Characterization of nanometric carbon materials by time-resolved fluorescence polarization anisotropy

In this work, time-resolved fluorescence polarization anisotropy (TRFPA) technique has been applied to the determination of the average size of asphaltenes and combustion-generated carbon nanoparticles. The characteristic depolarization time of fluorescence light following photon absorption is related to the typical particle size through the Stoke–Einstein rotational diffusion equation. The TRFPA technique employed in our experiment achieves sub-nanosecond time resolution, roughly corresponding to sub-nanometer accuracy in determining the particle size. The technique has been applied to both asphaltene and carbon nanoparticles, the former being a component of petroleum, whereas the latter result from combustion processes. Therefore, a complete and reliable characterization of such particles is of great importance in oil industry and atmospheric physics, respectively. Although the TRFPA technique has been developed and widely used on molecular and biological samples, it proves to be a very powerful tool for measuring the size of asphaltene and soot particles as small as few nanometers with a resolution of the order of 0.1 nm.     

Diffusivity in water and fluorescence properties of?organic nanoparticles produced in?flames

Rotational and translational diffusion properties in water of nano organic carbon (NOC) particles collected from premixed laminar ethylene/air flames have been investigated using both time resolved fluorescence polarisation anisotropy (TRFPA) and fluorescence correlation spectroscopy (FCS). Insight into the NOC sizes, structures and rigidity has been gained through diffusion properties exploiting their fluorescence in different spectral ranges. The TRFPA measurements revealed the presence of two classes of particles. The first composed of particles with a mean size of 1.5?nm which absorb and fluoresce in the UV, and a second class composed of slightly larger particles, about 2.2?nm, which absorb and fluoresce in the visible and were also detected by FCS. From FCS measurements particle concentration and fluorescence quantum yield have been evaluated.     

炸药爆炸冲击波合成纤锌矿型氮化硼

 本文报道了用国产石墨型氮化硼（gBN）为原料在炸药爆炸产生的冲击波作用下合成纤锌矿型氮化硼（wBN）的技术。对冲击波作用后的回收产物进行化学分离，得到杂质含量低于0.5%的wBN产品；回收产物的wBN的转化率高于50%；单发试验产量达11~12 g。目前已利用这一技术生产出少量wBN产品。在相同的冲击波条件下，对四种不同来源的gBN进行了合成试验。发现wBN的转化率强烈地依赖于原始gBN的结晶特性。比表面积测量及X射线衍射观察表明，冲击波合成的wBN是一种多晶微粉，平均颗粒度约0.1 μm，平均晶粒度约17.5 nm。差热分析显示放热反应起始温度为1 055 K，峰顶温度1 238 K。     

Fluorescence properties of biochemicals in dry NaCl composite aerosol particles and in solutions

Several fluorophores, such as tryptophan, NADH, NADPH, and riboflavin are found in airborne micro-organisms. In this work, the fluorescence properties of these biochemicals were studied both in dry NaCl composite aerosol particles and in saline solutions by means of laser-induced fluorescence. Fluorescence spectra were measured from individual, airborne aerosol particles and from solutions in cuvette. The excitation wavelength was varied in steps from 210 nm to 419 nm and the fluorescence was detected within a wavelength band of 310–670 nm. For each sample, the measured fluorescence emission spectra were combined into fluorescence maps. The fluorescence maximum of riboflavin in a dry NaCl composite particle is 20 nm red-shifted compared with the solution, whereas the maxima are blue-shifted by about 25 nm for tryptophan and 15 nm for NADH and NADPH. The molecular fluorescence cross sections have significant differences between the aerosol particles and the solutions, except for tryptophan. For NADH and NADPH the cross sections are over 20 times larger in the aerosol particles than in the solutions probably as a result of partial quenching of fluorescence in solution caused by the collision or stacking with the adenine moiety. The fluorescence cross section of riboflavin is almost 60 times larger in the solution than in the dry NaCl composite aerosol. This is probably caused by the different microenvironment around the fluorophore molecule and by the concentration quenching in the particles where the fluorescing molecules are relatively close to each other.     

