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A multi-target recoil chamber technique was applied to study online chemical properties of protactinium in chlorinating and brominating gas media using 226Pa (T 1/2 = 1.8 min) decaying by alpha emission (74%) and β+/EC decay (26%). A 58 MeV proton beam passing 15 × 50 μg/cm2 thick 232Th targets enabled production of 226Pa formed in the reaction 232Th(p,7n). Isothermal gas chromatography in quartz columns allowed for the determination of adsorption enthalpies of oxohalides and pure halides of Pa5+ compounds. On the basis of empirical correlations, these adsorption enthalpies (ΔH0 ads) could be converted to sublimation enthalpies (ΔH0 subl). Resulting values for the assumed compounds PaCl5, PaOCl3, PaBr5, and PaOBr3 were 113 ± 15, 329 ± 16, 165 ± 5 and 235 ± 17 kJ/mol, respectively. These values are rather similar to known ΔH0 subl data for group-5 elements Nb, Ta and Db in support of the assumption that Pa is a pseudo-group 5 element.

Using the Fast On-line Reaction Apparatus (FORA), the influence of various gas-purification columns onto the formation of metal carbonyl complexes (MCCs) under single-atom chemistry conditions was investigated. MCCs were synthesized from single atoms of Mo, Tc, Ru and Rh being produced by the spontaneous fission of 252Cf and recoiling into a CO-gas containing carrier gas atmosphere. The in-situ synthesized MCCs were volatile enough to be transported by the carrier gas to a charcoal trap where they were adsorbed and their subsequent decay was registered by γ-spectrometry. It was found that the type and combination of purification columns used to clean the applied CO-gas strongly influences the obtained formation and transport yields for all MCCs. With the exception of Rh-carbonyl, intense gas-purification strategies resulted in reduced formation and transport yields for MCCs in comparison with less efficient or even completely missing purification setups. It was postulated that the observed reduction in yield might depend on the content of Fe(CO)5 and Ni(CO)4, as well as potentially other MCCs, in the CO-gas, being formed by the interaction between CO and the steel-surfaces of FORA as well as from impurities in the used charcoal traps. Subsequently, it was shown that macro amounts of Fe(CO)5, Ni(CO)4, Mo(CO)6 and Re2(CO)10 added to the used process gas indeed increase significantly the overall yields for MCCs produced by 252Cf fission products. Ni(CO)4 appeared the most potent to increase the yield. Therefore, it was used in more detailed investigations. Using isothermal chromatography, it was shown that Ni(CO)4 does not affect the speciation of carbonyl species produced by the 252Cf fission product 104Mo. For 107Tc, 110Ru and 111Rh a speciation change cannot be excluded. For 111Rh a speciation change cannot be excluded. An inter-carbonyl transfer mechanism is suggested boosting the formation of MCCs. The current discovery might allow for new opportunities in various research fields, which are currently restricted by the low overall yields for MCCs produced under single-atom chemistry conditions. Examples are the chemical investigation of transactinides or the generation of radioactive ion beams from refractory metals at accelerators.

The formation and the chemical characterization of single atoms of dubnium (Db, element 105), in the form of its volatile oxychloride, was investigated using the on‐line gas phase chromatography technique, in the temperature range 350–600 °C. Under the exactly same chemical conditions, comparative studies with the lighter homologues of Group 5 in the Periodic Table clearly indicate the volatility sequence being NbOCl3 > TaOCl3 ≥ DbOCl3. From the obtained experimental results, thermochemical data for DbOCl3 were derived. The present study delivers reliable experimental information for theoretical calculations on chemical properties of transactinides., Dubnium obeys Mendeleev's periodicity. Fifty years after the discovery of this element, its chemical behavior was experimentally revisited. From the gas chromatographic investigation of the volatile oxychloride compound, a trend of decreasing volatility along Group 5 elements was deduced, in agreement with the expectations by the laws established in the Periodic Table.

