The design and synthesis of high-efficiency materials to convert solar to electrical energy is an increasingly important research field. Within the photovoltaic technologies, crystalline Si have an 80% share while the remaining 20% are mostly thin film solar cells based on Cu(In,Ga)(S,Se)2 (CIGSSe) and CdTe. However, the cost, the abundance and the environmental impact of the elemental components cannot be neglected. For these reasons, Cu2ZnSnS4 (CZTS), Cu2ZnSnSe4 (CZTSe) and their solid solutions CZTSSe has attracted much attention recently since they can provide the development of cost competitive solar cells. The CZTS-based solar cells consist of earth abundant and relatively inexpensive elements and represent an environmentally friendly alternative compared to the above mentioned systems. The energy conversion efficiency of the CZTS-based solar cells has increased from 0.66% in 1996 to 11.1% recently.

The present work shows preliminary results that are related to the characterization of CZTSSe monograin powders by scanning electron microscopy. High purity metal compounds, S and Se powders were used as precursors for the synthesis of the Cu2ZnSn(SSe)4 monograin powders. The precursor powders were mixed to the desired composition and, additionally, KI was added as a flux material. Afterwards, the powders were blended in a mixer and encapsulated in quartz ampoules. The blended powders were degassed under dynamic vacuum at room temperature, sealed and annealed isothermally between 700 ºC and 780 ºC for a time ranging between 44 h and 136 h. After synthesis the flux material was removed with deionized water and the powders were sieved into several fractions. The morphology, microstructure and chemical composition of the synthesized powders was obtained with a Philips XL30 field-emission scanning electron microscope (FE-SEM) equipped with a backscattered electron (BSE) detector and an integrated EDAX energy dispersive X-ray spectroscopy (EDS) microanalysis system.

The typical morphology obtained for the CZTSSe powders can be seen in Figure 1. Basically, the particles show a polyhedral morphology with some of them showing a needle shape, i.e. a large shape factor (L/D>>1). Moreover, it was also observed a slight increase of the median particle size with the increase of the synthesis temperature. Due to the complexity of the synthesis of CZTSSe monograins, the formation of binary or ternary phases is a common feature. A very good control over the synthesis parameters is then required not only to obtain the desired phase but also to have a tight control over the stoichiometry of the material. Taking this into account, SEM/BSE observations and EDS analysis are two powerful techniques for evaluate the degree of the compositional homogeneity of the CZTSSe monograins. Figure 2 puts in evidence the degree of the homogeneity of the CZTSSe monograins in relation to their size. Overall, and independently of the synthesis conditions, the powder particles consisted predominantly of CZTSSe monograins and, in a much smaller extent, of particles having a ZnS or ZnS(Se) core coated by a CZTSSe layer. The presence of undesired phases occurred more frequently in the larger powder particles (> 100 µm) and the degree of homogeneity was lower for the powders synthesized at lower temperature and for a shorter time. However, when the EDS results obtained for CZTSSe monograins belonging to different size fractions are compared no major variations in the content of the five elements can be inferred.

Tungsten (W) was select for an extensive use in nuclear fusion devices due to its low neutron activation, high melting point and sputtering threshold as well as low hydrogen inventory. Nevertheless, W is brittle at low and moderate temperatures, which results in abnormal thermal stress, component fracture and extra erosion under reactor operation due to inherent thermal cycling events. An attractive way to solve these problems involves the addition of other refractory metals in the W matrix and tantalum (Ta) is a natural candidate. It has a high ductility, toughness and radiation resistance relative to those of W and transmutes to W by high-energy neutron irradiation. Recently, IST proposed the production of W-Ta composite by mechanical synthesis.

The composite should reveal the individual properties of the pristine phases as long as the interdiffusion between the components is significantly avoided during the consolidation/sintering route of the final material. Sintering operations at temperatures higher than 1300ºC lead to significant improvements in the final densification and thermal conductivity of the composites, which is crucial for fusion applications. However, W and Ta interdiffusion can be relevant above 1300ºC, mainly due to diffusion of W into Ta, and the aim of the present work is to control the mechanism.

