Miquel Gimeno-Fabra

Instant MOFs: continuous synthesis of metal-organic frameworks by rapid solvent mixing.

A continuous flow reactor allows the preparation of porous metal-organic framework materials with crystallisation induced by rapid mixing of streams of preheated water and solutions of reagents in organic solvent: this gives high volume production (132 g h(-1)) with crystallite size of the products from nanoscale to micron.

The Rapid Size- and Shape-Controlled Continuous Hydrothermal Synthesis of Metal Sulphide Nanomaterials

Continuous flow hydrothermal synthesis offers a cheap, green and highly scalable route for the preparation of inorganic nanomaterials which has predominantly been applied to metal oxide based materials. In this work we report the first continuous flow hydrothermal synthesis of metal sulphide nanomaterials. A wide range of binary metal sulphides, ZnS, CdS, PbS, CuS, Fe(1-x)S and Bi2S3, have been synthesised. By varying the reaction conditions two different mechanisms may be invoked; a growth dominated route which permits the formation of nanostructured sulphide materials, and a nucleation driven process which produces nanoparticles with temperature dependent size control. This offers a new and industrially viable route to a wide range of metal sulphide nanoparticles with facile size and shape control.

In vitro degradation and mechanical properties of PLA-PCL copolymer unit cell scaffolds generated by two-photon polymerization.

The manufacture of 3D scaffolds with specific controlled porous architecture, defined microstructure and an adjustable degradation profile was achieved using two-photon polymerization (TPP) with a size of 2  ×  4  ×  2 mm(3). Scaffolds made from poly(D,L-lactide-co-ɛ-caprolactone) copolymer with varying lactic acid (LA) and ɛ -caprolactone (CL) ratios (LC16:4, 18:2 and 9:1) were generated via ring-opening-polymerization and photoactivation. The reactivity was quantified using photo-DSC, yielding a double bond conversion ranging from 70% to 90%. The pore sizes for all LC scaffolds were see 300 μm and throat sizes varied from 152 to 177 μm. In vitro degradation was conducted at different temperatures; 37, 50 and 65 °C. Change in compressive properties immersed at 37 °C over time was also measured. Variations in thermal, degradation and mechanical properties of the LC scaffolds were related to the LA/CL ratio. Scaffold LC16:4 showed significantly lower glass transition temperature (T g) (4.8 °C) in comparison with the LC 18:2 and 9:1 (see 32 °C). Rates of mass loss for the LC16:4 scaffolds at all temperatures were significantly lower than that for LC18:2 and 9:1. The degradation activation energies for scaffold materials ranged from 82.7 to 94.9 kJ mol(-1). A prediction for degradation time was applied through a correlation between long-term degradation studies at 37 °C and short-term studies at elevated temperatures (50 and 65 °C) using the half-life of mass loss (Time (M1/2)) parameter. However, the initial compressive moduli for LC18:2 and 9:1 scaffolds were 7 to 14 times higher than LC16:4 (see 0.27) which was suggested to be due to its higher CL content (20%). All scaffolds showed a gradual loss in their compressive strength and modulus over time as a result of progressive mass loss over time. The manufacturing process utilized and the scaffolds produced have potential for use in tissue engineering and regenerative medicine applications.

Combined release of platelet-rich plasma and 3D-mesenchymal stem cell encapsulation in alginate hydrogels modified by the presence of silica

We report the modified release of platelet-rich plasma from alginate platelet-rich plasma hydrogels altered by the presence of silica. These PRP–alginate–silica compositions can be used as injectable carriers for viable mesenchymal stem cells.

Continuous synthesis of dispersant-coated hydroxyapatite plates

A continuous flow hydrothermal synthetic route which allows the direct “in situ” capping/coating of hydroxyapatite nanoplates with functional dispersants in a single stage is reported. The methodology induced crystallisation by rapid mixing of streams of preheated water and solutions of reagents in water, whilst the hydrophobic surface modification of the HA platelets was achieved without morphological disruption. The effect of adding the hydrocarbon either before or after the HA platelet formation point has also been assessed, proving that the presence of surfactant at the reaction site does not interfere with the formation of HA and allows for a more efficient binding and extraction of the inorganic materials. The coupling mechanisms between the surfactant and the HA surface have been proposed to be a mixture of covalent and electrostatic interactions (i.e. all forms of chemisorption). This synthesis route is fully scalable to pilot (10 tons per year) and industrial (1000 tons per year) scales.