The usage of silver as a filtering material for removal of iodine from the gas phase of a lead–bismuth eutectic based nuclear reactor was investigated in various atmospheres representing normal operation as well as accident conditions. Thermochromatography experiments were performed to quantify the retention experienced on a silver surface by iodine species evaporated from a lead–bismuth eutectic sample. Measured adsorption enthalpies ranged from −171 to − 208 kJ mol−1 with observed differences attributed to various surface effects rather than a change in iodine speciation. The postulated adsorption mechanism is chemisorption of iodine atoms on the silver surface. Metallic silver fulfills the desired criteria for a capturing material in water-free filtering systems to be used as an alternative to traditional alkaline scrubbers commonly used in LWR systems.

Iodine evaporated from lead–bismuth eutectic (LBE) has been examined with respect to its adsorption behavior on stainless steel in various gases to establish a base for safety evaluations on LBE based nuclear reactors. In inert conditions the iodine forms a single species with an adsorption enthalpy between − 97 and − 106 kJ/mol. The adsorbed species is tentatively identified as bismuth monoiodide, BiI. Addition of moisture to the inert gas has no substantial influence on the adsorption behaviour. For the reducing hydrogen carrier gas depositions with adsorption enthalpies ranging from − 87 to − 134 kJ/mol were observed in dry and water saturated conditions. The larger variation of adsorption enthalpies compared to analogous experiments in helium likely result from surface effects induced by the reactive gas. Formation of highly volatile species such as hydrogen iodide HI was not observed. In oxidizing conditions multiple iodine species with adsorption enthalpies ranging from − 67 to − 83 kJ/mol were observed, with the exception of one experiment where only a lower limit of –ΔHads

The Fast On-line Reaction Apparatus (FORA) was used to investigate the influence of various reaction parameters onto the formation and transport of metal carbonyl complexes (MCCs) under single-atom chemistry conditions. FORA is based on a 252Cf-source producing short-lived Mo, Tc, Ru and Rh isotopes. Those are recoiling from the spontaneous fission source into a reaction chamber flushed with a gas-mixture containing CO. Upon contact with CO, fission products form volatile MCCs which are further transported by the gas stream to the detection setup, consisting of a charcoal trap mounted in front of a HPGe γ-detector. Depending on the reaction conditions, MCCs are formed and transported with different efficiencies. Using this setup, the impact of varying physical parameters like gas flow, gas pressure, kinetic energy of fission products upon entering the reaction chamber and temperature of the reaction chamber on the formation and transport yields of MCCs was investigated. Using a setup similar to FORA called Miss Piggy, various gas mixtures of CO with a selection of noble gases, as well as N2 and H2, were investigated with respect to their effect onto MCC formation and transport. Based on this measurements, optimized reaction conditions to maximize the synthesis and transport of MCCs are suggested. Explanations for the observed results supported by simulations are suggested as well.

As a step toward licensing a lead–bismuth eutectic (LBE) based reactor design, the adsorption behavior of iodine evaporated from LBE on fused silica was examined. Using inert and reducing carrier gases, depositions with an adsorption enthalpy of − 95 to − 113 kJ mol−1 were observed. These depositions are compatible with a single species, tentatively identified as bismuth monoiodide, BiI. When introducing oxidizing conditions, multiple iodine species with higher volatility form, with adsorption enthalpies ranging from − 67 to − 86 kJ mol−1. Based on an empirical correlation one of these species was identified as monatomic iodine. This work provides fundamental understanding of the LBE/iodine gaseous chemistry and related adsorption deposition behavior.

The efficient removal of the long-lived fission product 137Cs from radioactive water by a filter material based on whey protein fibrils and activated carbon.

The fundamental principles of the periodic table guide the research and development of the challenging experiments with transactinide elements. This guidance is elucidated together with experimental results from gas phase chemical studies of the transactinide elements with the atomic numbers 104–108 and 112–114. Some deduced chemical properties of these superheavy elements are presented here in conjunction with trends established by the periodic table. Finally, prospects are presented for further chemical investigations of transactinides based on trends in the periodic table.

Fission products recoiling from a 252Cf spontaneous fission source were stopped in various mixtures of inert gases containing CO and NO. For the elements of the transisition metal series Mo, Tc, Ru, and Rh previous observations of pure carbonyl complexes were reproduced. However, no formation of volatile mixed nitrosyl-carbonyl complexes or pure nitrosyl complexes for these elements have been observed. Instead, efficient production of volatile nitrosyl compounds for single iodine atoms, presumably nitrosyl iodide, NOI, was detected. This observation is of interest as potential transport path for iodine in nuclear accident scenarios and as a model for radiochemistry with the recently discovered heaviest halogen tennessine (Z=117).