W-Taf composites presenting 10 and 20 at.% of Ta where produced by alloying W powders and Ta fibres with a planetary ball milling route (MA) and by consolidating the mixture with spark plasma sintering (SPS) in the 1300-1600ºC temperature range. The final densifications remain fairly constant in both composites after sintering at different temperatures (83 to 87%) and the elemental interdiffusion remained low at 1300ºC. Nevertheless, the diffusivity of W in Ta became significant at 1600ºC, leading to the formation of a solid solution zone with a stoichiometry close to W16Ta84. The mechanism was followed by scanning electron and energy-dispersive X-ray spectroscopies (SEM/EDS; Figures 1 and 2, Table 1). Fabrication routes yielding high densifications and low interdiffusion are currently under investigation.

The work has been supported by the Contract of Association between Euratom and IST and by the Fund. Ciência e a Tecnologia contracts PTDC/CTM/100163/2008, Pest-OE/SADG/LA0010/2011 and PEST-OE/CTM-UI0084/2011.

The high melting point, high sputtering threshold and low tritium inventory rendered W as a potentially suitable material in fusion devices. The major problem associated with presently available tungsten grades as structural materials is its brittleness at lower temperatures. This is further worsened by irradiation embrittlement. A strategy for ductility improvement is producing a composite, with the brittle W matrix being reinforced by short fibres of tantalum. As Ta is more ductile than W it can therefore divert or stop cracks propagating in the W matrix. In the present research Ta short fibres and powder were used as reinforcement component for W by alloying Ta short fibres or powder in a W powder matrix. The composites were subsequently irradiated with deuterium to assess the retention of this hydrogenic species in the materials.

The irradiated composites, with Ta contents of 10 or 20 at%, were produced from pure elemental powders (W-Ta powder composites), and pure W powder and Ta fibre (W-Ta fibre composites) with 100 μm in diameter by low energy ball milling in argon atmosphere. These materials were consolidated via spark plasma sintering (SPS) in the temperature 1200 to 1600 ºC range. Pure W and Ta plates (controls) and W-Ta composites were irradiated with He+ ions (optional pre-implantation step) and D+ ion beams at room temperature with fluences in the 1020-1021 at/m2 range. Blistering and deuterium retention in W and Ta plates and in W-Ta composites were studied with scanning electron microscopy (SEM), X-ray diffraction and thermal desorption analysis. The deuterium concentration was evaluated trough nuclear reaction analysis (NRA) using 0.75 to 2.1 MeV 3He+ beam and the D(3He,p)α reaction.

The investigations showed that deuterium irradiation induced microstructural modifications producing blistering in Ta plates as well as in W-Ta composites (Figure 1). These effects increased substantially in the Ta and W-Ta materials with the He pre-implantation step, while blisters have not been observed in the W plates either for D+ or He+ plus D+ implantation. Higher deuterium retention was observed by thermal desorption for the composites than for the W plates. Moreover the present study revealed that D+ trapping in the composites is dependent on the microstructure with higher retention observed for fibers than for powder.

This work has been performed under the Contract of Association between EURATOM and Instituto Superior Tecnico. Financial support was also received from the Fundação para a Ciência Tecnologia (FCT) grants with references PTDC/CTM/100163/2008, Pest-OE/SADG/LA0010/2011 and PEST-OE/CTM-UI0084/2011. The authors wish to acknowledge Jorge Rocha the implantation in W-Ta samples.

Dispersing nanodiamond (nD) particles in metallic matrices can be achieved by ball milling resulting in metal-diamond composite powders. The matrices have been selected considering the whole range of carbon affinity: copper that shows extremely reduced affinity towards carbon phases, potentially compromising the composite interfaces, and nickel and tungsten that are mild and strong carbide formers, respectively, displaying thus intermediate and strong carbon affinities. For the latter matrices, dispersing carbon phases represent a challenge due to carbide conversion.

