蔽材料的选择和外径设计进行了初步优化,最终选择5 cm厚的钨屏蔽材料,其编码孔外径为1 cm。     

First neutron Bragg-edge imaging experimental results at CSNS

The neutron Bragg-edge imaging is expected to be a new non-destructive energy-resolved neutron imaging technique for quantitatively two-dimensional or three-dimensional visualizing crystallographic information in a bulk material, which could be benefited from pulsed neutron source. Here we build a Bragg-edge imaging system on the General Purpose Powder Diffractometer at the China Spallation Neutron Source. The residual strain mapping of a bent Q235 ferrite steel sample has been achieved with a spectral resolution of 0.15% by the time-of-flight neutron Bragg-edge imaging on this system. The results show its great potential applications in materials science and engineering.     

Recent improvements in the methodology of neutron imaging

The focus of this article is on further improvements of methods in neutron imaging: the increased spatial resolution for microtomography and options for energy-selective neutron imaging. Before going into details, some common statements are given in respect to the state-of-the-art in neutron imaging. A relation to the X-ray methods is mentioned, where complementary results are obtained. The potential for the energy selection is of particular interest for future installations at the new pulsed sources, based on spallation (SNS, J-PARC, ISIS-TS2). First results from preliminary studies look very promising for future material and industrial research. Therefore, statements about the set-up of the best possible imaging systems are included in the article.      

Development of neutron spin phase contrast imaging

We present an imaging technique utilizing a neutron spin interferometer. Neutron spin phase contrast is achieved in spatial resolved measurements of the phase difference between two superposed neutron spin states introduced by passing through a magnetic sample. Since the phase difference of spin states parallel and anti-parallel to the magnetic field is proportional to the magnetic field integral, it is possible to record images of the internal magnetic field distribution of the sample. Taking advantage of high transmission probabilities, neutron spin phase contrast provides non-destructive images of internal magnetic structures.     

Biomass pyrolysis in pulverized-fuel boilers: Derivation of apparent kinetic parameters for inclusion in CFD codes

Biomass combustion in pulverized-fuel boilers is a growing way to produce electricity from a renewable source of energy. Slagging and fouling limit however the reliability of the units that were initially designed for coal combustion. Computational Fluid Dynamics (CFD) codes aiming at studying those phenomena include simplified models of biomass particle pyrolysis, of which the pertinence has already been questioned for the typical conditions of interest. A comprehensive model has been developed to investigate pyrolysis of particles in pulverized-fuel boilers, with sizes ranging from 17 μm to 2.5 mm. The detailed model accounts for internal heat conduction, internal gaseous convection, moisture evaporation and particle shrinkage. It includes a competitive, multi-component kinetic scheme, improved for high temperatures. The discrepancy between the simplified models integrated in most CFD applications and the detailed simulations is highlighted. The simplified isothermal models underestimate pyrolysis time for the largest particles. Moreover, such models delay and shorten the volatiles release. The flame lengths, the local temperature fields and the pollutant emissions might be importantly impacted in global combustion simulations. Apparent kinetic parameters have been derived from the detailed simulations. Their use in existing simplified models improves the behavior of the biomass particles during pyrolysis, and offers therefore an efficient alternative to the integration of complex pyrolysis models in CFD codes.     

In situ SEOP polarised He neutron spin filter for incident beam polarisation and polarisation analysis on neutron scattering instruments

We discuss the development and characterisation of a new in situ spin exchange optical pumping (SEOP) based ³He neutron spin filter polarisation device. We present results from a recent test of the prototype system developed with the Institut Laue-Langevin. The polariser was installed on the polarised reflectometer CRISP at ISIS in the analyser position. The ³He was pumped continuously in situ on the beamline. The system also integrated a ³He adiabatic fast passage spin flipper that allowed reversal of the ³He and therefore neutron polarisation state, allowing for measurement of all four polarisation cross-sections. The system was run for a number of days reaching a ³He polarisation of 63%.     

Detailed modeling of hydrogen release and particle shrinkage during pyrolysis of inhomogeneous wood

Hydrogen release during pyrolysis of woody biomass is studied considering anisotropicity and inhomogeneity of wood structure. A new anisotropic shrinkage model is proposed based on the decomposition of main wood constituents, i.e., cellulose, hemicellulose, and lignin. The new shrinkage model can predict the temporal evolution of the wood structure, and the differences between axial and radial shrinkage during pyrolysis. The model agrees very well with several experimental data from the literature. Based on particle temperature during conversion, the pyrolysis is partitioned into four stages, and the hydrogen release and H${}_2$ formation from each stage are investigated. Stage (IV) of pyrolysis, from 1000 to 1273 K, is found to be efficient for H${}_2$ production owing to the production of considerable mass of H${}_2$ with a minimal amount of tar species. Furthermore, the char quality is found to be different at the end of stages (II), (III), and (IV), where around 67.7, 80.5, and 93.4% wt. of solid residue is made of carbon, respectively. The model is also used to explain how the heating rate affects the temperature distribution inside the particle and how it shifts the peak of hydrogen release. Finally, the pyrolysis of two inhomogeneous wood samples — a beech twig with bark and a beech dowel with growth rings — are investigated. The bark can affect the pyrolysis rate, products, and flow pattern inside the particle. The growth rings do not have a considerable effect on the pyrolysis rate and products, but they have a significant impact on the flow pattern. This has an important implication for char conversion studies where the internal surface area and porosity field distribution have a significant effect on the gasification and oxidation rates.     