The physical and chemical knowledge representing today's scientific basis of the periodic table of elements (Figure 1) has perpetually developed over the past one and a half centuries. However, the...

Accelerator driven fast nuclear reactors cooled by lead-bismuth eutectic (LBE) are developed for transmuting long-lived radionuclides in spent nuclear fuel. Due to the nature of the coolant, operating the reactor will result in a production of 210Po by neutron capture. Understanding the behavior of this highly radiotoxic nuclide in the event of a failure of the window separating the evacuated proton beam guide from the reactor core is required for safety assessments. The present work aims at acquiring this knowledge by studying the evaporation of polonium from neutron-irradiated LBE and its deposition in a scaled down model of the beam tube. Experimental results along with Monte Carlo simulations indicate that polonium adsorbs as a single species with an adsorption enthalpy of approximately −156 kJ/mol.

The hyperfine splitting of the 5g→4f transitions in muonic Re185,187 has been measured using high resolution high purity germanium detectors and compared to state-of-the-art atomic theoretical predictions. The spectroscopic quadrupole moment has been extracted using modern fitting procedures and compared to the values available in literature obtained from muonic x rays of natural rhenium. The extracted values of the nuclear spectroscopic quadrupole moment are 2.07(5) b and 1.94(5) b, respectively for Re185 and Re187.

The evaporation of iodine containing species from tellurium has been investigated together with their adsorption behavior on a fused silica surface. In inert gas, the formation of two species was observed with adsorption enthalpies of around − 90 to − 100 and − 110 to − 120 kJ/mol, respectively. For reducing environments, a single species identified as monatomic iodine was observed with an adsorption enthalpy around − 95 kJ/mol. In oxidizing conditions, species with low adsorption enthalpies ranging from − 65 to − 80 kJ/mol were observed. Presumably, these are iodine oxides as well as oxo-acids of iodine (HIOx). The results of the thermochromatography experiments performed here prove the usefulness of the employed production method for carrier-free iodine isotopes and enhance the understanding of the evaporation and deposition behavior of iodine under various chemical conditions.

Radionuclide production and development has a long history at the Paul Scherrer Institute (PSI) and dates back to the founding times of its forerunner institutions: the Federal Institute for Reactor Research and the Swiss Institute for Nuclear Research. The facilities used for this purpose have evolved substantially over the last five decades. Many radiometals in use today, as radiopharmaceuticals, are for the diagnosis and treatment of disease, with the most popular means of detection being Positron Emission Tomography. These positron emitters are easily produced at low proton energies using medical cyclotrons, however, developments at these facilities are lacking. Currently, the fixed 72 MeV proton beam at PSI is degraded at IP2 irradiation station to provide the desired energy to irradiate targets to produce the likes of 44Sc, 43Sc and 64Cu as a proof of principle, which are of great interest to the nuclear medicine community. This development work can then be implemented at facilities containing medical cyclotrons. A history of the development of radionuclides at PSI, along with current development and projects with partner institutions, is described., Chimia, 74 (12), ISSN:0009-4293

This article summarizes the results obtained studying the interaction between polonium and stainless steel 316L in different atmospheres by the thermochromatography method. This issue is particularly important in terms of licensing of the MYRRHA prototype ADS reactor, where highly radiotoxic α-emitting polonium isotopes are produced in lead-bismuth eutectic used as both spallation target material and coolant, while stainless steel 316L is going to be the main structural material. The polonium adsorption enthalpy on stainless steel 316L in inert atmosphere was measured as −147±6 kJ mol−1. The findings obtained using reducing atmospheres show that the affinity of polonium for stainless steel 316L increases with the metallic character of the stainless steel surface. The presence of moisture in inert and reducing atmosphere does not significantly influence the polonium adsorption. Oxidizing atmospheres induce the formation of polonium dioxide which has a stronger interaction with the stainless steel 316L, with an adsorption enthalpy of −225±6 kJ mol−1. A prolonged exposure of the stainless steel to strong oxidants, such as pure oxygen, reduces the metallic character of the stainless steel surface and, consequently, its affinity to the polonium oxide. Furthermore, it was found that in all experiments at least 5 ppm of the total polonium present in the starting material were not retained on the stainless steel 316L surface at all.

