Thermal properties of nanocomposites based on polyethylene and n-heptaquinolinum modified montmorillonite

The aim of the research was obtaining and application of smectic clay modifying agent. The organophilic clay is used as nanofiller in polymer nanocomposites [1]. A microwave-assisted reaction led to obtaining N-heptaquinolinum, which is amphiphilic compound, containing both hydrophobic (alkyl and aromatic) and hydrophilic sections in its structure [2]. N-heptaquinolinum was used as a montmorillonite clay modifying agent. Modification was carried out in formulated way [3, 4]. Modification efficiency was determined by X-ray diffraction (XRD) analysis and elementary analysis. Organophilic clay (Ch7) was introduced, using the extrusion method, into polyethylene matrix in different mass relations (1.5, 3 and 5?%) [3]. The structure of obtained materials was studied by means of XRD and SEM. To evaluate potential applications thermal properties of received nanocomposites were tested with thermogravimetric analysis and differential scanning calorimetry. The thermal stability of PE/clay composites can be improved in the case of loading 1.5 and 5?mass%.     

Further developments of a robust absolute calibration method utilizing beta/gamma coincidence techniques

Performing accurate and verifiable measurements is often the most challenging goal for any radiation detector and is especially challenging for the radio-xenon detectors deployed by the International Monitoring System (IMS) of the Preparatory Commission of the Comprehensive Test Ban Treaty Organization (CTBTO). Often the accuracy of the measurement is directly tied to how well the detector is calibrated, in both energy and efficiency. Standard methods often rely on using certified sealed sources to determine the absolute efficiency. Similarly, efforts to calibrate the absolute efficiency of radioactive gas cell detectors utilize a number of methodologies which allow adequate calibration but are time consuming and prone to a host of difficulties to determine uncertainties (McIntyre et al, J Radioanal Nucl Chem 282(3):755–759, 2009; Anderson et al, Stat Probab Lett 77(88):769–773, 2007). Utilizing methods developed in the 1960s for absolute measurements of activity with beta–gamma detector systems it has become clear that it is possible to achieve higher precision results that are consistent across a range of isotopes and activities (National Council on Radiation Protection and Measurement, A handbook of radioactivity measurements procedure NCPR report, 1985). Even more compelling is the ease with which this process can be used on routine samples to determine the total activity present in the detector. Additionally, recent advances in the generation of isotopically pure radio-xenon samples of ^131mXe, ¹³³Xe, and ¹³⁵Xe allow these measurement techniques to achieve much better results than have previously been possible when using mixed isotopic radio-xenon sources (Haas et al, J Radioanal Nucl Chem 282(3):677–680, 2009). This paper will discuss the beta/gamma absolute detection efficiency techniques of direct measurement of the efficiencies and the extrapolation method and compare the results using modeled and measured pure sources of ¹³³Xe and ¹³⁵Xe.     

Drawing information from the ground state G-particle-hole matrix to study electronic excited states

Very recently, we have shown the suitability to combine the G-particle-hole Hypervirial (GHV) equation method (Alcoba et?al. in Int J Quantum Chem 109:3178, 2009) with the Hermitian Operator (HO) method (Bouten et?al. in Nucl Phys A 202:127, 1973) for computing various energy differences of an electronic system spectrum (Valdemoro et?al. in J Math Chem 50:492, 2012). The purpose of this paper is to extend our preliminary studies by applying the combined GHV-HO method to obtain the set of ground and low-lying excited states potential energy curves of several selected electronic systems. The calculations confirm the reliability of the method.     

