D. Mata

Control of crystallite and particle size in the synthesis of layered double hydroxides: Macromolecular insights and a complementary modeling tool

Zinc-aluminum layered double hydroxides with nitrate intercalated (Zn(n)Al-NO3, n=Zn/Al) is an intermediate material for the intercalation of different functional molecules used in a wide range of industrial applications. The synthesis of Zn(2)Al-NO3 was investigated considering the time and temperature of hydrothermal treatment. By examining the crystallite size in two different directions, hydrodynamic particle size, morphology, crystal structure and chemical species in solution, it was possible to understand the crystallization and dissolution processes involved in the mechanisms of crystallite and particle growth. In addition, hydrogeochemical modeling rendered insights on the speciation of different metal cations in solution. Therefore, this tool can be a promising solution to model and optimize the synthesis of layered double hydroxide-based materials for industrial applications.

Processing strategies for smart electroconductive carbon nanotube-based bioceramic bone grafts

Electroconductive bone grafts have been designed to control bone regeneration. Contrary to polymeric matrices, the translation of the carbon nanotube (CNT) electroconductivity into oxide ceramics is challenging due to the CNT oxidation during sintering. Sintering strategies involving reactive-bed pressureless sintering (RB + P) and hot-pressing (HP) were optimized towards prevention of CNT oxidation in glass/hydroxyapatite (HA) matrices. Both showed CNT retentions up to 80%, even at 1300 °C, yielding an increase of the electroconductivity in ten orders of magnitude relative to the matrix. The RB + P CNT compacts showed higher electroconductivity by ∼170% than the HP ones due to the lower damage to CNTs of the former route. Even so, highly reproducible conductivities with statistical variation below 5% and dense compacts up to 96% were only obtained by HP. The hot-pressed CNT compacts possessed no acute toxicity in a human osteoblastic cell line. A normal cellular adhesion and a marked orientation of the cell growth were observed over the CNT composites, with a proliferation/differentiation relationship favouring osteoblastic functional activity. These sintering strategies offer new insights into the sintering of electroconductive CNT containing bioactive ceramics with unlimited geometries for electrotherapy of the bone tissue.

Carbon nanotube-based bioceramic grafts for electrotherapy of bone

Bone complexity demands the engineering of new scaffolding solutions for its reconstructive surgery. Emerging bone grafts should offer not only mechanical support but also functional properties to explore innovative bone therapies. Following this, ceramic bone grafts of Glass/hydroxyapatite (HA) reinforced with conductive carbon nanotubes (CNTs) - CNT/Glass/HA - were prepared for bone electrotherapy purposes. Computer-aided 3D microstructural reconstructions and TEM analysis of CNT/Glass/HA composites provided details on the CNT 3D network and further correlation to their functional properties. CNTs are arranged as sub-micrometric sized ropes bridging homogenously distributed ellipsoid-shaped agglomerates. This arrangement yielded composites with a percolation threshold of pc=1.5vol.%. At 4.4vol.% of CNTs, thermal and electrical conductivities of 1.5W·m(-1)·K(-1) and 55S·m(-1), respectively, were obtained, matching relevant requisites in electrical stimulation protocols. While the former avoids bone damaging from Joules heat generation, the latter might allow the confinement of external electrical fields through the conductive material if used for in vivo electrical stimulation. Moreover, the electrically conductive bone grafts have better mechanical properties than those of the natural cortical bone. Overall, these highly conductive materials with controlled size CNT agglomerates might accelerate bone bonding and maximize the delivery of electrical stimulation during electrotherapy practices.

Hierarchically organized Li–Al-LDH nano-flakes: a low-temperature approach to seal porous anodic oxide on aluminum alloys

This work suggests a low-temperature sealing approach for tartaric–sulfuric acid (TSA) anodized AA2024 based on hierarchically organized Li–Al-layered double hydroxide (LDH) structures. The new proposed sealing is expected to be directly competitive to the standard hot water sealing (HWS) approaches because of its reduced treatment temperature and high protection efficiency. A hierarchical organization of in situ formed LDH nano-flakes across the depth length of the TSA pores, from the macrodown to the nano-size range, was observed with transmission electron microscopy (TEM). Electrochemical impedance spectroscopy (EIS) studies showed that the densely packed LDH arrangement at the porous oxide layer is directly related to the drastically improved barrier properties of TSA. Moreover, LDH flake-like structures worked as “smart” reservoirs for corrosion inhibiting vanadium species (VOx) that are released on demand upon the onset of corrosion. This was confirmed using a scanning vibrating electrode technique (SVET), giving relevant insights into the time-resolved release activity of VOx and the formation of the passivation layer on cathodic intermetallics, corroborated with EDX and analytical Raman spectroscopy. Passive and active corrosion protection was imparted to the anodic layer via new Li–Al-LDH structures with long-term protection exceeding that of standard HWS procedures.