Here, we present the fabrication details and functional tests of diamond-based α-spectroscopic sensors, dedicated for high-temperature experiments, targeting the chemistry of transactinide elements. Direct heating studies with this sensor material, revealed a current upper temperature threshold for a safe α-spectroscopic operation of T det = 453 K . Up to this temperature, the diamond sensor could be operated in a stable manner over long time periods of the order of days. A satisfying resolution of ≈ 50 keV FWHM was maintained throughout all conducted measurements. However, exceeding the mentioned temperature limit led to a pronounced spectroscopic degradation in the range of 453 − 473 K , thereby preventing any further α-spectroscopic application. These findings are in full agreement with available literature data. The presented detector development generally enables the chemical investigation of more short-lived and less volatile transactinide elements and their compounds, yet unreachable with the currently employed silicon-based solid state sensors. In a second part, the design, construction, and α-spectroscopic performance of a 4-segmented diamond detector, dedicated and used for transactinide element research, is given as an application example.

A gas-phase chemical study of rhenium carbonyls was carried out using short-lived radioisotopes produced at a heavy-ion accelerator. The Re isotopes produced in the nuclear reactions of natGd(23Na,xn)172–177Re were pre-separated with a gas-filled recoil ion separator and their carbonyls were synthesized in a mixture of inert gas and carbon monoxide. Using a low temperature isothermal chromatography apparatus, the adsorption enthalpies of Re carbonyls were derived to be ΔHads = −42 ± 2 kJ mol−1 on a Teflon® surface by fitting the external chromatograms with a Monte Carlo simulation program. A chemical yield of 25% relative to that of the transport yield for Re by a He/KCl gas-jet was achieved. The laser-ablation time-of-flight mass-spectrometric technique was employed to identify the species of Re carbonyls produced in the gas phase. The most stable species was deduced to be Re(CO)5 based on the mass-spectrometric analysis as well as quantum chemistry calculations.

Here, we present a review on a fundamental radiochemical research topic performed by Swiss scientists in national and international collaborations, utilizing large accelerator facilities at the Paul Scherrer Institute as well as abroad. The chemical investigation of the heaviest elements of the periodic table is a truly multidisciplinary effort, which allows scientists to venture into a variety of fields ranging from nuclear and radiochemistry to experimental and theoretical work in inorganic and physical chemistry all the way to nuclear and atomic physics. The structure and fundamental ordering scheme of all elements in the periodic table, as established more than 150 years ago, is at stake: The ever increasing addition of new elements at the heavy end of the periodic table together with a growing influence of relativistic effects, raises the question of how much periodicity applies in this region of the table. Research on the heaviest chemical elements requires access to large heavy-ion accelerator facilities as well as to rare actinide isotopes as target materials. Thus, this scientific area is inevitably embedded in joint international efforts. Its fundamental character ensures academic relevance and thereby substantially contributes to the future of nuclear sciences in Switzerland.

In preparation of chemical investigations of the superheavy elements (SHEs) copernicium and flerovium, model experiments with 197Hg were conducted. The interaction of elemental mercury on a sulfur surface was investigated by off-line isothermal gas chromatography. Although the formation of HgS(s) is thermodynamically favored, a strong kinetic hindrance is observed at room temperature, and thus only adsorption interactions could be addressed. A dependence of the adsorption interaction strength on the allotropic transformations of the sulfur surface was observed. The high temperatures needed to promote the chemical interaction of Hg with S prevent sulfur from being a suitable chromatographic surface for SHEs experiments with the state-of-the-art gas phase technology.