The development of radioactive glass surrogates for fallout debris

The production of glass that emulates fallout is desired by the nuclear forensics community for training and measurement exercises. The composition of nuclear fallout is complex, with widely varying isotopic compositions (Fahey et al., Proc Natl Acad Sci USA 107(47):20207–20212, 2010; Bellucci et al., Anal Chem 85:7588–7593, 2013; Wallace et al., J Radioanal Nucl Chem, 2013; Belloni et al., J Environ Radioact 102:852–862, 2011; Freiling, Science 139:1058–1059, 1963; Science 133:1991–1999, 1961; Bunney and Sam Government Report: Naval Ordinance Laboratory, White Oak, 1971). As the gaseous cloud traverses from hotter to cooler regions of the atmosphere, the processes of condensation and nucleation entrain environmental materials, vaporized nuclear materials and fission products. The elemental and isotopic composition of the fission products is altered due to chemical fractionation (i.e. the fission product composition that would be expected from fission of the original nuclear material is altered by differences in condensation rates of the elements); the fallout may be enriched or depleted in volatile or refractory fission products. This paper describes preliminary work to synthesize, irradiate and fractionate the fission product content of irradiated particulate glass using a thermal distillation 2 h after irradiation. The glass was synthesized using a solution-based polymerization of tetraethyl orthosilicate. (Izrael, Radioactive fallout after nuclear explosions and accidents, 2002) Uranium was incorporated into the glass particulate at trace concentrations during polymerization. The particulate was subjected to a short thermal neutron irradiation then heated to 1,273 K approximately 2 h after the end of irradiation. Fission products of ^{133, 134, 135}I, ^{132, 134}Te, ¹³⁵Xe, ¹³⁸Cs and ^{91, 92}Sr were observed to be distilled from the particulate. The results of these preliminary studies are discussed.     

On-line optimizing control of the intermittent simulated moving bed process

The I-SMB process is one of the modifications to the standard SMB process that has been demonstrated both theoretically and experimentally to exhibit rather competitive performance (Katsuo and Mazzotti in J Chromatogr A 1217:1354, 2010a, 3067, 2010b; Katsuo et al. in J Chromatogr A 1218:9345, 2011). This work aims at showing that also the I-SMB process can be controlled and optimized by using the optimizing on-line controller developed at ETH Zurich for the standard SMB process (Erdem et al. in Ind Eng Chem Res 43:405, 2004a, 3895, 2004b; Grossmann et al. in Adsorption 14:423, 2008, AIChE J 54:1942008). This is achieved by using a virtual I-SMB unit based on a detailed model of the process; past experience with the on-line controller shows that the controller’s behavior on a virtual platform is essentially the same as in laboratory experiments.     

Numerical evaluation of second and third virial coefficients of some inert gases via classical cluster expansion

In this project we evaluate second virial coefficient of some inert gases via classical cluster expansion, assuming each atomic pair interaction is of Lennard-Jones type. We also try to numerically evaluate the third virial coefficient of Argon gas based on bipolar-coordinate integration (Mas et?al. in J Chem Phys 10:6694, 1999), assuming the same Lennard-Jones potential as before. The second virial coefficient (Vega et?al. in Phys Chem Chem Phys 4:3000–3007, 2002) calculated from our model are compatible to the experimental data [19] The temperature at which B ₂(T) → 0 is called the Boyle’s temperature T _B (Vega et?al. in Phys Chem Chem Phys 4:3000–3007, 2002) for the Lennard-Jines (12-6) potential. For the second virial coefficient of He, we obtain the Boyle’s temperature as follow: T _B ?=?34.9312438964844 (K) B ₂(T) = 9.82958 × 10^?6 (cm³/mol).     

Supramolecular architectures of metal–organic host–guest compounds

Metal?Corganic frameworks are a class of materials with new and interesting properties (Angew Chem Int Ed 43:2334, 2004; Coorg Chem Rev 38:1213, 2009; Adv Mater 23:249, 2011). In particular, porous metal organic systems are attracting considerable interest because of their potential use as sensors, catalysts and, in general, in host?Cguest chemistry (Acc Chem Res 43:1115, 2010). The so-called ??wheel and axle?? compounds play an important role in the developing of supramolecular chemistry and there are a lot of studies dealing with their inclusion properties and host?Cguest chemistry (Comprehensive supramolecular chemistry, 1996). Classical ??wheel and axle?? molecules have a long, thin, central part (the axle) with two bulky ends (the wheels). Here, new compounds with host properties are described, that we called ??wheel and axle metal?Corganic?? diols (WAMOD), that are decorated with OH groups in the wheel. In particular, their clathration properties are discussed in connection with their crystal structures. A modular strategy is applied to obtain WAMODs: coordination chemistry is used together with soft interactions (H-bond, ?ШC?? interaction), with the aim to realize a dynamic framework that is able to reversibly capture and release a guest. The coordination bond is robust and permits to obtain WAMODs with different arrangements of the axle; the hydrogen bonds and/or the other soft interactions are responsible for the thin adjustments in the crystal packing that allow reversible adsorption/desorption of the guest.     