Electrochemical deposition of Fe and Fe/CNTs composites from strongly alkaline hematite suspensions

Abstract Cathodic electrodeposition of Fe and Fe/CNTs composites from Fe2O3 suspensions in 10 M NaOH was reported for the first time. Triethanolamine (TEA) was used as an additive in the plating suspension and found to improve the morphology and adhesion of the deposits. TEA acted as an effective stabilizer for carbon nanotubes (CNTs) in strongly alkaline media and facilitated incorporation of CNTs into Fe matrix during the deposition, giving rise to Fe/CNTs composites. Current efficiency, microstructure, morphology of Fe deposits and Fe/CNTs composites as well as carbon content in Fe/CNTs revealed at different deposition conditions were determined.

ZnO micro/nanocrystals grown by laser assisted flow deposition

Laser assisted flow deposition (LAFD) is a very high yield method based on a vapor-solid mechanism, allowing the production of ZnO crystals in a very short time. The LAFD was used in the growth of different morphologies (nanoparticles, tetrapods and microrods) of ZnO micro/nanocrystals and their microstructural characterization confirms the excellent crystallinity of the wurtzite structure. The optical properties of the as-grown ZnO crystals investigated by low temperature photoluminescence (PL) evidence a well-structured near band edge emission (NBE) due to the recombination of free (FX), surface (SX) and donor bound (D0X) excitons. Among the most representative emission lines, the 3.31 eV transition was found to occur in the stacking faults-free microrods. The luminescence behavior observed in H passivated samples suggests a closer relationship between this optical center and the presence of surface states. Besides the unintentionally doped micro/nanocrystals, ZnO/Ag and ZnO/carbon nanotubes (CNT) hybrid structures were processed by LAFD. The former aims at the incorporation of silver as a p-type dopant and the latter envisaging photovoltaic applications. Silver-related spherical particles were found to be inhomogeneously distributed at the microrods surface, accumulating at the rods tips and promoting the ZnO nanorods re-nucleation. Despite the fact that energy dispersive X-ray measurements suggest that a fraction of the silver could be incorporated in the ZnO rods, no new related luminescence lines or bands were observed when compared with the as-grown samples. For the case of the ZnO/CNT composites two main approaches were adopted: i) a direct deposition of ZnO particles on the surface of vertically aligned multi-walled carbon nanotubes (VACNTs) forests without employing any additional catalyst and ii) new ZnO/CNT hybrids were developed as buckypaper nanocomposites. The use of the LAFD technique in the first approach preserves the CNTs structure and alignment and avoids the collapse of the VACNTs array, which is a major advantage of this method. On the other hand, LAFD grown ZnO nanoparticles and tetrapods were used to produce ZnO/CNT buckypaper nanocomposites. When compared with the as-grown samples the PL spectra of the composites structures behave differently. For the case of the ZnO/VACNTs no changes on the peak position and spectral shape were observed. Only an enhancement of the overall luminescence was found to occur. On contrary, for the buckypaper nanocomposites notable changes on the spectral shape and peak position were observed, likely due to distinct surface band bending effects for the ZnO nanoparticles and tetrapods embedded in the CNTs.

Ultra simple catalyst layer preparation for the growth of vertically aligned CNTs and CNT-based nanostructures

A simple and rapid route for the preparation of iron-based catalyst layers for CVD growth of carbon nanotubes is introduced. The catalyst was deposited by a microwave-assisted nonaqueous sol–gel process onto silicon wafers with or without an Al2O3 buffer layer and onto colloidal silica spheres. High quality vertically aligned carbon nanotube (VACNT) mats were grown on planar substrates. The versatility of the catalyst preparation is highlighted by the growth of CNTs onto non-planar surfaces such as the silica spheres.