Polonium isotopes are considered the most hazardous radionuclides produced during the operation of accelerator driven systems (ADS) when lead–bismuth eutectic (LBE) is used as the reactor coolant and as the spallation target material. In this work the use of gold surfaces for capturing polonium from the cover gas of the ADS reactor was studied by thermochromatography. The results show that gaseous monoatomic polonium, formed in dry hydrogen, is adsorbed on gold at 1058 K. Its adsorption enthalpy was calculated as –250±7 kJ mol−1, using a Monte Carlo simulation code. Highly volatile polonium species that were observed in similar experiments in fused silica columns in the presence of moisture in both inert and reducing gas were not detected in the experiments studying adsorption on gold surfaces. PoO2 is formed in both dry and moist oxygen, and its interaction with gold is characterized by transport reactions. The interaction of bismuth, present in large amounts in the atmosphere of the ADS, with gold was also evaluated. It was found that bismuth has a higher affinity for gold, compared to polonium, in an inert, reducing, and oxidizing atmosphere. This fact must be considered when using gold as a material for filtering polonium in the cover gas of ADS.

This work presents the results obtained from studying the interaction between polonium compounds formed in different atmospheres and platinum, palladium and silver surfaces obtained by thermochromatography. These results are of crucial importance for the design of cover gas filter systems for lead-bismuth eutectic (LBE)-based nuclear facilities such as accelerator driven systems (ADS). The results obtained from studying the interaction of polonium and platinum under inert atmosphere and reducing atmospheres with and without addition of moisture show that polonium is deposited at temperatures between 993 and 1221 K, with adsorption enthalpies ranging from –235 to –291 kJ mol−1, indicating a very strong adsorption of the polonium species present on platinum surfaces. The interaction between polonium and silver was investigated using purified inert, reducing and oxidizing carrier gases. Results show a deposition temperature between 867 and 990 K, with adsorption enthalpies ranging from –205 to –234 kJ mol−1. The interaction of polonium and palladium was studied in purified helium and purified hydrogen. For both conditions a deposition temperature of 1221 K was observed corresponding to an adsorption enthalpy of –340 kJ mol−1. No highly volatile polonium species was formed at any of the applied experimental conditions.

The decomposition behavior of group 6 metal hexacarbonyl complexes (M(CO)6) in a tubular flow reactor is simulated. A microscopic Monte-Carlo based model is presented for assessing the first bond dissociation enthalpy of M(CO)6complexes. The suggested approach superimposes a microscopic model of gas adsorption chromatography with a first-order heterogeneous decomposition model. The experimental data on the decomposition of Mo(CO)6and W(CO)6are successfully simulated by introducing available thermodynamic data. Thermodynamic data predicted by relativistic density functional theory is used in our model to deduce the most probable experimental behavior of the corresponding Sg carbonyl complex. Thus, the design of a chemical experiment with Sg(CO)6is suggested, which is sensitive to benchmark our theoretical understanding of the bond stability in carbonyl compounds of the heaviest elements.

An isothermal vacuum chromatography setup for superheavy element chemistry studies was developed and tested online at the one-atom-at-a-time level. As a model system, the adsorption behavior of thallium on quartz was chosen with respect to a future chemical characterization of its superheavy homologue, element 113 (E113, Z = 113), using the described setup. Short-lived 184Tl (t1/2 = 10.1(5) s) was produced in the reaction 152Gd(35Cl, 3n)184Tl and delivered as a mass-separated ion beam to the chemistry experiment: A subsurface implantation and a subsequent fast thermal release from a metal matrix was followed by isothermal vacuum chromatography as the chemical separation stage. Single atomic species passing this chromatographic separation were finally identified by time- and energy-resolved event-by-event α-spectroscopy using a diamond-based solid-state detector. The derived adsorption enthalpy of −ΔHadsSiO2(Tl) = 158 ± 3 kJ·mol–1 significantly exceeds available data but correlates well with the adsorption...

Chemical investigations of superheavy elements in the gas-phase, i.e. elements with Z≥104Z≥104, allow assessing the influence of relativistic effects on their chemical properties. Furthermore, for some superheavy elements and their compounds quite unique gas-phase chemical properties were predicted. The experimental verification of these properties yields supporting evidence for a firm assignment of the atomic number. Prominent examples are the high volatility observed for HsO4 or the very weak interaction of Cn with gold surfaces. The unique properties of HsO4 were exploited to discover the doubly-magic even–even nucleus 270Hs and the new isotope 271Hs. The combination of kinematic pre-separation and gas-phase chemistry allowed gaining access to a new class of relatively fragile compounds, the carbonyl complexes of elements Sg through Mt. A not yet resolved issue concerns the interaction of Fl with gold surfaces. While competing experiments agree on the fact that Fl is a volatile element, there are discrepancies concerning its adsorption on gold surfaces with respect to its daughter Cn. The elucidation of these and other questions amounts to the fascination that gas-phase chemical investigations exert on current research at the extreme limits of chemistry today.

