Arc-discharge synthesis of iron encapsulated in carbon nanoparticles for biomedical applications

The objective of the present work is to improve the protection against the oxidation that usually appears in core@shell nanoparticles. Spherical iron nanoparticles coated with a carbon shell were obtained by a modified arc-discharge reactor, which permits controlling the diameter of the iron core and the carbon shell of the particles. Oxidized iron nanoparticles involve a loss of the magnetic characteristics and also changes in the chemical properties. Our nanoparticles show superparamagnetic behavior and high magnetic saturation owing to the high purity α-Fe of core and to the high core sealing, provided by the carbon shell. A liquid iron precursor was injected in the plasma spot dragged by an inert gas flow. A fixed arc-discharge current of 40 A was used to secure a stable discharge, and several samples were produced at different conditions. Transmission electron microscopy indicated an iron core diameter between 5 and 9 nm. Selected area electron diffraction provided evidences of a highly crystalline and dense iron core. The magnetic properties were studied up to 5 K temperature using a superconducting quantum interference device. The results reveal a superparamagnetic behaviour, a narrow size distribution (), and an average diameter of 6 nm for nanoparticles having a blocking temperature near 40 K

Morphological and Magnetic Properties of Superparamagnetic Carbon-Coated Fe Nanoparticles Produced by Arc Discharge.

Spherical carbon coated iron particles of nanometric diameter in the 5-10 nm range have been produced by arc discharge at near-atmospheric pressure conditions (using 5-8·10 4 Pa of He). The particles exhibit a crystalline dense iron core with an average diameter 7.4 ± 2.0 nm surrounded by a sealed carbon shell, shown by transmission electron microscopy (TEM), selected-area diffrac- tion (SAED), energy-dispersive X-ray analysis (STEM-EDX) and electron energy loss spectroscopy (EELS). The SAED, EDX and EELS results indicate a lack of traces of core oxidized phases showing an efficient protection role of the carbon shell. The magnetic properties of the nanoparticles have been investigated in the 5-300 K temperature range using a superconducting quantum interference device (SQUID). The results reveal a superparamagnetic behaviour with an average monodomain diameter of 7.6 nm of the nanoparticles. The zero field cooled and field cooled (ZFC-FC)magnetization curves show a blocking temperature (TB)at room temperature very suitable for biomedical applications (drug delivery, magnetic resonance imaging-MRI-, hyperthermia)

Embroidered Copper Microwire Current Collector for Improved Cycling Performance of Silicon Anodes in Lithium-Ion Batteries

Si holds great promise as an alloying anode material for Li-ion batteries with improved energy density because of its high theoretical specific capacity and favorable operation voltage range. However, the large volume expansion of Si during electrochemical reaction with Li and the associated adverse effects strongly limit its prospect for application. Here, we report on the use of three-dimensional instead of flat current collectors for high-capacity Si anodes in an attempt to mitigate the loss of electrical contact of active electrode regions as a result of structural disintegration with cycling. The current collectors were produced by technical embroidery and consist of interconnected Cu wires of diameter <150 µm. In comparison to Si/Li cells using a conventional Cu foil current collector, the embroidered microwire network-based cells show much enhanced capacity and reversibility due to a higher degree of tolerance to cycling

Production and characterisation of carbon-encapsulated iron nanoparticles by arc-discharge plasma