In situ Raman imaging of osteoblastic mineralization

Hydroxyapatite (HA) is synthesized at early stages of bone formation by osteoblasts. Nondestructive observation of early stages of osteoblastic mineralization provides crucial information for biological mechanism of bone formation. Raman microscopy serves as an ideal tool to observe the osteoblastic mineralization process because it shows the chemical information of the sample at a minimally invasive level. In addition, HA is a marker for osteoblastic mineralization, and HA Raman signal is strong enough to identify mineralized spots in osteoblasts. In this research, we visualized the distribution of HA in cultured mouse osteoblasts by Raman imaging and observed the location of the mineralized spots in the culture. We monitored HA Raman signal from osteoblast culture for 3 days after administrating the osteogenic differentiation medium and observed Raman signal associated with HA. We identified mineralized spots of KUSA‐A1 by Raman imaging constructed from the distribution of HA Raman signal. We successfully visualized the distribution of the mineralized spots in the culture of KUSA‐A1. We compared our Raman images with Alizarin red S staining assay, which was a conventional method to evaluate the mineralization process. Raman imaging of the KUSA‐A1 culture visualized the mineralized spots more accurately than Alizarin red S staining assay. Raman imaging of HA serves as a powerful tool to identify the mineralized spots in an in vitro culture of osteogenic lineage cells. Copyright © 2014 John Wiley & Sons, Ltd.     

Generalized two-dimensional correlation infrared spectroscopy to reveal the mechanisms of lignocellulosic biomass pyrolysis

As the initial stage of combustion, pyrolysis plays a significant role in the combustion of biomass, a typical solid fuel that contains higher volatile contents than other solid fuels. To better understand the pyrolysis mechanism, we herein employed generalized two-dimensional correlation infrared spectroscopy (2D-PCIS) to analyze the functional group evolution in bamboo chars between 250 and 600 °C, and by combination of the volatile release properties, the biomass pyrolysis process mechanism was speculated. We found that below 250 °C, the hydrogen bonding network within the biomass macromolecular structure was broken, while at 250–300 °C, the branched structures were broken during hydration and decarboxylation reactions, resulting in the formation of H₂O, acetic acids, and CO₂. The subsequent formation of various phenols between 300 and 350 °C mainly originated from rupture of the ether bridges in the lignin structure. In addition, molecular rearrangement of the intermediates from the decomposition of holocellulose resulted in aromatic ring formation. Interestingly, analysis by 2D-PCIS demonstrated that the aromatic rings bearing adjacent substituents easily formed double active sites following breakage of the branched structures. These structures then easily produced fused ring systems below 400 °C, while dehydrogenation and polycondensation at?>?400 °C promoted the formation of fused rings from aromatic rings without adjacent substituents.     

In situ monitoring of uniformity by end point signal during plasma etching

A theory describing the etch rate uniformity based on the end point signal during the cleaning phase of etching is formulated for the case where the influence of residence time of the etching products and the loading effect can be neglected. An etch rate distribution function representing the probability density that the layer is etched at a given etch rate is introduced to calculate the relative root mean square of the etch rate across the wafer. The reduction in the size of the etched surface or the reduction of the flux of etching product molecules leaving the surface during the cleaning phase is used to determine the etch rate distribution function. A numerical simulation of the end point signal was used to illustrate possible applications of the theory. It is also shown that the slope of the end point curve itself cannot be used to characterize the etching nonuniformity as it is generally supposed. The theory was formulated with the aim of finding a simplein situ method applicable to statistical process control in semiconductor manufacturing when the nonuniformity of an etch process is characterized by a number (so-called 3σ method). Dedicated to Prof. Jan Janča on the occasion of his 60th birthday. This work was supported by the Slovak Grant Agency (No. 1/2312/95).     

Head and body imaging by hydrogen nuclear magnetic resonance

A hydrogen (¹H) nuclear magnetic resonance (NMR) imaging study of the normal head, thorax, and limbs is reported. The images are 10 to 15 mm thick transverse slices obtained in 2 to 4 min using a two-dimensional Fourier transform technique. Spatial resolution in the imaging plane is about 2 mm, enabling the optic nerve and many small blood vessels to be observed. Thorax scans show details of the cardiac chambers, aorta wall, and lungs without artefacts arising from physiological motion.     