Muonic atoms have been used to extract the most accurate nuclear charge radii based on the detection of X-rays from the muonic cascades. Most stable and a few unstable isotopes have been investigated with muonic atom spectroscopy techniques. A new research project recently started at the Paul Scherrer Institut aims to extend the highresolution muonic atom spectroscopy for the precise determination of nuclear charge radii and other nuclear structure properties of radioactive isotopes. The challenge to combine the high-energy muon beam with small quantity of stopping mass is being addressed by developing the concept of stopping the muon in a high-density, a high-pressure hydrogen cell and subsequent transfer of the muon to the element of interest. Status and perspectives of the project will be presented., EPJ Web of Conferences

Background The favorable decay properties of 43Sc and 44Sc for PET make them promising candidates for future applications in nuclear medicine. An advantage 43Sc (T1/2 = 3.89 h, Eβ+ av = 476 keV [88%]) exhibits over 44Sc, however, is the absence of co-emitted high energy γ-rays. While the production and application of 44Sc has been comprehensively discussed, research concerning 43Sc is still in its infancy. This study aimed at developing two different production routes for 43Sc, based on proton irradiation of enriched 46Ti and 43Ca target material. Results 43Sc was produced via the 46Ti(p,α)43Sc and 43Ca(p,n)43Sc nuclear reactions, yielding activities of up to 225 MBq and 480 MBq, respectively. 43Sc was chemically separated from enriched metallic 46Ti (97.0%) and 43CaCO3 (57.9%) targets, using extraction chromatography. In both cases, ~90% of the final activity was eluted in a small volume of 700 μL, thereby, making it suitable for direct radiolabeling. The prepared products were of high radionuclidic purity, i.e. 98.2% 43Sc were achieved from the irradiation of 46Ti, whereas the product isolated from irradiated 43Ca consisted of 66.2% 43Sc and 33.3% 44Sc. A PET phantom study performed with 43Sc, via both nuclear reactions, revealed slightly improved resolution over 44Sc. In order to assess the chemical purity of the separated 43Sc, radiolabeling experiments were performed with DOTANOC, attaining specific activities of 5–8 MBq/nmol, respectively, with a radiochemical yield of >96%. Conclusions It was determined that higher 43Sc activities were accessible via the 43Ca production route, with a comparatively less complex target preparation and separation procedure. The product isolated from irradiated 46Ti, however, revealed purer 43Sc with minor radionuclidic impurities. Based on the results obtained herein, the 43Ca route features some advantages (such as higher yields and direct usage of the purchased target material) over the 46Ti path when aiming at 43Sc production on a routine basis. Electronic supplementary material The online version of this article (10.1186/s41181-017-0033-9) contains supplementary material, which is available to authorized users.

A set of optimized deposition conditions for the inner wall coating of fused silica tubes with amorphous selenium was elaborated. The method is based on the vapor transport deposition of pure elemental selenium on a cooled substrate held at liquid nitrogen temperatures. Morphological and structural examination of the deposited layer was performed by optical microscopy and X-ray diffraction studies. Neutron activated selenium was used to monitor the deposition pattern and its stability under high gas flows. Monte Carlo simulations allowed the estimation of the different Se species composing the amorphous phase, at the given experimental deposition conditions. The versatility of the coating method presented in this work allows for the coating of tubes of different lengths and diameters, opening the way for several applications of amorphous selenium films in various fields.

Rapid in situ formation of metal carbonyl complexes with short-lived nuclides has been demonstrated to be feasible with recoiling ions formed in nuclear fusion and fission reactions. These carbonyl complexes are highly volatile and can be transported rapidly in a gas-stream to counting or chemistry devices. This method was already successfully applied in the chemical investigation of the superheavy element seaborgium (Z = 106) and appears promising for various fields of nuclear research. In this article, we give an overview on the current status of metal carbonyl complex studies with short-lived d-element isotopes.