不同土壤物理性质下石油类污染物LIF发射特征研究

利用激光诱导荧光技术可对土壤中石油类污染物快速检测,不同土壤物理性质下,污染物荧光发射特征具有一定差异。为实现外场检测时快速制备合适的土壤样品,实验研究了土壤疏松度、颗粒度、湿度与土壤中石油类污染物荧光强度及光谱稳定性之间的关系。压片机压强大于2 MPa时土壤样品荧光光谱的稳定性较好,九种不同疏松度的土壤样品荧光强度的相对标准偏差为3.51%。不同粒径的机油土壤样品荧光强度差异较小,其中100目土壤样品的荧光光谱RSD值为2.25%。结果表明,土壤样品表面呈平整洁净时,所得样品荧光光谱的稳定性较好,土壤疏松度和颗粒度对荧光光谱的影响较小。湿度对土壤样品荧光发射的影响较大,当土壤湿度低于10%,荧光强度变化较小;湿度范围大于10%时,荧光强度变化较大。为利用LIF技术对外场土壤中石油类污染物检测时,快速有效制备土壤样品及准确测量提供参考。     

全反射X射线荧光分析植物粉末样品的制样方法研究

全反射X射线荧光光谱(TXRF)分析是一种应用广泛、经济快捷的多元素显微与痕量分析方法。随着现代科技机器自动化的快速发展,样品制备成为TXRF分析定量的关键问题。本实验以茶叶粉末为分析对象,探讨了在TXRF分析过程中分散剂、样品量及粒径对粉末悬浮样品的制样效果、制样过程重复性及测量准确性的影响。结果表明：（1）通过分析粒径范围大于180目的茶叶粉末样品的五个独立重复试样,测试了TXRF法的整体精密度,分析了仪器的稳定性与样品制备过程中的不确定度,结果表明不论在何种元素与浓度范围下,与样品制备步骤相关的不确定度对获得的结果的全局精度都有显著贡献（>60%）,样品的制备是分析误差的主要来源;（2）通过将粒径范围大于180目的茶叶粉末样品分散于1% Triton X-100与去离子水两种分散剂中,对分散剂的影响进行了研究,相较于非离子型表面活性剂,去离子水重复性更好,RSD在2.45%～11.64%之间,更适合作为粒径大于180目的茶叶粉末样品的分散剂,使得中、高Z元素的定量更为准确;（3）通过添加不同质量的粉末样品于5 mL去离子水中对样品量进行分析。样品量过低会导致制样重复性较差,而过高的进样量会导致样品薄膜厚度超过射线的测量厚度,有可能不再处于全反射条件下。对于植物粉末样品20 mg/5 mL是一个较为合适的样品量;（4）通过对7种粒径范围的粉末样品进行测量分析,研究了粒径对测量结果的影响。在粒径小于180目的范围内净计数随粒径的减小而增大;在粒径小于200目的范围内精密度随粒径的减小而提升;除Mn之外的元素粒径对准确性未有显著影响;在80～200目的范围内,不确定度迅速降低,大于200目后不确定度低于10%。综合考虑净计数、精密性与准确性,在制样过程中粒径范围建议研磨至200～300目之间,该研究结果可为植物粉末样品制样方法提供有效借鉴。     