Velocity imaging by ex situ NMR

A pulsed field gradient stimulated spin-echo NMR sequence is combined with imaging methods to spatially resolve velocity distributions and to measure 2D velocity maps ex situ. The implementation of these techniques in open sensors provides a powerful non-invasive tool to measure molecular displacement in a large number of applications inaccessible to conventional closed magnets. The method is implemented on an open tomograph that provides 3D spatial localization by combining slice selection in the presence of a uniform static magnetic field gradient along the depth direction with pulsed field gradients along the two lateral directions. Different pipe geometries are used to demonstrate that the sequence performs well even in the extremely inhomogeneous B0 and B1 fields of these sensors.     

In the wonderland of ultra-parallel neutron beams

Bragg reflections from single crystals yield angular widths of a few arcsec for thermal neutron beams. The Bonse-Hart proposal to attain a sharp, nearly rectangular profile by Bragg reflecting neutrons multiply from a channel-cut single crystal, was realized in its totality three and a half decades later by achieving the corresponding Darwin reflection curves for 5.23 Å neutrons. This facilitated SUSANS (Super USANS) measurements in the Q ～ 10^?5 Å^?1 range. The polarized neutron option was introduced into the SUSANS set-up by separating the up- and down-spin neutron beams by ～10 arcsec with a magnetic (air) prism. The neutron angular width has recently been reduced further by an order of magnitude to ～0.6 arcsec by diffracting 5.3 Å neutrons from a judiciously optimized Bragg prism. This constitutes the most parallel monochromatic neutron beam produced to date. I present the first SUSANS spectra probing the Q ～ 10^?6 Å^?1 domain, recorded with this beam.     

In situ growth of silver nanoparticles in mesoporous silica by spray pyrolysis

Silver-dispersed mesoporous silica was in situ synthesized in aerosol phase. The solidification of silica was catalyzed in the presence of the silver, which increased the order and d values of the mesophase at given reactor temperature. Silver nanoparticles grew confined in the pores when the atomic % of silver to Si was below 10 and the pore wall turned to be impermeable above 400 °C. Silver permeated through the pore wall below 400 °C to grow freely in the carrier gas. The mesophase deteriorated using spray pyrolysis above 800 °C due to the further densification of silica, or above 10 at.% of silver due to the excessive growth within the phase. The highest dispersion of silver ~4 nm in diameter with the highest order of the mesoporosity was obtained at 600 °C with 5 at.% silver. Calcination following the spray pyrolysis further densified the silica phase to freeze the growth of silver particles as well as lower the d value of the mesophase.     

中子散射成像探测角分辨研究

中子散射成像技术是近年来国外正在发展的一项新型辐射成像技术, 在深空宇宙探测、核材料监控等方面具有广阔的应用前景. 角分辨是衡量该技术成像能力的一项重要参数. 研究了位置不确定度和能量分辨对角分辨的影响. 理论分析表明: 以不同角度散射, 成像的角分辨不同; 位置不确定不仅直接影响角分辨, 还通过影响能量不确定度对角分辨间接贡献; 位置分辨主要来源于探测器的结构尺寸, 当探测器尺寸小于5 cm, 影响角分辨的主要来源是能量不确定度. 利用所获得的理论结果指导设计了原理探测系统, 并对设计的原理系统开展了初步实验研究. 结果表明, 分析结果与实验得到的角分辨参数基本一致.     

In situ multielemental monitoring in coral skeleton by CF-LIBS

Corals contain organic constituents identical to that of human skeleton, including Ca, Sr, Mg, Na, K, etc. Calibration-Free Laser-Induced Breakdown Spectroscopy (CF-LIBS) technique has been applied for quantitative estimation of the elements in coral samples. Laser-induced plasma emission at the sample surface, without any pretreatment, has been used for recording the spectra. The stoichiometric ablation and LTE criteria have been validated for the application of CF-LIBS. A data processing program in MATLAB for CF-LIBS has been developed for the determination of Ca, Sr, Mg, C, O, Na, K, and Fe concentration in these coral samples.     

中子半影成像的数值模拟

半影成像具有灵敏度高的特点,该技术是未来惯性约束聚变（ICF）中子成像的主要技术路线。基于中子半影成像的基本要求,利用蒙特卡罗方法,采用偏移抽样法和面通量的体通量替代技巧,模拟中子在半影成像系统中的输运,得到2维图像,并通过图像重建程序得到重建的源区图像。利用模拟结果,对编码孔屏蔽材料的选择和外径设计进行了初步优化,最终选择5 cm厚的钨屏蔽材料,其编码孔外径为1 cm。     

Structural modifications of dodecatungstophosphoric acid hexahydrate induced by temperature in the 10–358 K range. In situ high-resolution neutron powder diffraction investigation

Dodecatungstophosphoric acid hexahydrate H₃PW₁₂O₄₀·6H₂O crystal structure has been investigated by neutron powder diffraction (NPD) at different temperatures in the 10–358 K range. A nonconvergent reversible phase transition has been noticed at about 320 K. This transition is associated with a change in dynamic equilibrium of hydrate species and partial reduction/oxidation (redox) W⁶⁺↔W⁵⁺. Expressive structure changes lie in the P---O bonding inside Keggin's anion and the H₅O₂⁺ conformational angle.