Summary. Volatile metal complexes of the group 4 elements Zr and Hf with hexafluoroacetylacetonate (hfa) have been studied using short-lived radioisotopes of the metals. The new technique of physical preseparation has been employed where reaction products from heavy-ion induced fusion reactions are isolated in a physical recoil separator – the Berkeley Gas-filled Separator in our work – and made available for chemistry experiments. Formation and decomposition of M(hfa)4 (M = Zr, Hf) has been observed and the interaction strength with a fluorinated ethylene propylene (FEP) Teflon surface has been studied. From the results of isothermal chromatography experiments, an adsorption enthalpy of −ΔHa = (57 ± 3) kJ/mol was deduced. In optimization experiments, the time for formation of the complex and its transport to a counting setup installed outside of the irradiation cave was minimized and values of roughly one minute have been reached. The half-life of 165 Hf , for which conflicting values appear in the literature, was measured to be (73.9 ± 0.8) s. Provided that samples suitable for α-spectroscopy can be prepared, the investigation of rutherfordium (Rf), the transactinide member of group 4, appears possible. In the future, based on the studies presented here, it appears possible to investigate short-lived single atoms produced with low rates (e.g., transactinide isotopes) in completely new chemical systems, e.g., as metal complexes with organic ligands as used here or as organometallic compounds.

Gas-phase chromatography studies of nihonium (Nh, $Z=113$ ) were carried out at the one-atom-at-a-time level. For the production of nihonium, the heavy-ion-induced nuclear fusion reaction of 48Ca with 243Am was used. This leads to isotopes 284,285Nh, as the direct descendants of the $\alpha$ -decaying precursors 288,289Mc. Combining the Dubna Gas-Filled Recoil Separator with gas-phase chromatographic separation, the experiment was sensitive to elemental nihonium and its adsorption behavior on Teflon, theoretically predicted by modern relativistic density functional theory. The non-observation of any decays of Nh after the chemical separation indicates a larger than expected retention of elemental Nh on a Teflon surface.

The adsorption behavior of 197Hg and 183–185Hg on red amorphous selenium (red a-Se) and trigonal selenium (t-Se) was investigated experimentally by off-line and on-line gas chromatographic methods, in preparation of a sensitive chemical separation and characterization of the transactinides copernicium (Cn, Z = 112) and flerovium (Fl, Z = 114). Monte-Carlo simulations of a diffusion controlled deposition were in good agreement with the experimental results, assuming as interaction limits −ΔH ads red a-Se (Hg) > 85 kJ/mol, and −ΔH ads t-Se (Hg)

We report on the in-situ synthesis of metal carbonyl complexes with short-lived isotopes of transition metals. Complexes of molybdenum, technetium, ruthenium and rhodium were synthesized by thermalisation of products of neutron-induced fission of 249Cf in a carbon monoxide-nitrogen mixture. Complexes of tungsten, rhenium, osmium, and iridium were synthesized by thermalizing short-lived isotopes produced in 24Mg-induced fusion evaporation reactions in a carbon monoxide containing atmosphere. The chemical reactions took place at ambient temperature and pressure conditions. The complexes were rapidly transported in a gas stream to collection setups or gas phase chromatography devices. The physisorption of the complexes on Au and SiO2 surfaces was studied. We also studied the stability of some of the complexes, showing that these start to decompose at temperatures above 300 ℃ in contact with a quartz surface. Our studies lay a basis for the investigation of such complexes with transactinides.

Phenomena related to the volatilization of polonium and its compounds are critical issues for the safety assessment of the innovative lead–bismuth cooled type of nuclear reactor or accelerator driven systems. The formation and volatilization of different species of polonium and their interaction with fused silica was studied by thermochromatography using carrier gases with varied redox potential. The obtained results show that under inert and reducing conditions in the absence of moisture, elemental polonium is formed. Polonium compounds more volatile than elemental polonium can be formed if traces of moisture are present in both inert and reducing carrier gas. The use of dried oxygen as carrier gas leads to the formation of polonium oxides, which are less volatile than elemental polonium. It was also found that the volatility of polonium oxides increases with increasing oxidation state. In the presence of moisture in an oxidizing carrier gas, species are formed that are more volatile than the oxides and less volatile than the elemental polonium. Considering the redox potential of the carrier gas those species are likely oxyhydroxides.

