动态光散射法测量颗粒粒径的溯源性

分别对动态光散射粒径测量仪的入射波长、散射角度、测量池温度进行校准,并对影响测量结果准确性各因素的不确定度分量进行了评价,校准后动态光散射仪的测量结果可溯源至国家计量标准。为消除多重散射、颗粒间相互作用、颗粒粒径分布对动态光散射测量结果的影响,建立了动态光散射测量结果修正方法。其中为消除多重散射及颗粒间相互作用的影响,需采用多浓度测量或线性回归的方法得到特定浓度下的颗粒粒径;为修正颗粒粒径分布对动态光散射测量结果的影响,需先采用SEM方法准确测量颗粒粒径分布,然后根据光强加权动力学平均粒径和数量平均粒径的理论公式,得到二者之间的差异。     

Uncertainty-based measurement quality control

According to a simple acceptance decision rule for measurement quality control, a measured value will be accepted if the expanded uncertainty of the measurements is not greater than a preset maximum permissible uncertainty. Otherwise, the measured value will be rejected. The expanded uncertainty may be calculated as the z-based uncertainty (the half-width of the z-interval) when the measurement population standard deviation σ is known or the sample size is large (30 or greater), or by a sample-based uncertainty estimator when σ is unknown and the sample size is small. The decision made based on the z-based uncertainty will be deterministic and may be assumed to be correct. However, the decision made based on a sample-based uncertainty estimator will be uncertain. This paper develops the mathematical formulations for computing the probability of acceptance for two sample-based uncertainty estimators: the t-based uncertainty (the half-width of the t-interval) and an unbiased uncertainty estimator. The risk of incorrect decision-making, in terms of the false acceptance probability and false rejection probability, is derived from the probability of acceptance. The theoretical analyses indicate that the t-based uncertainty may result in significantly high false rejection probability when the sample size is very small (especially for samples of size 2). For some applications, the unbiased uncertainty estimator may be superior to the t-based uncertainty for measurement quality control. Several examples from acoustic Doppler current profiler streamflow measurements are presented to demonstrate the performance of the t-based uncertainty and the unbiased uncertainty estimator.     

Evaluation of the uncertainty of environmental measurements of radioactivity

Results obtained by measurement of radioactivity have traditionally been associated with an expression of their uncertainty, based on the so-called counting statistics. This is calculated together with the actual result on the assumption that the number of counts observed has a Poisson distribution with equal mean and variance. Most of the nuclear scientific community has, therefore, assumed that it already complied with the latest ISO 17025 requirements. Counting statistics, however, express only the variability observed among repeated measurements of the same sample under the same counting conditions, which is equivalent to the term repeatability used in quantitative analysis. Many other sources of uncertainty need to be taken into account before a statement of the uncertainty of the actual result can be made. As the first link in the traceability chain calibration is always an important uncertainty component in any kind of measurement. For radioactivity measurements in particular we find that counting geometry assumes the greatest importance, because it is often not possible to measure a standard and a control sample under exactly the same conditions. In the case of large samples we have additional uncertainty components associated with sample heterogeneity and its influence on self-absorption and counting efficiency. In this paper we prepared an uncertainty budget for existing data for ¹³⁷Cs in Danish soil, which is shown to account adequately for all sources of uncertainty. This revised version was published online in July 2006 with corrections to the Cover Date.     

140La/140Ba ratio dating of a nuclear release

In May 2010, air sampling stations in South Korea, Japan and the Russian Federation detected different unstable xenon isotopes and their progenies attached to aerosol particles. The origin of these fission products remains unclear. Previous studies have suggested that a possible reason for these observations is a nuclear test performed in North Korea in May 2010. In the present paper, preliminary spectra recorded at 2 h intervals at the particulate sampling station in Okinawa, Japan are analysed with rigorous mathematical methods. Based on the activity ratios of the ¹⁴⁰Xe progenies ¹⁴⁰Ba and ¹⁴⁰La in a sudden release scenario, the analysis provides an estimate of 12 May 16:00 (UTC) for the release date of the nuclear debris in the form of ¹⁴⁰Xe. The 95 % uncertainty limits for the release date are 11 May 9:00–13 May 13:00 (UTC). The result is very sensitive to the coincidence correction factor of the measurement setup and a larger uncertainty interval cannot be excluded. A continuous release scenario could also explain the data, possibly referring to a leak in a running nuclear reactor either on shore or in a vessel. No studies were made on the attribution of the observations to a release site. However, our conclusion is that fresh nuclear debris has been detected in East Asia, and further studies are required in an international forum to reanalyse the data. Of particular importance for the time-zero analysis is the a posteriori calibration of the Okinawa station with a ¹⁴⁰Ba sample to resolve the uncertainty related to the coincidence correction and other factors.     