In-situ imaging sensors for bioprocess monitoring: state of the art

Over the last two decades, more and more applications of sophisticated sensor technology have been described in the literature on upstreaming and downstreaming for biotechnological processes (Middendorf et al. J Biotechnol 31:395–403, 1993; Lausch et al. J Chromatogr A 654:190–195, 1993; Scheper et al. Ann NY Acad Sci 506:431–445, 1987), in order to improve the quality and stability of these processes. Generally, biotechnological processes consist of complex three-phase systems—the cells (solid phase) are suspended in medium (liquid phase) and will be streamed by a gas phase. The chemical analysis of such processes has to observe all three phases. Furthermore, the bioanalytical processes used must monitor physical process values (e.g. temperature, shear force), chemical process values (e.g. pH), and biological process values (metabolic state of cell, morphology). In particular, for monitoring and estimation of relevant biological process variables, image-based inline sensors are used increasingly. Of special interest are sensors which can be installed in a bioreactor as sensor probes (e.g. pH probe). The cultivation medium is directly monitored in the process without any need for withdrawal of samples or bypassing. Important variables for the control of such processes are cell count, cell-size distribution (CSD), and the morphology of cells (Höpfner et al. Bioprocess Biosyst Eng 33:247–256, 2010). A major impetus for the development of these image-based techniques is the process analytical technology (PAT) initiative of the US Food and Drug Administration (FDA) (Scheper et al. Anal Chim Acta 163:111–118, 1984; Reardon and Scheper 1995; Schügerl et al. Trends Biotechnol 4:11–15, 1986). This contribution gives an overview of non-invasive, image-based, in-situ systems and their applications. The main focus is directed at the wide application area of in-situ microscopes. These inline image analysis systems enable the determination of indirect and direct cell variables in real time without sampling, but also have application potential in crystallization, material analysis, polymer research, and the petrochemical industry.

Certification of the mass fractions of trace elements and pentachlorophenol in an impregnated wood reference material

The resource-saving utilisation of recovered waste wood is a matter of growing concern. In several European countries, this utilisation is governed by regulations and is dependent on the contents of certain trace elements and organic compounds. Thus, for decision-making with respect to waste wood management (recycling or combustion), reliable analytical data are needed and, due to their great economic and environmental impact, must be assured by appropriate quality control. To support the improvement in quality assurance in waste wood analysis, for the first time, a wood reference material was certified for its mass fractions of arsenic, cadmium, chromium, copper, lead, mercury, and pentachlorophenol (PCP). These analytes were selected because they represent typical constituents of wood preservatives most widely used in the past. Material preparation and testing of homogeneity and stability were carried out by BAM Federal Institute for Materials Research and Testing. The certification measurements were performed involving selected laboratories with documented expertise in the field of waste wood analysis. The certified values and their corresponding uncertainties were assigned in full compliance with the requirements of ISO Guide 35. The certified mass fractions and their expanded uncertainties (k = 2) are as follows: (3.1 ± 0.5) mg/kg for As, (3.02 ± 0.24) mg/kg for Cd, (36.4 ± 2.6) mg/kg for Cr, (22.9 ± 1.7) mg/kg for Cu, (0.60 ± 0.14) mg/kg for Hg, (39 ± 4) mg/kg for Pb, and (7.9 ± 0.6) mg/kg for PCP. The certified material is available as European Reference Material ERM^®-CD100.     

