Risk assessment in a research laboratory during sol–gel synthesis of nano-TiO2

The occupational risks in the nanotechnology research laboratories are an important topic since a great number of researchers are involved in this area. The risk assessment performed by both qualitative and quantitative methods is a necessary step for the management of the occupational risks. Risk assessment could be performed by qualitative methods that gather consensus in the scientific community. It is also possible to use quantitative methods, based in different technics and metrics, as indicative exposure limits are been settled by several institutions. While performing the risk assessment, the information on the materials used is very important and, if it is not updated, it could create a bias in the assessment results. The exposure to TiO2 nanoparticles risk was assessed in a research laboratory using a quantitative exposure method and qualitative risk assessment methods. It was found the results from direct-reading Condensation Particle Counter (CPC) equipment and the CB Nanotool seem to be related and aligned, while the results obtained from the use of the Stoffenmanager Nano seem to indicate a higher risk level.

Tailored magnetic and magnetoelectric responses of polymer-based composites

The manipulation of electric ordering with applied magnetic fields has been realized on magnetoelectric (ME) materials, however, their ME switching is often accompanied by significant hysteresis and coercivity that represents, for some applications, a severe weakness. To overcome this obstacle, this work focus on the development of a new type of ME polymer nanocomposites that exhibits tailored ME response at room temperature. The multiferroic nanocomposites are based on three different ferrite nanoparticles, Zn0.2Mn0.8Fe2O4 (ZMFO), CoFe2O4 (CFO) and Fe3O4 (FO), dispersed in a piezoelectric co-polymer poly(vinylindene fluoride-trifluoroethylene), P(VDF-TrFE), matrix. No substantial differences were detected on the time-stable piezoelectric response of the composites (≈ -28 pC.N−1) with distinct ferrite fillers and for the same ferrite content of 10wt.%. Magnetic hysteresis loops from pure ferrite nanopowders showed different magnetic responses. ME results of the nanocomposite films with 10wt.% ferrite content revealed that the ME induced voltage increases with increasing DC magnetic field until a maximum of 6.5 mV∙cm−1∙Oe−1, at an optimum magnetic field of 0.26 T, and 0.8 mV∙cm−1∙Oe−1, at an optimum magnetic field of 0.15T, for the CFO/P(VDF-TrFE) and FO/P(VDF-TrFE) composites, respectively. On the contrary, the ME response of the ZMFO/P(VDF-TrFE) exposed no hysteresis and high dependence on the ZMFO filler content. Possible innovative applications such as memories and information storage, signal processing, ME sensors and oscillators have been addressed for such ferrite/PVDF nanocomposites.

Synthesis, physical and magnetic properties of BaFe12O19/P(VDF-TrFE) multifunctional composites

Composite films with filler microparticles of Barium ferrite dispersed within P(VDF-TrFE) as polymeric matrix have been prepared by solvent evaporation. The lowest BaFO content of 1% wt acts as a small defect within the polymeric matrix, reducing the values of the dielectric and mechanical properties of the pure P(VDF-TrFE). For filler contents up to a 20%, the BaFO filler reinforces the matrix and measured properties increase their values. This trend is not followed by the electrical conductivity. We extended the study to fibers composed by BaFe12O19 microparticles in a PVDF matrix. Due to the big size of BaFO particles (1 micron in diameter), proper fabrication of the fiber shaped composites has not been achieved. We found that true BaFO content are always lower than nominal ones. Results are discussed in terms of the influence of size and morphology of the BaFO particles on the initial properties of the polymeric matrix.

One-step in situ synthesis of polyamide microcapsules with inorganic payload and their transformation into responsive thermoplastic composite materials

Well-dispersed loads of finely powdered metals, metal oxides, several carbon allotropes or nanoclays are incorporated into highly porous polyamide 6 microcapsules in controllable amounts via an original one-step in situ fabrication technique. It is based on activated anionic polymerization (AAP) of ε-caprolactam in a hydrocarbon solvent performed in the presence of the respective micro- or nanosized loads. The forming microcapsules with typical diameters of 25-50 µm entrap up to 40 wt% of load. Their melt processing produces hybrid thermoplastic composites. Mechanical, electric conductivity and magnetic response measurements show that transforming of in situ loaded microcapsules into composites by melt processing (MP) is a facile and rapid method to fabricate materials with high mechanical resistance and electro-magnetic characteristics sufficient for many industrial applications. This novel concept requires low polymerization temperatures, no functionalization or compatibilization of the loads and it is easy to scale up at industrial production levels.