石英砂-聚乙烯二元混合体系的太赫兹光谱特性研究

太赫兹时域光谱技术目前逐渐应用于对岩石的研究中。在制备样品时通常需要将岩石磨碎后与粘合剂混合压片,岩石的含量、粒径等都会对测试结果造成影响。将自然界中常见的石英砂粉末（不同粒径）与聚乙烯（PE）微粒以不同的比例混合,通过压片的手段将其制成适用于太赫兹系统测试的样品,用以探究样品中石英砂的含量以及其粒径对实验结果的影响。首先研究石英砂含量对实验结果造成的影响。在保持样品中石英砂的粒径不变的情况下,发现不同石英砂含量样品的时域光谱图中,时间延迟以及峰值都呈现出非单调的变化趋势。为了探究出现这种现象的原因,对样品的折射率以及吸收系数做了进一步的分析。结果表明样品的折射率会随着样品中石英砂含量的增加而逐渐增大,通过适用于本实验的有效介质理论能够解释这一现象。样品对于太赫兹波段的吸收系数随着石英砂含量的增加呈现出先增大后减小的现象,并且在石英砂质量分数为60%时达到最大值。为了解释这一现象产生的原因,利用扫描电子显微镜对样品的微观形貌进行观察,发现随着石英砂含量的增加,在压制样品时PE颗粒破碎程度加剧,导致PE的粒径变小。根据米氏散射以及瑞利散射的原理,石英砂粒径不变而PE粒径减小,随之降低的散射强度与石英砂的吸收效应发生竞争,从而导致了吸收系数先增大后减小的现象。进一步研究了石英砂粒径对实验结果的影响,对不同粒径的石英砂样品进行测试,发现折射率不随石英砂粒径的变化而改变,但其吸收系数随着石英砂粒径的减小而逐渐减小。根据米氏散射,样品吸收系数的变化是由于散射强度随石英砂粒径的减小而逐渐减小。研究表明,样品中石英砂的含量和粒径都会对实验结果产生影响。石英砂粒径相同时,样品的吸收系数随石英砂含量的增加呈现先增大后减小的趋势,样品的折射率随石英砂含量的增加而逐渐增大;石英砂含量相同时,样品的吸收系数随石英砂粒径的减小而逐渐减小,而样品的折射率基本不变。这一结论对矿物样品的制备以及对混合物的实验结果分析有一定程度的指导意义。     

Direct Fluorescence Monitoring of Coal Organic Matter Released in Seawater

Whenever immersed in seawater after a collier accident, a fossil fuel such as coal could become a source of pollution to the marine environment. To study the effect of such a contamination, four coal samples from different origins were used. A first analysis on those coals enabled us to determine the content of polycylic aromatic hydrocarbons. Seawater was then mixed with coal to study the organic matter released from coal into seawater. Fluorescence was used for its sensitivity to aromatic compounds, with the additional purpose of evaluating the relevance of using an immerse fluorescence probe to monitor water pollution. Excitation–emission matrices were recorded and the excitation–emission wavelength range corresponding to the highest fluorescence intensity was 230 nm/[370 nm; 420 nm]. The samples with coal happened to fluoresce more than the coal-free samples, the difference depending on the coal origin. The fluorescence intensity increased with coal mass, up to some limit. The particle size also influenced the fluorescence intensity, the finest particles releasing more fluorescing substances, due to their higher exchange surface. When seawater percolated through coal, the samples fluoresced highly at the beginning, and then the fluorescence intensity decreased and reached the seawater level. However, even with a 10 ns acquisition time shift, the fluorescence spectra were not specific enough to show the presence of PAHs in the samples, which were too diluted to be detected, whenever released from coal into seawater. The lifetimes of the seawater and of the coal samples were respectively 4.7 and 3.8 ns, indicating that the substances released from coal mainly consisted of short-lived fluorescing substances, such as natural humic or fulvic substances. Consequently, the presence of coal does not seem to be too detrimental to the marine environment, and a direct fluorescence probe could be used to monitor the seawater organic charge increase due to the immersion of coal in seawater.     

Colloidal Analysis of Particles Extracted from Microalloyed Steels

Different colloidal particle characterization methods are examined for their suitability to determine the particle size distribution of particles extracted from steels. Microalloyed steels are dissolved to extract niobium and titanium carbonitride particles that are important for the mechanical properties of these steels. Such particles have sizes ranging from several nanometers to hundreds of nanometers depending on the precipitation stage during the thermomechanically controlled rolling process. The size distribution of the particles is analyzed by dynamic light scattering (DLS), analytical ultracentrifugation (AUC), and hollow fiber flow field-flow fractionation (HF5) and compared to data obtained for reference particles as well as data from electron microscopy, the standard sizing technique used in metallurgy today. AUC and HF5 provide high-quality size distributions, average over large particle numbers that enables statistical analysis, and yield useful insights for alloy design; however, DLS fails due to a lack of resolution. Important aspects in the conversion and comparison of size distributions obtained for broadly distributed particle systems with different measurement principles and the role of surfactants used in sample preparation are discussed.     

