Uncertainty evaluation of the thermal expansion of simulated fuel

Thermal expansions of simulated fuel (SS1) are measured by using a dilatometer (DIL402C) from room temperature to 1900 K. The main procedure of an uncertainty evaluation was followed by the strategy of the UO₂ fuel. There exist uncertainties in the measurement, which should be quantified based on statistics. Referring to the ISO (International Organization for Standardization) guide, the uncertainties of the thermal expansion are quantified in three parts—the initial length, the length variation, and the system calibration factor. Each part is divided into two types. The A type uncertainty is derived from the statistical iterative measurement of an uncertainty and the B type uncertainty comes from a non-statistical uncertainty including a calibration and test reports. For the uncertainty evaluation, the digital calipers had been calibrated by the KOLAS (Korea Laboratory Accreditation Scheme) to obtain not only the calibration values but also the type B uncertainty. The whole system, the dilatometer (DIL402C), is composed of many complex sub-systems and in fact it is difficult to consider all the uncertainties of sub-systems. Thus, a calibration of the system was performed with a standard material (Al₂O₃), which is provided by NETZSCH. From the above standard uncertainties, the combined standard uncertainties were calculated by using the law of a propagation of an uncertainty. Finally, the expanded uncertainty was calculated by using the effective degree of freedom and the t-distribution for a given confidence level. The uncertainty of the thermal expansion for a simulated fuel was also compared with those of UO₂ fuel.     

Thermochemical properties of free radicals from G3MP2B3 calculations

For a set of 32 selected free radicals, energy minimum structures, harmonic vibrational wave numbers ω_e, principal moments of inertia I_A, I_B, and I_C, heat capacities C°_p(T), entropies S°(T), thermal energy contents H°(T) ? H°(0), and standard enthalpies of formation Δ_fH°(T) were calculated at the G3MP2B3 level of theory in the temperature range 200–3000 K. In this article, thermodynamic functions at T = 298.15 K are presented and compared with recent experimental values. The mean absolute deviation between calculated and experimental Δ_fH°(298.15) values resulted in 3.91 kJ mol^?1, which is close to the average experimental uncertainty of ± 3.55 kJ mol^?1. The influence of hindered rotation on thermodynamic functions is studied for isopropyl and tert‐butyl radicals. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 550–560, 2002     

Conformational analysis—129: Heats of formation and thermodynamic parameters for hydrocarbons,calculated by the molecular mechanics method including the effects of molecular vibrations,

A force field is presented in which the zero point energies and the effects of vibrational thermal excitation are included in the heat of formation calculations. The standard deviation of the difference between the calculated and experimental heats of formation of a diverse set of 44 hydrocarbons is 0.38 $\text{kcal}\text{mole}$, which is the same as the average experimental error for this set of compounds. This standard deviation is substantially lower than in previous similar force fields which did not include vibrational effects, and it is argued that much of this improvement is due to the inclusion of vibrational terms in the heat of formation. This force field also reproduces the experimental structures of compounds well.     

Investigating parameters on the preparation of mesoporous activated carbons by the combination of chemical and physical activations using the Taguchi method

Mesoporous activated carbons were prepared from coconut shell by the combination of chemical and physical activation methods. Zinc chloride and CO₂ were used as chemical and physical agents, respectively. Optimum parameters were obtained from investigating the effect of various factors at different levels on the methane storage of wet activated carbons using the Taguchi experimental design method. Soaking time, carbonization temperature, and carbonization time were found as effective parameters in the methane storage. Finally, after achieving optimum levels for each factors based on the enhancement of methane storage, a confirmation experiment was conducted. Methane uptakes of the activated carbons were measured at temperature of 2?^°C up to the pressure of 80 bar and it turned out that the maximum amount of methane storage (241?V/V) had a good agreement with the predicted result from the Taguchi method.     