Certification of reference materials for ochratoxin A analysis in coffee and wine

Mycotoxins are important non-anthropogenic food and feed contaminants, which can be present on almost every agricultural commodity. Effective consumer protection therefore essentially depends on food surveillance by reliable quantitative analysis enabled by appropriate quality control. Certified (matrix) reference materials (CRMs) are versatile tools to support quality assurance. However, in the case of ochratoxin A (OTA), a hepato- and nephrotoxic mycotoxin, which is regulated in various foods, there is a lack of suitable CRMs. This lack has now been overcome by the development of two European Reference Materials (ERM^?) for the determination of OTA in roasted coffee (ERM^?-BD475) and red wine (ERM^?-BD476). This article discusses the material preparation process as well as the results of homogeneity and stability testing. Furthermore, the results of the in-house certification studies carried out at BAM Federal Institute for Materials Research and Testing are presented and discussed. Interlaboratory comparison studies involving selected expert laboratories with documented expertise in the field of mycotoxin analysis were conducted to confirm the certified values determined by BAM. The certified ochratoxin A values and their corresponding expanded uncertainties (k?=?2) were assigned in full compliance with the requirements of ISO Guide 35 and are as follows: (6.0?±?0.6)???g?kg^?1 for roasted coffee, ERM^?-BD475, and (0.52?±?0.11)???g?L^?1 for red wine, ERM^?-BD476.     

Identifying and quantifying short-lived fission products from thermal fission of HEU using portable HPGe detectors

Due to the emerging potential for trafficking of special nuclear material, research programs are investigating current capabilities of commercially available portable gamma ray detection systems. Presented in this paper are the results of three different portable high-purity germanium (HPGe) detectors used to identify short-lived fission products generated from thermal neutron interrogation of small samples of highly enriched uranium. Samples were irradiated at the Washington State University Nuclear Radiation Center’s 1 MW TRIGA reactor. The three portable, HPGe detectors used were the ORTEC MicroDetective [1], the ORTEC Detective [2], and the Canberra Falcon [3]. Canberra’s GENIE-2000 software was used to analyze the spectral data collected from each detector. Ultimately, these three portable detectors were able to identify a large range of fission products showing potential for material discrimination.     

Nondestructive assay of plutonium in empty stainless steel boxes by apparent mass method

Apparent mass method (Venkataraman and Croft, Nucl Instrum Methods Phys Res A 505:527, 2003), initially standardized for the assay of Pu (Agarwal et al., J Nucl Mater 651:386, 2007) has been used to get Pu amount in empty stainless steel boxes generally used for storing and transferring plutonium oxide powders. The results have been compared with the neutron coincidence counting results and have been found to match well. The advantage of the method is that it can be used for any sample with nonstandard geometry and with uncertain source distribution.     

Production of three certified reference materials for water content based on mixed solutions of butanol, xylene and propylene carbonate

Certified reference materials (CRMs) for water content with good accuracy and homogeneity are required for calibration or validation of the Karl Fischer titration and for establishing the traceability of water content results. Three such CRMs were produced and certified: GBW 13512, 13513 and 13514 are based on solvent mixtures consisting of butanol, xylene and propylene carbonate with water contents of 10.01, 1.067 and 0.139?mg/g, respectively, certified by the Karl Fischer coulometric and volumetric methods. These CRMs were prepared, dispensed and sealed under a humidity equal to the equilibrated humidity of their headspace. In this way, the between-bottle homogeneity uncertainty (u _H,rel) could be kept as low as u _H,rel?=?0.12?% for GBW 13512. The certification methods, that is, Karl Fischer coulometric and volumetric methods, were calibrated using in-house water standards prepared by gravimetry. The results were traceable to the SI unit of mass. The relative deviation of the water contents between the two methods for GBW 13512 was only 0.05?%. The expanded uncertainty (U, k?=?2) of three CRMs was 0.12, 0.024 and 0.012?mg/g, respectively. These CRMs for water content with good accuracy can be applied in the calibration or validation of measurement procedures to ensure accurate and comparable results.     