El text de la “Part III – Results” ha estat retirat seguint instruccions de l’autora de la tesi, en existir participació d’empreses, existir conveni de confidencialitat o existeix la possibilitat de generar patents / The text of this chapter (“Part III – Results”) has been withdrawn on the instructions of the author, as there is participation of undertakings, confidentiality agreement or the ability to generate patent[eng] Carbon-encapsulated iron nanoparticles have being researched heavily, since they present advantageous properties over other protective coatings such as polymer or silica. The carbon coating protects the iron core from oxidation, chemical and thermal degradation and hence, magnetic cores present stable magnetic properties when nanoparticles are exhibited in air or other environments. Several studies about carbon-encapsulated magnetic nanoparticles were already reported. However, nanoparticles are obtained rather polydisperse and not very uniform in composition, making very difficult their use for several applications. The aim of this thesis is the production and characterisation of carbon-encapsulated iron nanoparticles showing very narrow size distributions with well-characterised magnetic properties for several applications, in particular, those related to the biomedical field (hyperthermia, drug delivery or as agents contrast in MRI). However, the systematic study of these applications was not the framework of this thesis. The content of this dissertation comprises the design of two arc-discharge plasma (ADP) reactors (a conventional and a modified one); the experimental study of the different reactor parameters involved; the morphological, structural and magnetic characterisation of the obtained nanoparticles; the comprehension of the mechanisms involve in the formation of this kind of nanoparticles in comparison with nanoparticles obtained by other methods; and finally, a first approach to the functionalisation of the nanoparticles for the biomedical applications. This thesis is structured in four parts: Backgrounds (Chapter 1), Nanotools (Chapter 2 and Chapter 3), Results (from Chapter 4 to Chapter 8) and finally, the Conclusions. Chapter 1 - Basis of carbon-encapsulated iron nanoparticles: A general introduction of the nanoparticle properties derived from their nanometric dimensions is presented in this chapter. The state of the art about the formation mechanisms and techniques used for the generation of carbon-encapsulated iron nanoparticles is described. Several applications of this kind of nanoparticles in fields such as biomedicine, electronics or food and environmental, are also presented. Chapter 2 - Characterisation methods: The most common characterisation techniques used to investigate the morphological, composition, structural and magnetic properties are described within this chapter. Details about the equipments and conditions used during this thesis for the characterisation of the nanoparticles are also reported. Chapter 3 - Experimental set-up: In this chapter, the description of two different arc-discharge reactors used during this thesis is presented. A first reactor (the conventional ADP) was developed by following similar experimental setups described in the literature. Second reactor (a modified ADP) was designed to overcome the disadvantages from the first reactor and to obtain high quality nanoparticles (narrower size distribution, uniform composition). Chapter 4 - Preliminary studies from conventional ADP reactor: This chapter presents a design of experiments (DOE) based on the Plackett-Burman design in order to evaluate the reactor parameters that influence the most the final characteristics of the nanoparticles. The study was performed using the conventional ADP reactor and the preliminary results were very useful for the development of next generation of experiments using the second reactor, the modified ADP. Chapter 5 - Generation of nanoparticles by a modified ADP reactor: Morphological and structural properties of the nanoparticles obtained by the modified ADP reactor are presented. The discussion of the effect of the most relevant parameters on the formation of the nanoparticles was reported. Iron core diameters with corresponding size distribution as well as the carbon shell formation obtained under different parameter conditions were investigated. Chapter 6 - Magnetic properties of the nanoparticles: A systematic study of the magnetic properties of the nanoparticles obtained in Chapter 5 is performed. Size-dependent variables such as magnetic moments, coercivity values, blocking temperature and anisotropy energies were presented. Magnetic properties were in agreement with the morphological characteristics of the nanoparticles. Chapter 7 – Thermally induced structural evolution of the nanoparticles: The comparison of annealed nanoparticles obtained by mADP and chemical vapour deposition (CVD) method is presented in this chapter. Differences on the morphological, structural and magnetic properties were studied. Structural evolution of nanoparticles during annealing under in-situ TEM observations was investigated. Chapter 8 - First approach to biomedical applications: As a first approach to biomedical applications, the stabilisation of the nanoparticles in aqueous solution by using polyvinyl-alcohol was investigated. Results of the internalisation of the nanoparticles into HeLa cells are presented.[cat] Les nanopartícules magnètiques de ferro recobertes de carboni s’estan investigant en gran mesura, ja que presenten avantatjoses propietats sobre d’altres recobriments protectors del nucli magnètic com els polímers o la sílice. El recobriment de carboni protegeix el nucli de ferro de l’oxidació, la degració química i tèrmica, d’aquesta manera els nuclis presenten propietats magnètiques estables quan les nanopartícules s’exhibeixen en aire o en un altre medi. S’han realitzat diversos estudis sobre aquest tipus de nanopartícules, però aquest tipus de nanopartícules s’obtenen amb gran dispersió de grandàries i poca uniformitat en les seves característiques. És encara un repte en aquest camp la producció de nanopartícules de ferro recobertes de carbon amb propietats morfològiques i estructurals, així com l’estudi sistemàtic de les seves propietats magnètiques. Per aquest motiu, l’objectiu d’aquesta tesi es centra en la producció i caracterització de nanopartícules superparamagnètiques de ferro recobertes de carboni amb estreta distribució de mides i amb propietats magnètiques ben caracteritzades per diverses aplicacions, en particular, les relacionades amb el camp de la biomedicina. No obstant això, l’estudi sistemàtic d’aquestes aplicacions es troba fora del marc d’aquesta tesi. El contingut s’estructura en quatre parts: • La primera part d’introducció conté els aspectos bàsics sobre aquest tipus de nanopartícules, així com les propietats derivades de la seva mida nanomètrica, les tecnologies que s’utilitzen per generar aquest tipus de nanopartícules, una explicació sobre els possibles mecanismes responsables de la seva formació i les principals aplicacions d’aquestes nanopartícules. • La segona part descriu les tècniques utilitzades per la seva caracterització que engloben tècniques de microscopia, de difracció de raigs-X, d’espectroscòpia Raman, per la caracterització col•loidal de les nanopartícules fins la seva caracterització magnètica. També inclou la descripció detallada dels equips basats en la descàrrega d’arc utilitzats per la seva producció. El primer equip es va dissenyar seguint les característiques d’un reactor convencional (conventional ADP reactor). El segon equip basat en la mateixa tecnologia de descàrrega d’arc, però modificat (mADP reactor) i dissenyat especialment amb l’objectiu de millorar les característiques del producte final. • La tercera part exposa els resultats obtinguts durant aquesta tesi. L’estudi previ del reactor convencional basat en un disseny d’experiments de Plackett-Burman per avaluar l’efecte dels diferents paràmetres del reactor en la grandària dels nuclis de ferro. A partir d’aquest estudi, es va realitzar un estudi més específic en el nou reactor modificat on es van estudiar l’efecte del corrent d’arc utilizat, la velocitat del flux d’heli i el contigut de ferrocè com a matèria prima del ferro. Després es va realitzar l’estudi sistemàtic de les seves propietats magnètiques observant la dependència d’aquestes propietats amb la grandària dels nuclis de ferro. A continuació, es va presentar la comparació d’aquestes nanopartícules amb d’altres obtingudes mitjantçant el mètode de dipòsit químic en fase vapor (CVD). A partir d’aquesta comparació es va estudiar l’evolució estructural d’aquestes nanopartícules sotmetes a un tractament tèrmic en observació in-situ d’un microscopi de transmissió electrònica. Finalment, es va presentar un primer estudi de les propietats col•loidals en suspensió d’aquestes nanopartícules recobertes amb un polímer d’alcohol de polivinil (PVA). Es presenta un primer estudi de l’internalització d’aquestes nanopartícules en cèl•lules tumorals HeLa. • Per acabar es presenten les conclusions i l’apèndix que conté informació sobre les mostres produïdes i un llistat de publicacions, congressos, patents resultants d’aquest treball