The evaporation behavior of polonium as one of the most hazardous radionuclides produced in spallation based neutron sources with liquid lead–bismuth targets has been quantified in this study. The normalized apparent vapor pressure, i.e. the Henry constant of polonium over liquid lead–bismuth eutectic was determined in the temperature range relevant for operation of such targets, i.e. 164–500 °C. For comparison and better fundamental understanding, the Henry constant of polonium over pure liquid bismuth was determined in a temperature range of 300–500 °C. The Henry constants of polonium in this temperature range were found to be orders of magnitude higher than expected from earlier studies at higher temperatures. Possible mechanisms responsible for this unexpected behavior are discussed.

First experimental results of a chemical investigation of element 113 independently confirm the synthesis of the new elements 115 and 113 in the nuclear fusion reaction of Ca 48 + Am 243 and indicate a chemical behaviour resembling a species with a high volatility a weak interaction with inert surfaces and an enhanced reactivity towards gold surfaces.

Previously reported preparation method for Pd-based intermetallic targets (Usoltsev, et al., 2012) [1] has been successfully applied for producing two stationary 243Am/Pd targets. Both targets have been irradiated at the U-400 cyclotron at Flerov Laboratory of Nuclear Reactions Dubna (Russian Federation) using high intensity beams (up to 0.83 μApart) of 48Ca18+. Alpha-particle spectroscopy and light microscopy allowed for a comprehensive characterization of the intermetallic targets before and after irradiation. A natNd/Pd intermetallic target and a solely electroplated 243Am/Ti target were similarly investigated for comparison.

The thermal release rate of nuclear reaction products was investigated in offline annealing experiments. This work was motivated by the search for a high melting catcher material for recoiling products from heavy ion induced nuclear fusion reactions. Polycrystalline refractory metal foils of Ni Y Zr Nb Mo Hf W and Re were investigated as catcher metals. Diffusion data for various tracer/host combinations were deduced from the measured release rates. This work focuses on the diffusion and the release rate of volatile p elements from row 5 and 6 of the periodic table as lighter homologues of the superheavy elements with Z = 113 to be studied in future experiments. A massive radiation damage enhancement of the diffusion velocity was observed. Diffusion trends have been established along the groups and rows of the periodic table based on the dependence of diffusion velocity on atomic sizes. © 2013 Elsevier Ltd. All rights reserved.

A new method of intermetallic target preparation is described. Based on the molecular plating technique followed by “coupled reduction”, this method allows producing stable and homogeneous metallic targets for high intensity irradiations. In the first step, the target material is electroplated on a noble metal surface, ensuring homogeneous distribution of the desired element on the target backing. In the second step, the foil with the plated material is heated in a hydrogen flow. Due to the formation of an intermetallic compound with the noble metal support, reduction of the target material with hydrogen at high temperatures becomes thermodynamically possible. Nitrates of all six investigated elements (U, Th, Am, Gd, Nd, and Eu) were electroplated with excellent yields on Pd backing foils by the molecular plating technique and completely reduced in hydrogen atmosphere. A homogeneous distribution of the target material over the whole thickness of the Pd foil was observed suggesting a pronounced diffusion of the reduced metals into the backing material already during the reduction process. A first test irradiation experiment with a thin 3.5 μm U/Pd intermetallic target is described.

Element 114 was discovered in 2000 by the Dubna-Livermore collaboration, and in 2012 it was named flerovium. It belongs to the group 14 of the periodic table of elements. A strong relativistic stabilisation of the valence shell 7s 2 7p 2 1/2 is expected due to the orbital splitting and the contraction not only of the 7s 2 but also of the spherical 7p 2 1/2 closed subshell, resulting in the enhanced volatility and inertness. Flerovium was studied chemically by gas-solid chromatography upon its adsorption on a gold surface. Two experimental results on Fl chemistry have been published so far. Based on observation of three atoms, a weak interaction of flerovium with gold was suggested in the first study. Authors of the second study concluded on the metallic character after the observation of two Fl atoms deposited on gold at room temperature.