Assessing the life cycle environmental impacts of titania nanoparticle production by continuous flow solvo/hydrothermal syntheses

Continuous-flow hydrothermal and solvothermal syntheses offer substantial advantages over conventional processes, producing high quality materials from a wide range of precursors. In this study, we evaluate the “cradle-to-gate” life cycle environmental impacts of alternative titanium dioxide (TiO2) nanoparticle production parameters, considering a range of operational conditions, precursors, material properties and production capacities. A detailed characterisation of the nano-TiO2 products allows us, for the first time, to link key nanoparticle characteristics to production parameters and environmental impacts, providing a useful foundation for future studies evaluating nano-TiO2 applications. Five different titanium precursors are considered, ranging from simple inorganic precursors, like titanium oxysulphate (TiOS), to complex organic precursors such as titanium bis(ammonium-lactato)dihydroxide (TiBALD). Synthesis at the laboratory scale is used to determine the yield, size distribution, crystallinity and phase of the nanoparticles. The specifications and operating experience of a full scale plant (>1000 t per year) are used to estimate the mass and energy inputs of industrial scale production for the life cycle assessment. Overall, higher process temperatures are linked to larger, more crystalline nanoparticles and higher conversion rates. Precursor selection also influences nano-TiO2 properties: production from TiOS results in the largest particle sizes, while TiBALD achieves the smallest particles and narrowest size distribution. Precursor selection is the main factor in determining cradle-to-gate environmental impacts (>80% in some cases), due to the production impact of complex organic precursors. Nano-TiO2 production from TiOS shows the lowest global warming potential (GWP) (<12 kg CO2-eq. per kg TiO2) and cumulative energy demand (CED) (<149 MJ kg−1 TiO2) due to the low environmental impact of the precursor, the use of water as a solvent and its high yield even at lower temperatures. Conversely, the TiBALD precursor shows the highest impact (86 kg CO2-eq. per kg TiO2 and 1952 MJ kg−1 TiO2) due to the need for additional post-synthesis steps and complexity of precursor manufacturing. The main purpose of this study is not a direct comparison of the environmental impacts of TiO2 nanoparticles manufactured utilizing various precursors under different conditions, but to provide an essential foundation for future work evaluating potential applications of nano-TiO2 and their life cycle environmental impacts.

Degradation and Characterization of Resorbable Phosphate-Based Glass Thin-Film Coatings Applied by Radio-Frequency Magnetron Sputtering

Quinternary phosphate-based glasses of up to 2.67 μm, deposited by radio-frequency magnetron sputtering, were degraded in distilled water and phosphate-buffered saline (PBS) to investigate their degradation characteristics. Magnetron-sputtered coatings have been structurally compared to their compositionally equivalent melt-quenched bulk glass counterparts. The coatings were found to have structurally variable surfaces to melt-quenched glass such that the respective bridging oxygen to nonbridging oxygen bonds were 34.2% to 65.8% versus 20.5% to 79.5%, forming metaphosphate (PO3)(-) (Q(2)) versus less soluble (P2O7)(4-) (Q(1)) and (PO4)(3-) (Q(0)), respectively. This factor led to highly soluble coatings, exhibiting a t(1/2) degradation dependence in the first 2 h in distilled water, followed by a more characteristic linear profile because the subsequent layers were less soluble. Degradation was observed to preferentially occur, forming voids characteristic of pitting corrosion, which was confirmed by the use of a focused ion beam. Coating degradation in PBS precipitated a (PO3)(-) metaphosphate, an X-ray amorphous layer, which remained adherent to the substrate and seemingly formed a protective diffusion barrier, which inhibited further coating degradation. The implications are that while compositionally similar, sputter-deposited coatings and melt-quenched glasses are structurally dissimilar, most notably, with regard to the surface layer. This factor has been attributed to surface etching of the as-deposited coating layer during deposition and variation in the thermal history between the processes of magnetron sputtering and melt quenching.

Organic semiconductors with a charge carrier life time of over 2 hours at room temperature

Recently, Gao et al. reported being able to measure significant quantities of photogenerated charge up to one hour after it had been generated in an organic semiconductor device. The aim of this paper is twofold; (a) to provide conclusive experimental evidence to support the picture of device operation; and (b) to understand and demonstrate how changes to the device structure and materials can be used to tune the charge carrier lifetime. By tuning both the materials used, and the device structure we are able to observe a charge carrier life time of over 2 hours and still extract significant amounts of charge from the device after 5 hours. This is achieved by engineering the band structure of the device to control the spatial overlap of the stored photoexcited electron and hole populations and thus the recombination rate. By performing lifetime measurements as a function of charge carrier density and applied voltage we find the recombination rate has a 0th order dependence on carrier density, and elucidate the mechanisms responsible for these long charge carrier life times. This work is of technological significance for the development of organic electronic high sensitivity photodetectors and memory elements.

Design of electrical system for racing electric motorcycles

The electric motorcycle recently constructed at The University of Nottingham is considered to be a high performance vehicle, competing with its internal combustion engine driven counterparts. This paper presents pertinent design decisions taken to maximise the vehicle performance in race conditions, along with modelling undertaken to gain an insight into the system interaction as a whole. Readings recorded from races are presented to support the described simulation work.