Arc-discharge synthesis of iron encapsulated in carbon nanoparticles for biomedical applications

The objective of the present work is to improve the protection against the oxidation that usually appears in core@shell nanoparticles. Spherical iron nanoparticles coated with a carbon shell were obtained by a modified arc-discharge reactor, which permits controlling the diameter of the iron core and the carbon shell of the particles. Oxidized iron nanoparticles involve a loss of the magnetic characteristics and also changes in the chemical properties. Our nanoparticles show superparamagnetic behavior and high magnetic saturation owing to the high purity α-Fe of core and to the high core sealing, provided by the carbon shell. A liquid iron precursor was injected in the plasma spot dragged by an inert gas flow. A fixed arc-discharge current of 40 A was used to secure a stable discharge, and several samples were produced at different conditions. Transmission electron microscopy indicated an iron core diameter between 5 and 9 nm. Selected area electron diffraction provided evidences of a highly crystalline and dense iron core. The magnetic properties were studied up to 5 K temperature using a superconducting quantum interference device. The results reveal a superparamagnetic behaviour, a narrow size distribution (), and an average diameter of 6 nm for nanoparticles having a blocking temperature near 40 K

Size Control of Carbon Encapsulated Iron Nanoparticles by Arc Discharge Plasma Method

Size control of core@shell nanostructures is still a challenge. Carbon encapsulated iron nanoparticles (CEINPs) were synthesized by arc discharge plasma method in this study. CEINPs size can be controlled by varying gas composition, due to change in plasma properties. The morphology and structural features were investigated using scanning electron microscopy, transmission electron microscopy (TEM) and high-resolution TEM. Magnetic properties were studied to confirm the changes in CEINPs size by using superconducting quantum interference device. In order to evaluate the carbon shell protection and ensure the absence of iron oxide, selected area electron diffraction technique, energy-dispersive x-ray spectroscopy and electron energy loss spectroscopy were employed. Moreover, the degree of carbon order–disorder was studied by Raman Spectroscopy. It was concluded that arc discharge method is a suitable technique for precise size control of CEINPs

New Three-Dimensional Porous Electrode Concept: Vertically-Aligned Carbon Nanotubes Directly Grown on Embroidered Copper Structures