Combined application of alpha-track and fission-track techniques for detection of plutonium particles in environmental samples prior to isotopic measurement using thermo-ionization mass spectrometry

The fission track technique is a sensitive detection method for particles which contain radio-nuclides like ²³⁵U or ²³⁹Pu. However, when the sample is a mixture of plutonium and uranium, discrimination between uranium particles and plutonium particles is difficult using this technique. In this study, we developed a method for detecting plutonium particles in a sample mixture of plutonium and uranium particles using alpha track and fission track techniques. The specific radioactivity (Bq/g) for alpha decay of plutonium is several orders of magnitude higher than that of uranium, indicating that the formation of the alpha track due to alpha decay of uranium can be disregarded under suitable conditions. While alpha tracks in addition to fission tracks were detected in a plutonium particle, only fission tracks were detected in a uranium particle, thereby making the alpha tracks an indicator for detecting particles containing plutonium. In addition, it was confirmed that there is a linear relationship between the numbers of alpha tracks produced by plutonium particles made of plutonium certified standard material and the ion intensities of the various plutonium isotopes measured by thermo-ionization mass spectrometry. Using this correlation, the accuracy in isotope ratios, signal intensity and measurement errors is presumable from the number of alpha tracks prior to the isotope ratio measurements by thermal ionization mass spectrometry. It is expected that this method will become an effective tool for plutonium particle analysis. The particles used in this study had sizes between 0.3 and 2.0 μm.     

Influence of size and functionality of polymeric nanoparticles on the adsorption behavior of sodium dodecyl sulfate as detected by isothermal titration calorimetry

Isothermal titration calorimetry was used to monitor the adsorption of the surfactant sodium dodecylsulfate (SDS) on different sized pure and carboxy functionalized polystyrene nanoparticles prepared by the mini-emulsion process. The ITC experiment gives, additionally to the CMC values, information about the interaction of the surfactant molecules to the particle’s surface due to the particle surface properties. The adsorption heat depends on the chemical composition of the polymer as well on the particle size. It also provides information about the surface coverage with surfactant and the number of additional adsorbed molecules per particle until full coverage by surfactant is obtained. The surfactant adsorption increases from 0.3 molecules per nm² for 50 nm to 8.5 molecules per nm² for carboxy functionalized particles with diameters larger than 160 nm. The area A _Surf-dens after the adsorption process gives information about the packing density of surfactant molecules on the particles in dependence of carboxy groups: an increasing number of carboxylic groups decreases the area occupied per SDS molecule. The adsorption process was also monitored by zeta potential measurements, where an increasing potential during the adsorption was detected.     

Investigation of the homogeneity of solids with a linear regression model

Testing of the hemogeneity of solids is usually based on the comparison of the variance of measurements at several sample points with the variance of repeated measurements. In the case of destructive analytical methods, empirical mathematical models are needed because repetitions at the same subsample are impossible. Successful application of such models depends on the adequacy of the mathematical model and the type of distribution observed. Gradients and textures with low or medium local frequency require other tests than stochastic distributions with high local frequency. A simple regression model base on a 2² factorial allows conclusions about the type of distribution without great mathematical effort.     

Coordinate measurements and operators

Relativistic quantum-field theory provides the machinery for calculating wave functions or probability amplitudes depending upon space-time coordinates. The currently accepted theory, however, fails to provide position operators and a means of measuring particle coordinates that are consistent with Dirac's properties of physical observables. This is because it calls for a space position probability distribution at a specified time. This paper shows, however, that space-time event coordinate operators, together with a corresponding measurement procedure, can be found that are consistent with Dirac's requirements. This is done through a reinterpretation of the amplitudes computed by field theory and does not involve any change in that mathematical formalism. The measurement of the space-time coordinates of an event is accomplished by detecting the absorption of a photon by a particle from each of two light pulses designed to overlap at a given point at a given time. If a final emitted photon has an energy whose sum with the final particle energy approximately equals the sum of the mean energies of the pulses, then the absorption of the two pulse photons must certainly have taken place within a distance the order of a Compton wavelength of the small space-time region of overlapping pulses. This is clear from the fact that the high energy required to confine the pulses to very small volumes must throw a particle absorbing them far off the mass shell. Thus the absorption of the two photons throws the particle into a narrowly confined spatial wave function that must decay extremely rapidly—to within a Compton wavelength, a delta function in space-time. This delta function is the eigenfunction of space-time coordinate operators X^μ and is the scalar product of vectors in a Hilbert space spanned by spin–space-time kets large enough to contain the operators of the Poincaré group. These event operators transform properly under the action of Poincaré operators but do not commute with the mass. If the Compton wavelength is not negligible compared to the accuracy desired in the coordinate measurements, individual coordinate measurements are no longer possible. Nevertheless, a large number of repeated coordinate measurements can be carried out to produce a coordinate probability distribution. This distribution can be unfolded to find a true coordinate probability distribution if the charge form factor is known from basic theory. An analysis of laboratory particle detection techniques shows that they actually determine space coordinates and energy rather than spatial coordinates at a given time. When this fact is included, the Klein–Nishina formula can be derived using the electromagnetic four-vector potential as the photon probability amplitude wave. To clarify the meaning of the observables, a mass-momentum measurement is described.     