Particle Size Characterization of an Extra Fine Milled Product

The present research aims to characterize the particle size distribution of sub micron particles suspended in a liquid. The particles milled are an organic poorly water soluble crystalline product. To characterize the size of these particles, different techniques have been tested: imaging techniques (SEM, CryoTEM), static light scattering techniques, dynamic light scattering techniques, centrifugation and flow field flow fractionation. The results indicate that the studied milled particles have a primary particle size close to 180nm and there is strong evidence of larger particles which are very likely aggregates. This is clearly seen from the Cryo TEM results. All the above mentioned techniques should in principle be able to measure samples of dispersion containing particles of ca 180 nm but several are disturbed by the presence of large aggregates. It is difficult to estimate the amount of aggregate present, but most of the time one is interested in what the primary particle size distribution is. It is clear that no single piece of equipment is capable of exactly determining the particle size distribution of our samples, but the static light scattering with low shear on mixing does give a good representation of what is seen with the image analysis by cryo TEM.     

Approaches to solid sample preparation based on analytical depth for reliable X‐ray fluorescence analysis

In this paper, we discuss approaches to prepare solid samples for X‐ray fluorescence spectrometry (XRF). Although XRF can be used to analyze major and minor elements in various solid samples including powders and grains without dissolution techniques, to obtain reliable XRF results, the prepared sample must meet certain criteria related to homogeneity, particle size, flatness, and thickness. The conditions are defined by the analytical depth of fluorescent X‐rays from analytes, and the analytical depth can be estimated from the X‐ray absorption related to the energy of each X‐ray and the composition and density of the sample. For example, when the sample flatness and particle size are less than the analytical depth and the sample possesses homogeneity within a depth less than the analytical depth, the XRF results are representative of the entire sample. Furthermore, an appropriate sample thickness that is larger than the analytical depth or constant can prevent changes in fluorescent X‐ray intensity with variations in sample thickness. To obtain accurate and reproducible measurements, inhomogeneous solid samples must be pulverized, homogenized, and prepared as loose powder, powder pellets, or glass beads. This paper explains the approaches used to prepare solid samples for XRF analysis based on the analytical depths of fluorescent X‐rays. Copyright © 2016 John Wiley & Sons, Ltd.     

Analysis of precipitates in ultrafine-grained metallic materials

In the present work, new possibilities of the X-ray diffraction for investigations of the phase composition, size, shape and volume fraction of particles in ultrafine-grained ferritic/martensitic steel and the Cu-Cr-Zr alloy have been demonstrated. For the first time, the method of X-ray diffraction in the transmission mode was used to identify particles with a volume fraction of less than one percent in the ultrafine-grained materials studied. The small-angle X-ray scattering method was used to estimate the size and shape of dispersed particles. Specific features of the ultrafine-grained structure determined by the X-ray diffraction and transmission electron microscopy studies were used for estimation of dispersion hardening in the samples obtained by equal-channel angular pressing in comparison with the samples subjected to standard treatment.     