New three-dimensional (3D) porous electrode concepts are required to overcome limitations in Li-ion batteries in terms of morphology (e.g., shapes, dimensions), mechanical stability (e.g., flexibility, high electroactive mass loadings), and electrochemical performance (e.g., low volumetric energy densities and rate capabilities). Here a new electrode concept is introduced based on the direct growth of vertically-aligned carbon nanotubes (VA-CNTs) on embroidered Cu current collectors. The direct growth of VA-CNTs was achieved by plasma-enhanced chemical vapor deposition (PECVD), and there was no application of any post-treatment or cleaning procedure. The electrochemical behavior of the as-grown VA-CNTs was analyzed by charge/discharge cycles at different specific currents and with electrochemical impedance spectroscopy (EIS) measurements. The results were compared with values found in the literature. The as-grown VA-CNTs exhibit higher specific capacities than graphite and pristine VA-CNTs found in the literature. This together with the possibilities that the Cu embroidered structures offer in terms of specific surface area, total surface area, and designs provide a breakthrough in new 3D electrode concepts

Water-based slurries for high-energy LiFePO4 batteries using embroidered current collectors

Greater specific energy densities in lithium-ion batteries can be achieved by using three-dimensional (3D) porous current collectors, which allow for greater areal mass loadings of the electroactive material. In this paper, we present the use of embroidered current collectors for the preparation of thick, pouch-type Li-ion batteries. Experiments were performed on LiFePO 4 (LFP) water-based slurries using styrene-butadiene rubber (SBR) as binder and sodium carboxymethyl cellulose (CMC) as thickener, and formulations of different rheological characteristics were investigated. The electrochemical performance (cyclic voltammetry, rate capability) and morphological characteristics of the LFP half-pouch cells (X-ray micro computed tomography and scanning electron microscopy) were compared between the formulations. An optimum electrode formulation was identified, and a mechanism is proposed to explain differences between the formulations. With the optimum electrode formulation, 350 µm casted electrodes with high mechanical stability were achieved. Electrodes exhibited 4–6 times greater areal mass loadings (4–6 mAh cm −2 ) and 50% greater electroactive material weight than with foils. In tests of half- and full-pouch embroidered cells, a 50% capacity utilization at 1C-rate and 11% at 2C-rate were observed, with a full recovery at C/5-rate. The cycling stability was also maintained over 55 cycles

Arc-discharge synthesis of iron encapsulated in carbon nanoparticles for biomedical applications

The objective of the present work is to improve the protection against the oxidation that usually appears in core@shell nanoparticles. Spherical iron nanoparticles coated with a carbon shell were obtained by a modified arc-discharge reactor, which permits controlling the diameter of the iron core and the carbon shell of the particles. Oxidized iron nanoparticles involve a loss of the magnetic characteristics and also changes in the chemical properties. Our nanoparticles show superparamagnetic behavior and high magnetic saturation owing to the high purity α-Fe of core and to the high core sealing, provided by the carbon shell. A liquid iron precursor was injected in the plasma spot dragged by an inert gas flow. A fixed arc-discharge current of 40 A was used to secure a stable discharge, and several samples were produced at different conditions. Transmission electron microscopy indicated an iron core diameter between 5 and 9 nm. Selected area electron diffraction provided evidences of a highly crystalline and dense iron core. The magnetic properties were studied up to 5 K temperature using a superconducting quantum interference device. The results reveal a superparamagnetic behaviour, a narrow size distribution (), and an average diameter of 6 nm for nanoparticles having a blocking temperature near 40 K

New three-dimensional porous electrode concept: vertically-aligned carbon nanotubes directly grown on embroidered copper structures

New three-dimensional (3D) porous electrode concepts are required to overcome limitations in Li-ion batteries in terms of morphology (e.g., shapes, dimensions), mechanical stability (e.g., flexibility, high electroactive mass loadings), and electrochemical performance (e.g., low volumetric energy densities and rate capabilities). Here a new electrode concept is introduced based on the direct growth of vertically-aligned carbon nanotubes (VA-CNTs) on embroidered Cu current collectors. The direct growth of VA-CNTs was achieved by plasma-enhanced chemical vapor deposition (PECVD), and there was no application of any post-treatment or cleaning procedure. The electrochemical behavior of the as-grown VA-CNTs was analyzed by charge/discharge cycles at different specific currents and with electrochemical impedance spectroscopy (EIS) measurements. The results were compared with values found in the literature. The as-grown VA-CNTs exhibit higher specific capacities than graphite and pristine VA-CNTs found in the literature. This together with the possibilities that the Cu embroidered structures offer in terms of specific surface area, total surface area, and designs provide a breakthrough in new 3D electrode concep