Chemically modified activated carbon with S-benzyldithiocarbazate as a new solid-phase extractant for preconcentration of mercury prior to ICP-AES determination

A new sorbent S-benzyldithiocarbazate (SBDTC) modified activated carbon (AC-SBDTC) was prepared and studied for preconcentration for trace mercury(II) prior to inductively coupled plasma atom emission spectrometry (ICP-AES). The experimental conditions were optimised with respect to different experimental parameters using both batch and column procedures in detail. The optimum pH value for the separation of Hg(II) on the new sorbent was 3, while the adsorption equilibrium was achieved in less than 5?min. Complete elution of the adsorbed metal ions from the sorbent surface was carried out using 5?mL of 0.25?mol?L^?1 of HCl and 2% CS(NH₂)₂. Common coexisting ions did not interfere with the determination. The maximum static adsorption capacity of the sorbent under optimum conditions was found to be 0.55?mmol?g^?1. The detection limit of the present method was found to be 0.09?ng?mL^?1, and the relative standard deviation (RSD) was lower than 2.0%. The procedure was validated by analysing the certified reference river sediment material (GBW 08301, China), the results obtained were in good agreement with standard values. This sorbent was successfully employed in the separation and preconcentration of trace Hg(II) from the natural water samples yielding 80-fold concentration factor.     

Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN4 Sites for Oxygen Reduction

FeN₄ moieties embedded in partially graphitized carbon are the most efficient platinum group metal free active sites for the oxygen reduction reaction in acidic proton‐exchange membrane fuel cells. However, their formation mechanisms have remained elusive for decades because the Fe?N bond formation process always convolutes with uncontrolled carbonization and nitrogen doping during high‐temperature treatment. Here, we elucidate the FeN₄ site formation mechanisms through hosting Fe ions into a nitrogen‐doped carbon followed by a controlled thermal activation. Among the studied hosts, the ZIF‐8‐derived nitrogen‐doped carbon is an ideal model with well‐defined nitrogen doping and porosity. This approach is able to deconvolute Fe?N bond formation from complex carbonization and nitrogen doping, which correlates Fe?N bond properties with the activity and stability of FeN₄ sites as a function of the thermal activation temperature.     

Anwendung der Differential-Thermoanalyse zur Bestimmung der Zündtemperatur von Schwel- und Hochtemperaturkoks

The application of differential thermal analysis to the determination of the ignition temperature of coke from low-temperature and high-temperature carbonization is treated. The sample mixed with NaNO₂ was heated at a rate of 10?/min, using kaolin as inert substance. As ignition temperature, that of the high exothermic peak on the DTA curve was taken. It has been stated that the ignition temperature of the untreated coal increases from 310 to 365? as the degree of carbonization increases. The ignition temperature of coke from low-temperature carbonization was found to vary between 350 and 370?, and that of coke from high-temperature carbonization between 380 and 400?.     

The metrology of unstable measurands

 Type A statistical uncertainty in measurements is usually derived from the standard deviation of the measured data. This is correct as long as the measurand is stable over time and has a meaningful constant value. In such a case the average measurement and the standard deviations are meaningful. However, as measurement methods are refined and become more precise, we can observe that a given measurand may be unstable and change with time and the uncertainty in measurement must be redefined. This is specifically true in the metrology of time which can be measured today more precisly than any other measurand. We argue that in such a case the uncertainty in the prediction of the next measurement should be used instead of the uncertainty in measurement. Both uncertainties coincide for a stable measurand. The prediction of the next measurement is achieved by means of predictors. In this paper we describe the application of linear predictors and especially optimum linear predictors to predict in the presence of various types of instability. To illustrate the issues we use clock instabilities and clock metrology as this field is most developed. A measurand can be unstable but still predictable and thus useful. This is well known in the case of white noise about a linear drift for which the optimum predictor is a linear regression. Since the deviations from prediction of optimum prediction are of white noise, we can now use simple statistics to estimate the uncertainty of the optimum or close to optimum prediction. In this paper we present the various optimum or close to optimum linear predictors optimized for different types of instability and estimate the associated prediction uncertainties.     