微颗粒X射线荧光强度MCNPX模拟与WDXRF实验

为研究样品微颗粒在X射线荧光(XRF)分析中对测量结果的影响,运用蒙特卡罗模型MCNPX对X射线荧光仪进行建模,研究了样品颗粒粒径对X射线荧光特征峰强度、峰总比和源峰探测效率的影响,并设计波长色散X射线荧光光谱法(WDXRF)分析实验对模拟结果进行了检验。结果表明：对于样品微颗粒X射线荧光强度与粒径尺寸的关系,MCNPX模拟值与理论计算值保持一致;MCNPX模拟结果与WDXRF实验结果存在一定差异,这取决于MCNPX模型对待测样品状态的假设与实际情况存在一定的差异性;运用样品粉碎、研磨至小颗粒并进行压片处理的办法,可使WDXRF实测结果尽可能的减小与MCNPX理论模拟结果的差异性;在待测样品的颗粒粒径达到一定尺寸时,其峰总比、源峰探测效率、特征峰X射线荧光计数均趋于稳定值;颗粒粒径在某一特定尺寸范围之内,颗粒度效应的影响不容忽视;除此之外,颗粒度效应的影响基本可以忽略。论文充分考虑了待测样品颗粒粒径对XRF分析结果的影响,为减小因颗粒度效应引起分析结果的不确定性提供了一种可行的研究思路,该方法也可为X射线分析的生产实践提供一定的技术参考。     

Calculation of Particle Size Distributions from Ultrasonic Measurements: A Mineral Slurry Case Study

Ultrasonic transmission measurements have been used extensively to determine the particle size of solids in slurries. This case study examines the application of mathematical inversion techniques to the determination of the particle size distribution of a mineral slurry from data collected at a minerals processing plant. A new mathematical inversion technique, based on an extension of modified Chahine iteration combined with the principle of maximum entropy has been developed. Four algorithms were constructed and used to calculate particle size distributions from synthetic and raw plant data. These incorporated modified Chahine iteration and its extension, together with two different approaches to applying a density measurement constraint on the particle size distribution. In general the algorithms performed well with regression errors below 3 %. The correlation coefficients and slopes for this technique were 0.86 and 1.35 for the weight fraction of particles less than 75 microns when compared with the laser diffraction analysis. A better match was obtained for the plant data by using the new inversion technique, into which the principle of maximum entropy has been incorporated whereas this was not the case with the synthetic data, illustrating the need to match the inversion technique to the problem.     

EDXRF and TXRF analysis of elemental size distributions and environmental mobility of airborne particles in the city of Riga,Latvia

Airborne particles were investigated in the central part of Riga during October 2000. Mass, black carbon and elemental concentrations of airborne particles were measured on Teflon filters from a dichotomous impactor, which samples fine (<2.5 µm) and coarse (2.5–10 µm) fractions of particles. In order to obtain more detailed information on the size distributions of different elements, a seven‐stage Batelle cascade impactor was used, in which quartz plates treated with silicone grease were utilized as backing for the different stages. Total reflection x‐ray fluorescence (TXRF) and energy‐dispersive x‐ray fluorescence (EDXRF) spectrometry were used for elemental analysis on the quartz plates and Teflon filters. The environmentally mobile part of the fine particle elements in the aerosol was determined by subtraction of x‐ray spectra measured before and after sequential leaching of the aerosol filters. The results of the different measurements show that naturally generated street dust and soil particles are dominant in coarse particles, whereas particles generated by human activities are dominant in the size fraction <0.5 µm. Copyright © 2004 John Wiley & Sons, Ltd.     

Using simple particle shapes to model the Stokes scattering matrix of ensembles of wavelength-sized particles with complex shapes: possibilities and limitations

We investigate to what extent the full Stokes scattering matrix of an ensemble of wavelength-sized particles with complex shapes can be modeled by employing an ensemble of simple model shapes, such as spheres, spheroids, and circular cylinders. We also examine to what extent such a simple-shape particle model can be used to retrieve meaningful shape information about the complex-shaped particle ensemble. More specifically, we compute the Stokes scattering matrix for ensembles of randomly oriented particles having several polyhedral prism geometries of different sizes and shape parameters. These ensembles serve as proxies for size-shape mixtures of particles containing several different shapes of higher geometrical complexity than the simple-shaped model particles we employ. We find that the phase function of the complex-shaped particle ensemble can be accurately modeled with a size distribution of volume-equivalent spheres. The diagonal elements of the scattering matrix are accurately reproduced with a size-shape mixture of spheroids. A model based on circular cylinders accurately fits the full scattering matrix including the off-diagonal elements. However, the modeling results provide us with only a rough estimate of the effective shape parameter of the complex-shaped particle ensemble to be modeled. They do not allow us to infer detailed information about the shape distribution of the complex-shaped particle ensemble.     