Novel carbon materials for thermal energy harvesting

To decrease the consumption of fossil fuels, research has been done on utilizing low grade heat, sourced from industrial waste streams. One promising thermoenergy conversion system is a thermogalvanic cell; it consists of two identical electrodes held at different temperatures that are placed in contact with a redox-based electrolyte [1, 2]. The temperature dependence of the direction of redox reactions allows power to be extracted from the cell [3, 4]. This study aims to increase the power conversion efficiency and reduce the cost of thermogalvanic cells by optimizing the electrolyte and utilizing a carbon based electromaterial, reduced graphene oxide, as electrodes. Thermal conductivity measurements of the K₃Fe(CN)₆/K₄Fe(CN)₆ solutions used, indicate that the thermal conductivity decreases from 0.591 to 0.547?W/m?K as the concentration is increased from 0.1 to 0.4?M. The lower thermal conductivity allowed a larger temperature gradient to be maintained in the cell. Increasing the electrolyte concentration also resulted in higher power densities, brought about by a decrease in the ohmic overpotential of the cell, which allowed higher values of short circuit current to be generated. The concentration of 0.4?M K₃Fe(CN)₆/K₄Fe(CN)₆ is optimal for thermal harvesting applications using R-GO electrodes due to the synergistic effect of the reduction in thermal flux across the cell and the enhancement of power output, on the overall power conversion efficiency. The maximum mass power density obtained using R-GO electrodes was 25.51?W/kg (three orders of magnitude higher than platinum) at a temperature difference of 60?°C and a K₃Fe(CN)₆/K₄Fe(CN)₆ concentration of 0.4?M.     

A strategy for selecting the frequency in trigonometrically-fitted methods based on the minimization of the local truncation errors and the total energy error

Trigonometrically-fitted methods have been largely used for solving second-order differential problems, and particularly for solving the radial Schrödinger equation (see for instance Alolyan and Simos in J Math Chem 50:782–804, 2012; Simos in J Math Chem 34:39–58, 2003, 44:447–466, 2008; Vigo-Aguiar and Simos in J Math Chem 29:177–189, 2001, 32:257–270, 2002 and the references therein contained). It is well-known that for periodic or oscillatory problems, trigonometrically fitted methods are more efficient than non-fitted methods. A large number of different approaches have been considered in the scientific literature to obtain analytical approximations to the frequency of oscillation in case of periodic solutions, which are valid for a large range of amplitudes of oscillation. However, these techniques have been limited to obtaining only one or two iterates because of the great amount of algebra involved. In this paper we consider the use of a trigonometrically fitted method to obtain numerical approximations for the solutions. This yields very acceptable results provided that the approximation of the parameter of the method is done with great accuracy. Many trigonometrically fitted methods have been reported in the literature, but there is no decisive way to obtain the optimal frequency value. We present a strategy for the choice of the parameter value in the adapted method, based on the minimization of the sum of the total energy error and the local truncation errors in the solution and in the derivative. We include an example solved numerically that confirms the good performance of the strategy adopted.     

The first metals in Mendeleiev’s Table: Part II. A new argument against the placement of hydrogen atop the alkali metal column

Every so often an experiment trying to give reliable evidence for a metallic hydrogen solid is reported. Such evidence is, however, not too convincing. As Eric Scerri has recently reiterated, “the jury is still out on that issue” (Scerri 2012). This search stems from the common spectroscopy shared by the hydrogen atom and all the alkali metal atoms, and perhaps is guided by a desire to place hydrogen atop the alkali metals, in Mendeleiev’s Table, reinforced by the fact pointed out by Scerri (The Periodic Table, its story and its significance, Oxford University Press, Oxford, 2007, 2012) that there is no other obvious place for hydrogen in said Table. But H₂ is a light gas at room temperature, while Li, Na, K and the other alkali elements form solid metal crystals. At very low temperatures, of course, hydrogen solidifies, but it is formed by H₂ molecules (see for example, Van Kranendonk in Solid hydrogen, Plenum Press, New York, 1983). Our purpose here is to use a new argument to break this impasse: “should H be grouped with the alkali metals with which it shares a common spectroscopy, but which solidifies in a completely different fashion?” This argument has been proposed before in a couple of papers in this journal to establish a similar question for He and the alkaline earths (Novaro in Found Chem 10:4, 2008, Ramírez-Solís and Novaro in Found Chem, 2012), as is discussed in “Precedents” section.     