Use of multivariate statistical analysis to evaluate experimental results for certification of two pharmaceutical reference materials

This paper demonstrates the use of the multivariate analysis for the quick and easy evaluation of the experimental results from the homogeneity test of two new certified reference materials (CRM) of active pharmaceutical ingredients (API): metronidazole and captopril. The principal component analysis (PCA) and the hierarchical cluster analysis (HCA) indicated that some results from the homogeneity test were statistically different when the concentrations of all API impurities were considered simultaneously. Through the use of these statistical tools, it was possible to reduce the standard uncertainty due to between-bottle (in)homogeneity (u _bb) and consequently the combined standard uncertainty of the certified reference materials (u _CRM) with 95% confidence level.     

Electron delocalization contribution to single crystal thermal expansion of a polydiacetylene

The thermal expansion contribution due to temperature-dependent π-electron delocalization is evaluated from spectral measurements on a single crystal polydiacetylene (poly-2,4-hexadiyne-1,6-diol bisphenylurethane). The observed temperature independence of backbone associated vibrations (less than ±1 cm^?1 change in ν_C?C and ν_C?C between 25 and 90°C) implies that thermal conformational fluctuations and equilibrium defect formation (which produce a negative thermal expansion coefficient) do not measurably affect π-electron delocalization. The separation of equilibrium defects is either much longer than that of nonequilibrium defects or much longer than required to appreciably limit π-electron delocalization in an effectively defect-free polymer. Arguments presented indicate that, in the experimental temperature interval, the observed thermal expansion coefficient in the chain direction is over an order of magnitude larger than the delocalization-associated contribution.     

Facile one-step extraction and oxidative carboxylation of cellulose nanocrystals through hydrothermal reaction by using mixed inorganic acids

A facile and efficient approach to prepare carboxylated cellulose nanocrystals (CCNCs) is presented through a novel one-step hydrothermal procedure by using a mixed acid system of hydrochloric acid and nitric acid (HCl/HNO₃). The as-prepared cellulose nanoparticles were characterized by scanning electron microscopy, wide angle X-ray diffraction, conductometric titrations, Fourier transform infrared spectrometry and thermal gravimetric analysis. The results showed that the combination of the mixed acid and hydrothermal reaction can speed up the process of CCNC preparation, and then high quality of the product could be obtained at relatively low acid concentration. It is found that the addition of nitric acid could not only promote the conversion of surface groups on the cellulose nanocrystals (CNCs), but also have significant influences on the yield, particle size and microstructure of CNCs. For the volume ratio of HCl/HNO₃ of 7:3, the as-prepared CCNCs exhibited the largest length to diameter ratio and narrowest dimension distributions as well as maximum degree of oxidation of 0.12. In addition, high dispersion stability for the CCNCs could be observed due to the existence of negative carboxyl groups. This approach based on one-step oxidative carboxylation greatly simplified the preparation of CCNCs with high yield and high crystallinity under mild hydrothermal condition.     

Thermal conductivity of the ferrites Ni0.65Zn0.35CuxFe2−xO4

A series of samples of the type Ni_0.65Zn_0.35Cu_xFe_2?xO₄ (x=0, 0.1, 0.2, 0.3, 0.4 and 0.5) were prepared by a ceramic technique. The existence of a single phase was confirmed by X-ray studies. The thermal conductivity and specific heat were measured at 53°C. The thermal conductivity had a minimum value atx=0.3, due to the maximum porosity at this composition. The phonon frequency was estimated to have an optimum value at x=0.3, due to the increase in phonon scattering.     