PARTICLE SIZE DISTRIBUTION IN CONTINUOUS EMULSION POLYMERIZATION WITH FREE RADICAL DESORPTION

A mathematical model of particle size distribution in continuous emulsion polymerization which accounts for the free radical desorption from polymer particles is presented. The desorption rate is based on the diffusion theories which suggest the rate coefficient should be inversely proportional to the surface area of the polymer particles. The number density and total particle number are estimated by our model.

The average number of radicals per particle approaches Smith-Ewart case II In the range of large particle sizes. A means for predicting the nature of average desorption rate is proposed, and it seems to be influenced by concentrations of emulsifier and initiator, and residence times as well     

Radio-microanalytical particle measurements method and application to Fukushima aerosols collected in Japan

A nondestructive analytical method based on autoradiography and gamma spectrometry was developed to perform activity distribution analysis for particulate samples. This was applied to aerosols collected in Fukushima Japan, 40 km north of the Daiichi nuclear power plant for a 6 week period beginning shortly after the March 2011 tsunami. For an activity distribution of 990 “hot particles” from a small filter area, the hottest particle was nearly one Bq ^137+134Cs but most of the activity in the filter was produced by particles having <50 mBq each. ¹³⁴Cs/¹³⁷Cs activity ratios corrected to March 20, 2011 ranged from 0.68 (u _c = 28 %) to 1.3 (u _c = 15 %). The average ratio for a large quantity of particles was 0.92 (u _c = 4 %). Virtually all activity collected was beta and not alpha, suggesting little if any direct fuel debris was present at this site and time. These findings are expected to assist with separate efforts to better understand the emission events, radionuclide transport and potential environmental or biological uptake. The methods should be applicable to general environmental, radiotoxicological and similar studies for which activity distribution and particle chemistry are of importance.     

Preparation of in-house calibration source for the use in radioactivity analysis of the environmental samples: consideration of homogeneity

An in-house reference material has been prepared in Kuwait Institute for Scientific Research radioecology laboratory, for quality control purposes of gamma spectrometer systems. The material contains a known amount of uranium ore reference material (prepared by the International Atomic Energy Agency and coded as IAEA-RGU-1) which is mixed with marine sediment collected from Kuwait bay. The IAEA-RGU-1 has been certified that it is in equilibrium state with the decay daughters, and stable to be used for quality control purposes. Nevertheless, the homogeneous distribution of the doped material with the prepared source should be verified. This has been examined using gamma spectrometry measurements in conjunction with analysis of variance statistical tools, Dixon, box plots and Grubbs tests. The calculated total uncertainty has been utilized to establish the recommended specific activity ranges of ²²⁶Ra, ²²⁴Th, ²¹⁴Pb, ²¹⁴Bi and ²¹⁰Pb radioisotopes in the prepared source. The obtained results showed that the estimated uncertainty arising from the sample inhomogeneity has a significant contribution in the total uncertainty. The stability control charts of the ultra-low background gamma spectrometry system demonstrated the suitability of the prepared material for the purpose of quality control. However, the emitted gamma-rays from the prepared source covers the required energy range for determination of natural and artificial radionuclides in different species of environmental samples such as marine sediment, soil samples, and samples contaminated by naturally occurring radioactive material produced by oil industry. In addition, the material might be used for system calibration in case its traceability is proven. The experimental data revealed the significance of the homogeneity in preparing environmental samples for radioactivity measurements; in particular when small sample quantities of environmental samples are required to be analyzed.     