Concrete with triphasic conductive materials for self-monitoring of cracking development subjected to flexure

In this study, the macro steel fiber (SF), carbon fiber (CF) and nano carbon black (NCB) as triphasic conductive materials were added into concrete, in order to improve the conductivity and ductility of concrete. The influence of NCB, SF and CF on the post crack behavior and conductivity of concrete was explored. The effect of the triphasic conductive materials on the self-diagnosing ability to the load–deflection property and crack widening of conductive concrete member subjected to bending were investigated. The relationship between the fractional change in surface impedance (FCR) and the crack opening displacement (COD) of concrete beams with conductive materials has been established. The results illustrated that there is a linear relationship between COD and FCR.

An experimental investigation on nano-TiO2 and fly ash based high performance concrete

High performance concrete (HPC) offers several advantages over normal-strength concrete, namely, high mechanical strength and high durability. Therefore, HPC allows for concrete structures with less steel reinforcement and a longer service life, both of which are crucial issues in the eco-efficiency of construction materials. Nevertheless international publications on the field of concrete containing nanoparticles are scarce when compared to Portland cement concrete (around 1%) of the total international publications. HPC nanoparticle-based publications are even scarcer. This article presents the results of an experimental investigation on the mechanical properties and durability of HPC based on nano-TiO2 and fly ash. The durability performance was assessed by means of water absorption by immersion, water absorption by capillarity, ultrasonic pulse velocity, electric resistivity, chloride diffusion and resistance to sulphuric acid attack. The results show that the concretes containing an increased content of nano-TiO2 show decreased durability performance. The results also show that concrete with 1% nano-TiO2 and 30% fly ash as Portland cement replacement show a high mechanical strength (C55/C67) and a high durability. However, it should be noted that the cost of nano-TiO2 is responsible for a severe increase in the cost of concrete mixtures.

Optimization of magnetoelectric composites based on electroactive polymers for energy harvesting and sensor application

Tese de Doutoramento em Engenharia de Materiais.

Síntesis y Caracterización de Materiales Nanoestructurados para el Almacenamiento de Hidrógeno. Hidrogen storage: Synthesis and characterization of nanostructured materials.