Control of the10B/11B isotopic ratio in H3BO3 samples by SSMS

The¹⁰B/¹¹B isotopic ratio in the H₃BO₃ presented in the liquid moderator of a nuclear reactor is used as monitor of the performance of the reactor during the first year of operation. Usually this determination is performed by TIMS due to its high precision. An alternate technique to thermal ionization mass spectrometry /TIMS/ for the determination of the¹⁰B/¹¹B isotopic ratio by SSMS is presented. The modifications introduced in the general analytical method produced very good results. Furthermore, the relative standard deviation was 5% against the typical value of 10–20%.SSMS: spark source mass spectrometry.     

Multielement comparison of instrumental neutron activation analysis techniques using reference materials

Several instrumental neutron activation analysis techniques (parametric, comparative, and k_o-standardization) are evaluated using three reference materials. Each technique is applied to National Institute of Standards and Technology standard reference materials, SRM 1577a (Bovine Liver) and SRM 2704 (Buffalo River Sediment), and the United States Geological Survey standard BHVO-1 (Hawaiian Basalt Rock). Identical (but not optimum) irradiation, decay, and counting schemes are employed with each technique to provide a basis for comparison and to determine sensitivities in a routine irradiation scheme. Fifty-one elements are used in this comparison; however, several elements are not detected in the reference materials due to rigid analytical conditions (e.g., insufficient length of irradiation or activity for radioisotope of interest decaying below the lower limit of detection before counting interval). Most elements are normally distributed around certified or consensus values with a standard deviation of 10%. For some elements, discrepancies are observed and discussed. The accuracy, precision, and sensitivity of each technique are discussed by comparing the analytical results to consensus values for the Hawaiian Basalt Rock to demonstrate the diversity of multielement applications.     

Assessment of permissible ranges for results of pH-metric acid number determinations using uncertainty calculation

 An approach to assess the permissible ranges for results of replicate determinations using uncertainty calculation is discussed. The approach is based on the known range distribution for normalized "range/standard deviation" values, which is equivalent to the distribution of the range for normalized results of replicate determinations having an average of 0 and a standard deviation of 1. It is shown that the permissible ranges can be assessed using tabulated percentiles of this distribution and calculated values of the determination (analysis) standard uncertainty. When the standard uncertainty calculation is performed before the analytical method validation, the permissible ranges can be predicted. As an example, the range is predicted for a new pH-metric method for acid number determination without titration in petroleum oils (basic, white and transformer). The results of the prediction are in good conformity with the experimental data. Received: 23 May 1999 · Accepted: 14 November 1999     

Thermochemical properties from G3MP2B3 calculations,Set‐2: Free radicals with special consideration of CH2CH?C•CH2, cyclo−•C5H5, •CH2OOH,HO?•CO,and HC(O)O•

After a set of 32 free radicals was presented (Int J Chem Kin 34, 550–560, 2002), an additional 60 free radicals (Set‐2) were studied and characterized by energy minimum structures, harmonic vibrational wave numbers ω_e, moments of inertia I_A, I_B, and I_C, heat capacities C^o_p(T), standard entropies S^o(T), thermal energy contents H^o(T) ? H^o(0), and standard enthalpies of formation Δ_fH^o(T) at the G3MP2B3 level of theory. Thermodynamic functions at T = 298.15 K are presented and compared with recent experimental values where these are available. The mean absolute deviation between calculated and experimental Δ_fH^o(298.15) values by the previous set of 32 radicals is 3.91 kJ mol^?1. For the sake of comparison, only 49 species out of the 60 radicals of Set‐2 are characterized by experimental enthalpies of formation, and the corresponding mean absolute deviation between calculated and experimental Δ_fH^o(298.15) values is 8.96 kJ mol^?1. This situation is cause for demand of more and also more accurate experimental values. In addition to the above properties, parent molecules of a large set of the respective radicals are calculated to obtain bond dissociation energies D^o(298.15). Radical stabilization owing to resonance is discussed using the complete sets of total atomic spin densities ρ as a support. In particular, a short review about recent developments of the first‐order Jahn–Teller radical c‐C₅H₅^? is presented. In addition, radicals with negative bond energies are described, such as ^?CH₂OOH where the reaction path to CH₂O + HO^? has been calculated, as well as radicals which have two different parent molecules, for example C?N? O^?. For the reaction HO^? + CO → H^? + CO₂, two reaction paths are characterized by a total of 14 stationary points where the intermediate radicals HO? ^?CO and HC(O)O^? are involved. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 661–686, 2004     