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.     

Brownian dynamics of polydisperse colloidal hard spheres: Equilibrium structures and random close packings

Recently we presented a new technique for numerical simulations of colloidal hard-sphere systems and showed its high efficiency. Here, we extend our calculations to the treatment of both 2- and 3-dimensional monodisperse and 3-dimensional polydisperse systems (with sampled finite Gaussian size distribution of particle radii), focusing on equilibrium pair distribution functions and structure factors as well as volume fractions of random close packing (RCP). The latter were determined using in principle the same technique as Woodcock or Stillinger had used. Results for the monodisperse 3-dimensional system show very good agreement compared to both pair distribution and structure factor predicted by the Percus-Yevick approximation for the fluid state (volume fractions up to 0.50). We were not able to find crystalline 3d systems at volume fractions 0.50–0.58 as shown by former simulations of Reeet al. or experiments of Pusey and van Megen, due to the fact that we used random start configurations and no constraints of particle positions as in the cell model of Hoover and Ree, and effects of the overall entropy of the system, responsible for the melting and freezing phase transitions, are neglected in our calculations. Nevertheless, we obtained reasonable results concerning concentration-dependent long-time selfdiffusion coefficients (as shown before) and equilibrium structure of samples in the fluid state, and the determination of the volume fraction of random close packing (RCP, glassy state). As expected, polydispersity increases the respective volume fraction of RCP due to the decrease in free volume by the fraction of the smaller spheres which fill gaps between the larger particles.     

基于微束X射线荧光光谱的粉末冶金高温合金成分定量分布分析及应用

粉末冶金高温合金中元素偏析以及粉末原始颗粒边界是影响材料性能的重要因素,由于其颗粒粒径通常为几十微米,宏观的成分分布分析方法无法实现粉末原始颗粒边界处成分分布的精细表征。微束X射线荧光光谱（μ-XRF）是近年来发展起来的无损微区成分分布分析技术,可实现材料较大范围内元素快速、高分辨分布分析,目前在地质、考古、生物等领域有了较多的应用,但在复杂块状金属成分定量分布表征方面还存在一定困难,在粉末冶金工业领域还未见有应用报道。该试验研究了高温合金中各元素的荧光光谱行为,通过类型匹配的高温合金块状标准样品对元素定量模型进行了校正,建立了基于μ-XRF的高温合金成分定量分布分析方法,满足了粉末冶金工业对于较大范围内粉末边界成分分布精细定量表征的需求。该实验以经高纯钴合金化处理的放电等离子体烧结（SPS）粉末高温合金样品为研究对象,对经不同球磨时间混合处理后的粉末烧结样品中的Ni,Co,Cr,Mo,W,Ta,Ti和Al进行了定量统计分布分析,探讨了不同球磨时间对烧结样品成分分布的影响规律;发现样品中存在大量原始颗粒边界,且成分分布较不均匀,颗粒中心处仍然为原始高温合金颗粒成分,经球磨混合加入的纯Co粉颗粒仅存在于高温合金颗粒的外层,导致颗粒边缘Co含量明显高于颗粒中心。当球磨时间较短时,原始颗粒边界处存在很多Co富集区,当球磨时间增加到24 h时,由于在机械混粉过程中超细钴粉与高温合金的合金化,使烧结样品成分分布均匀性有了较大改善,原始颗粒边界处Co的含量显著下降,而其他元素的含量有所增加,说明球磨时间的延长,样品中各元素发生了明显的扩散,这将有助于元素偏析的改善,据此,该粉末冶金高温合金的制备工艺将得以改进。该法亦可应用于其他各种粉末冶金工业产品的成分定量分布表征,可为粉末冶金工艺优化、产品质量的改进提供数据支撑。