Combined effects of Ca2+ and humic acid on colloid transport through porous media

We report the separate and combined effects of humic acid and Ca²⁺ ions on the transport of colloidal particles through a sand-packed column. Polystyrene latex particles with a sulfate functional group were used as model colloids. The concentrations of both the inlet solution and the effluent solutions were measured during each experimental run. Breakthrough curves were obtained by taking the ratios of each effluent sample concentration to the inlet solution concentration. In the absence of humic acid, the results indicate that increasing the concentration of Ca²⁺ increases particle attachment to the sand, thus causing decreased transport rates of latex particles through the porous bed matrix. Once 4 mg/l humic acid was added to the system, changes were observed in the effect that Ca²⁺ has on latex particle breakthrough. In a system containing calcium, increasing the humic acid concentration was shown to reduce particle attachment and increase transport rates. In the absence of calcium, the ratios for the outlet-to-inlet concentrations were similar for each concentration of humic acid. The electrophoretic mobility was also measured in order to determine the role of electrostatic repulsion in the latex particle transport. The electrophoretic mobility of the latex particles was found to be dependent on humic acid concentration in the absence of Ca²⁺ but not in its presence. Received: 2 February 2001 Accepted: 6 2001     

Emulsion polymerization. III. Theoretical prediction of the effects of slow termination rate within latex particles

The Smith-Ewart theory predicts that there is an interval during an isothermal homopolymerization when the conversion varies linearly with time. This prediction rests on the assumptions that, during this interval II, the particle number is constant, the monomer concentration in the particles is constant, and the termination rate within the particles is instantaneous, so that the average number of radicals per particle Q is half. In this paper this latter assumption is abandoned. If the termination rate is slow, two or more radicals can coexist in a particle. The termination rate within a particle becomes a function of the particle size because of the decreased probability that two radicals meet for termination in a given time when the volume in which these radicals are located increases. It follows that with increasing conversion the termination rate decreases. Stockmayer's calculations based on this model neglected the variation of particle volume with time, and it was assumed that a steady state of radical concentration in particles exists. In the present calculations these restrictive assumptions were not used. Stockmayer calculated only how Q should vary with conversion. In the present paper several experimentally verifiable consequences of the model are shown. The new calculations show that the interval II conversion-time curve can be represented by the formula At² + Bt, where B is the Smith-Ewart rate and is proportional to the particle number and the parameter A is independent of the particle number and depends mainly on initiation and termination rates. From A and B and propagation and termination rate constants can be calculated. With the aid of parameters A and B the conversion dependence of molecular weight and of Q can also be predicted for interval II. In the theoretical calculations the distribution of radicals among particles is established. It is shown that for a given value of Q this distribution is unique, independent of the experimental conditions leading to this Q. This distribution was derived solely from kinetic considerations and is analogous to the statistical Poisson distribution. With increasing Q, i.e., with increasing conversion, this distribution broadens. Since each particle grows proportionally to the number of radicals in it, particles must grow at greatly varying rates if there is broad distribution of radicals among them. It follows that the particle size distribution has to broaden with increasing conversion, contrary to predictions based upon the Smith-Ewart model. At present it is not yet possible to predict quantitatively the shape of the conversion-time curve in interval III, the interval following the disappearance of monomer droplets. The reason for this is that the functional dependence of the termination rate constant upon monomer concentration in the particles is not known. However, once the conversion-time curve is experimentally determined, it is possible to calculate from it the interval III values of Q and of molecular weight.     

Charged particle activation analysis of light elements at sub-ppb level

We have developed charged particle activation analysis to determine light elements at a sub-ppb level. This analytical method is characterized by sample bombardment with charged particles at a few tens of mA and substoichiometric separation for¹³N,¹¹C and¹⁸F within two half-life times and with decontamination factors of more than 10⁸. Nuclear reactor interference is also estimated with this method. This analytical method is confirmed to be useful for characterizing highly purified materials from analytical results for boron, carbon, nitrogen and oxygen in Nb refined by the floating zone melting method.     

Intercomparison study of inductively coupled plasma mass spectrometry, thermal ionization mass spectrometry and fission track analysis of µBq quantities of 239Pu in synthetic urine

Even today, some Marshall Islanders are looking forward to permanentlyresettling their islands after five decades. The U.S. Department of Energyand the resettled residents require reasonable but cost-prudent assurancethat the doses to residents from residual ²³⁹Pu will not exceedrecognized international standards or recommendations, as estimated from theexcretion of ²³⁹Pu in urine. The goal of this study was to evaluatethe bias, uncertainty and sensitivity of analytical techniques that measure3–56 µBq ²³⁹Pu in synthetic urine. The analytical techniquesstudied in this work included inductively coupled plasma mass spectrometry,thermal ionization mass spectrometry and fission track analysis. The resultsof the intercomparison demonstrated that all three techniques were capableof making the measurements, although not with equal degree of bias and uncertainty.The estimated minimum detectable activity was 1 µBq of ²³⁹Puper synthetic urine sample. This exercise is also the first effort to certifytest materials of plutonium in the nBq . g –1 range.     