Separation and determination of six catechins in tea by pressurized capillary electrochromatography

An efficient pressurized capillary electrochromatography (pCEC) method has been successfully developed for the determination of six catechins in tea. The separation was performed on a reversed-phase EP-100-20/45-3-C18 capillary column (total length of 45?cm, effective length of 20?cm, diameter of 100?μm, ODS packing inside for 3?μm). The mobile phase ratio of organic phase, the concentration of phosphate buffer and sodium heptanesulfonate, separation voltage, and other experimental conditions were investigated and optimized. The mobile phase was 15?mM NaH₂PO₄ and 12?mM sodium heptanesulfonate (pH 3.0)/methanol (64:36) at a flow rate of 0.04?mL/min. Under optimal conditions including applied voltage of ?4?kV and a UV detection wavelength of 230?nm, the six catechins in the tea were well separated. The calibration curves for the analytes had good linearity in the range of 8.02?μg/mL–202.13?μg/mL with a correlation coefficient of 0.9928–0.9997. The limits of detection (LOD) for the six catechins were 4.62?μg/mL–11.63?μg/mL (S/N?=?3). The recoveries of the six catechins were 96.2%–108.4% with a relative standard deviation (RSD) between 0.78% and 4.51%. The method has been used for the determination of six catechins in tea samples with good results.     

The effect of thermal stress on the thermal expansion coefficient and glass transition temperature of glass fiber–polymer composites

The thermal expansion coefficients of glass fiber–polymer composites were calculated applying the solid cylindrical model taking into account the interaction effects among the glass fibers. The stress and displacement in the composite model were determined as functions of the thermal stress. It was found theoretically that the deviation of the thermal expansion coefficient from the linear mixture relationship based on volume additivity appeared at around T_g + 20 K upon cooling. The thermal expansion coefficient of the composite was also found to be markedly dependent on the dispersion state of the glass fibers. An expression for the difference in the T_g of the matrix resin in the composite from that in the unloaded resin was obtained on the assumption that the volume change of the matrix resin caused by mixing was compensated by free volume expansion. The experimental results obtained by differential scanning calorimetry (DSC) measurements were found to agree well with the theoretically predicted ones.     

Polymer microfluidic chip for online monitoring of microarray hybridizations

A disposable single use polymer microfluidics chip has been developed and manufactured by micro injection molding. The chip has the same outer dimensions as a standard microscope slide (25 x 76 x 1.1 mm) and is designed to be compatible with existing microscope slide handling equipment like microarray scanners. The chip contains an inlet, a 10 microL hybridization chamber capable of holding a 1000 spot array, a waste chamber and a vent to allow air to escape when sample is injected. The hybridization chamber ensures highly homogeneous hybridization conditions across the microarray. We describe the use of this chip in a flexible setup with fluorescence based detection, temperature control and liquid handling by computer controlled syringe pumps. The chip and the setup presented in this article provide a powerful tool for highly parallel studies of kinetics and thermodynamics of duplex formation in DNA microarrays. The experimental setup presented in this article enables the on-chip microarray to be hybridized and monitored at several different stringency conditions during a single assay. The performance of the chip and the setup is demonstrated by on-line measurements of a hybridization of a DNA target solution to a microarray. A presented numerical model indicates that the hybridization process in microfluidic hybridization assays is diffusion limited, due to the low values of the diffusion coefficients D of the DNA and RNA molecules involved.