Determination of elemental sulfur in phosphorous pentasulfide by temperature modulated differential scanning calorimetry

Phosphorous pentasulfide is an important starting material for a number of commercial chemicals. Examples include lubricant additives (Spikes, Trib Lett 17:469?C489, 2004), agricultural insecticides (Kirk-Othmer, Enycl Chem Technol 14:549?C552, 1995), and mining ore flotation agents. Phosphorous pentasulfide is a mixture of several components, one of which is free elemental sulfur, present at levels of approximately 50?ppm to 20,000?ppm (2?%). The amount of free sulfur present in the phosphorous pentasulfide can impact manufacturing, such as zinc dithiosulfate processing. Therefore, an accurate and fast analytical method to measure elemental sulfur in phosphorous pentasulfide would be of value compared to what is available now.     

Certification of the mass fractions of Pt, Pd and Rh in a used car catalyst reference material

The high economic value of catalysts containing the platinum group elements platinum, rhodium and palladium as active components causes the need to be able to measure the precious metal loading with small uncertainty and to have suitable certified reference materials fulfilling high demands on the quality of the certified values. In European Reference Material ERM^®-EB504, a used cordierite-based car catalyst material, mass fractions of platinum, palladium and rhodium were certified. The raw material was milled, homogenised and annealed before analysis. Seventeen laboratories experienced in precious metals analysis participated in the certification interlaboratory comparison, most of them analysing with inductively coupled plasma optical emission spectrometry using different sample pretreatment techniques. Homogeneity testing was carried out using X-ray fluorescence spectrometry. The certified mass fractions of Pt, Pd and Rh and their expanded uncertainties (k = 2) in ERM^®-EB504 are (1777 ± 15), (279 ± 6) and (338 ± 4) mg/kg respectively.     

The Homfly polynomial of double crossover links

Motivated by double crossover DNA polyhedra (He et al. in Nature 452:198, 2008; Lin et al. in Biochemistry 48:1663, 2009; Zhang et al. in J Am Chem Soc 131:1413, 2009; Zhang et al. in Proc Natl Acad Sci USA 105:10665, 2008; He et al. in Angew Chem Int Ed 49:748, )2010, in this paper, we construct a new type of link, called the double crossover link, formed by utilizing the “ $n$ -point star” to cover each vertex of a connected graph $G$ . The double crossover link can be used to characterize the topological properties of double crossover DNA polyhedra. We show that the Homfly polynomial of the double crossover link can be obtained from the chain polynomial of the truncated graph of $G$ with two distinct labels. As an application, by using computer algebra (Maple) techniques, the Homfly polynomial of a double crossover tetrahedral link is obtained. Our result may be used to characterize and analyze the topological structure of DNA polyhedra.     

Modified TTA method for the determination of plutonium

The spent fuel from Fast Breeder Test Reactor of various burnups from 25 to 155?GWd/te is being reprocessed in CORAL (COmpact Reprocessing of Advanced fuels in Lead shielded cell) using a modified PUREX (Plutonium Uranium Recovery by EXtraction) process. Total plutonium (Pu^{238, 239, 240, 241 & 242}) concentration in the sample is analysed by HTTA (Thenoyl Trifluoro Acetone) extraction method wherever interference from other alpha emitting nuclides (Raffinate) and bulk natural uranium (uranium products) are present "as reported by Milyukov et al. (Analytical chemistry of plutonium, 1967) and Natarajan and Subba Rao (BARC, pp. 38?C43, 2007)". This method requires the addition of corrosive reagents such as NH₂OH.HCl which is a problem in waste disposal for reduction. A salt-free reagent such as Hydroxyurea is studied as a reducing agent which has the ability to reduce both Pu(VI) and Pu(IV) to Pu(III) "as reported by Zhaowu (260(3):601?C606, 2004) and Zhaowu (262(3):707?C711, 2004)". Pu(III) thus formed can be easily oxidised to Pu(IV) by NaNO₂ for the extraction of Pu by HTTA.