The materials produced are designated as Cu-10nD, Ni-10nD and W-20nD (where 10 and 20 indicate the atomic fraction of nD). Close monitoring of the milling conditions enabled to homogeneously disperse the carbon phases and obtain nanostructured matrices (Figures 1 (a-c)), as well as to minimize milling media contamination and carbide formation, especially in the case of the W-based composite. Apparent interfacial bonding could be inferred the from transmission electron microscopy (TEM) images.

The metallic matrices have been subsequently dissolved to allow for a detailed analysis of nanodiamond. Electron diffraction demonstrated that its crystalline structure was preserved during milling (Figure 2). Microhardness measurements revealed remarkable strength enhancements of the nanostructured composites over that of pure metals of comparable grain sizes (Table 1). The strengthening mechanisms that justify the hardness increments in Cu-10nD and Ni-10nD include second-phase reinforcement (due to the potential load bearing ability of diamond), as well as Orowan and solid solution strengthening. The hardening effect observed in the W-20nD composite over that of pure milled tungsten is probably related to the nanodiamond reinforcement, nevertheless the influence of a fine dispersion of carbides cannot be ruled out.

This work has been performed under the Contract of Association between EURATOM and Instituto Superior Tecnico. Financial support was also received from the Fundação para a Ciência Tecnologia (FCT) grants with references PTDC/CTM/100163/2008, Pest-OE/SADG/LA0010/2011 and PEST-OE/CTM-UI0084/2011.

The use of a high-brightness field-emission gun (FEG) in scanning electron microscopy (SEM) is a powerful technique to examine microstructures at very high spatial resolution down to nanometer level and has significantly enhanced our ability to solve challenging materials problems, allowing studies of nanoprecipitates.

The microstructures of tungsten, molybdenum and copper wires used as Langmuir probes at ISTTOK edge plasma have been investigated. The probes cross-sections evidenced extensive grain growth, intergranular bubbles and increased hardness at the plasma exposed regions. Internal surfaces of large bubbles exhibited slip bands resulting from plastic deformation induced by high H2 pressure. Elastic recoil detection analysis was used to measure H concentration profiles. The present results suggest that H2 bubble formation in first wall components under long-term high thermal loads should be closely monitored in nuclear fusion devices. Strategies for H damage mitigation are proposed and discussed.

A novel material design for nuclear fusion reactors is proposed based on Cu-Diamond and W-Diamond nanocomposites. The proposed design involves the production of W/W-Diamond/CuDiamond/Cu functionally graded material. W, W-Diamond, Cu-Diamond and Cu nanostructured composite powders were produced independently by mechanical alloying and subsequently consolidated/welded through spark plasma sintering. Modulation of processing parameters allowed controlling the extent of unfavourable conversion of Diamond into tungsten carbide, as well as to overcome the Diamond intrinsically difficult bonding to copper. Microstructural features and microhardness of the as-produced materials are presented.

Results of the microstructural characterization of four different RAFM ODS Eurofer 97 batches are presented and discussed. Analyses and observations were performed by nuclear microprobe and scanning and transmission electron microscopy. X-ray elemental distribution maps obtained with proton beam scans showed homogeneous composition within the proton beam spatial resolution and, in particular, pointed to a uniform distribution of ODS (yttria) nanoparticles in the Eurofer 97 matrix. This was confirmed by transmission electron microscopy. Scanning electron microscopy coupled with energy dispersive spectroscopy made evident the presence of chromium carbide precipitation. Precipitates occurred preferentially along grain boundaries (GB) in three of the batches and presented a discrete distribution in the other, as a result of different thermo-mechanical routes. Additional electron backscattered diffraction experiments revealed the crystalline textures in the ferritic polycrystalline structure of the ODS steel samples.