Untersuchungen zur Acidität und katalytischen Spaltaktivität dekationisierter NaY-Zeolithe

Investigation on Acidity and Catalytic Activity of Deep-Bed Calcinated Zeolites NH₄ NaY NMR and infrared techniques are applied to decationated zeolites NaY to study Brönsted acidity. The results are compared with measurements of catalytic activity and crystallinity of this zeolites. The number of OH groups which are able to form a pyridinium ion (PyH⁺) increases with increasing exchange degree and with increasing temperature of the sample. The rate of pyridinium ion formation as an equivalent of Brönsted acidity and the catalytic activity increase similarly with increasing exchange degree up to such values where a loss of crystallinity occurs.     

2011年约稿： 电感耦合等离子体原子发射光谱法测定铜合金中锆量的不确定度评定

讨论了采用电感耦合等离子体发射光谱法测定铜合金中锆量分析结果不确定度产生的原因。建立了数学模型,对测量重复性,标准溶液,标准曲线变动性,试液体积,试样称量,数字修约等引起的不确定分量进行评定,计算了合成标准不确定度和扩展不确定度,并给出铜合金中锆量测定结果的报告。评定结果表明：测量重复性,标准曲线线性回归引起的不确定度对总不确定度影响最大。所以,在测定中应进行多次平行测定,特别注意标准曲线的校正和绘制校准曲线所用标准样品的选择。     

Particle formation in interval III of the emulsion polymerization of styrene with aerosol‐MA as an emulsifier

Particle nucleation in the seeded emulsion polymerization of styrene in the presence of Aerosol‐MA emulsifier micelles and in the absence of monomer droplets (interval III) was investigated. The seed particles were swollen with different amounts of the styrene monomer before the experiments. A larger number of polymer particles formed in interval III than in the corresponding seeded batch operation in the presence of monomer droplets. The increase in the number of particles could be attributed to the reduced rate of growth of new particles, which retarded the depletion of emulsifier micelles. The number of secondary particles initially increased with the initial polymer weight ratio in the seed particles (w_p0) but decreased at a higher range of w_p0, after reaching a maximum at w_p0 = 0.60, and eventually was reduced to zero. At high values of w_p0 (>0.75), polymerization occurred in the seed particles, whereas few or no new particles were formed despite the presence of micelles. The cessation of particle formation at high conversions was ascertained with a semibatch process in which the neat monomer feed was added to the reaction vessel containing the seed particles and emulsifier micelles. For w_p0 > 0.85, the emulsifier micelles were disintegrated to stabilize the seed particles with no secondary particle formation. The possible reasons for the cessation of particle formation at high w_p0 were examined. The size distribution of secondary particles showed a positive skewness in terms of volume because of the declining rate of growth for particles, together with a low rate of growth for small particles. The distribution breadth of new particles sharpened with increasing w_p0. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1652–1663, 2002     

Determination of <Superscript>90</Superscript>Sr in preparedness: Optimization of total analysis time for multiple samples

In radiological emergency, rapid determination of radiostrontium will be necessary. The required quantification levels will be relatively high which offers smaller sample sizes and shorter ingrowth and counting times. In this paper a rapid method for the determination of ⁹⁰Sr in fresh milk in emergency preparedness is presented. The method is based on microwave digestion, chemical separation of Sr, ingrowth of ⁹⁰Y and Cherenkov measurements. In order to minimize the total analysis time, a mathematical model was developed. For a given number of samples the model minimizes the analysis time by optimizing the ingrowth and counting time in order to reach a detection limit fit-for-purpose.     

In-flight particle diagnostics in induction plasma processing

A laser Doppler anemometer combined with a particle-emission spectrometer, are used for the study of the induction plasma spraying process. For this, the effects of chamber pressure, spray distance and torch nozzle design on the particle surface temperature and velocity as well as the fraction of hot particles included in the stream of processed material, were investigated. A comparison between the velocity measurements by laser Doppler anemometry (LDA) and by the particle time-of-flight technique is presented in order to emphasize the deference between the velocity of the hot particles, and that of the total particle population, cold and hot. The influence of the individual particle mass on particle entrainment in the plasma jet from the ambient atmosphere in the vacuum chamber is discussed.