El hidrógeno tiene, actualmente, una atención considerable por su posible uso como combustible limpio y otros usos industriales y se ha demostrado que es posible hacer funcionar motores de combustión interna, por lo tanto es una alternativa viable respecto de fuentes de energía no renovables como el petróleo y tal vez sea en el futuro la tecnología más prometedora para reducir la contaminación, conservando el suministro de combustibles fósiles. Uno de los principales problemas para la utilización del hidrógeno como combustible es el del almacenamiento para que pueda ser seguro y transportable con todos los riesgos que esto supone. En este sentido el estudio de la adsorción de polímeros conductores (tal como polianilina, PANI o polipirrol PPy) y su posterior polimerización sobre hospedajes como aluminosilicatos meso y microporosos y carbones mesoporosos, es de suma importancia por sus propiedades para el almacenamiento de H2. El objetivo general de este proyecto es Investigar el almacenamiento de hidrógeno en nuevos composites nano/microestructurados. La síntesis de materiales micro/mesoporosos (MFI, MEL, BEA, L, MS41, SBA-15, SBA-1, SBA-3, SBA-16, CMK-3) para usos como hospedaje se realizan por sol-gel o síntesis hidrotérmica y se modificarán con TiO2, CeO2, ZrO2 y eventualmente con Ir, Ni, Zr. Muestras de estos hospedajes serán expuestos a vapores del monómero puro (anilina o pirrol). Luego se polimerizarán por polimerización oxidativa. Los nanocomposites sintetizados se caracterizarán por XRD, FTIR, DSC, TGA, SEM, TEM, EXFAS, XANES, UV-Vis. La adsorción de hidrógeno sobre los composites se llevará a cabo en un Reactor Parr, desde presiones atmosféricas y a altas presiones y varias temperaturas de adsorción . Los estudios de desorción de hidrogeno se llevarán a cabo en un equipo Chemisorb Micrometrics y se realizarán estudios termogravimétricos y de capacidad de retención de Hidrogeno por el nanocomposite. La importancia del estudio de este proceso tiene importantes implicancias económicas y sociales que serán preponderantes en el futuro debido a las cada vez más exigentes regulaciones ambientales. Además se contribuirá al avance del conocimiento científico, ya que es posible diseñar nuevos materiales, los que además permitirán generar reservorios de H2 con alta eficiencia. Por lo consiguiente: - Se desarrollarán nuevos materiales nanoestructurados, micro y mesoporosos y nanoclusters de especies activas en los hospedajes como así también la inclusión de polímeros (PANI, PPy) dentro de los canales de estos materiales. - Se caracterizarán estos materiales por métodos espectroscópicos (fisicoquímica de superficie). - Se estudiará la adsorción /absorcion de H2 en los nuevos materiales desarrollados. -Se aplicarán métodos de diseño de experimento (RDS), para optimizar el proceso de almacenamiento de H2, nivel de interacción de variables sinérgicas o colinérgicas.

Preparació de materials híbrids orgànico-inorgànics a partir de sals d'imidazoli

Estudi elaborat a partir d’una estada a l’ Ecole Nationale Supérieure de Chimie de Montpellier, França, durant 2006. S’han sintetitzat materials híbrids orgànico-inorgànics mitjançant el procés sol-gel i altres estratègies sintètiques. En alguns casos, s’ha intentat estructurar aquests materials, ja sigui per autoestructuració o per mitjà de tensioactius. Com a catalitzadors de les reaccions d'hidròlisi i policondensació s’han utilitzat àcids, bases i fluorurs. Els materials obtinguts s’han caracteritzat mitjançant diferents tècniques: BET (Brunauer-Emmett-Teller), TEM (microscopia electrònica de transmissió), SEM (microscòpia electrònica de rastreig), raigs X en pols , IR i RMN (ressonància magnètica nuclear) en estat sòlid. Amb aquests materials es pretén preparar catalitzadors heterogenis de Pd per reaccions d’acoblament creuat, i de Ru per reaccions de metàtesi. També s’han sintetitzat sals d'imidazoli amb cadenes hidrocarbonades llargues amb l'objectiu de preparar gels de sílice amb aquestes molècules atrapades dins la matriu inorgànica. Aquests materials s’utilitzaran com a organocatalitzadors i també es prepararan els corresponents catalitzadors de Pd per reaccions de Heck, Suzuki i Sonogashira. Les sals d’imidazoli s’han utilitzat com a tensioactius en la preparació de gels de sílice estructurats. Aquestes molècules han resultat ser cristalls líquids i s’han caracteritzar mitjançant DSC (differential scanning calorimetry), microscopia òptica i raigs X.

Direct magnetic resonance arthrography of the wrist with axial traction: A feasibility study to assess joint cartilage.

PURPOSE: To assess the impact of axial traction during acquisition of direct magnetic resonance (MR) arthrography of the wrist with regard to joint space width and amount of contrast material between the opposing cartilage surfaces. MATERIALS AND METHODS: Fifteen consecutive patients (12 male, mean age 38.1 years) were included in this Institutional Review Board-approved prospective study. Three-compartment wrist MR arthrographies were performed between October and December 2009 on a 3 T unit using a fat-suppressed T1-weighted isotropic high-resolution volumetric interpolated breathhold examination (VIBE) sequence in the coronal plane, with and without axial traction (3 kg). Two radiologists measured radiocarpal (radioscaphoid, radiolunate) and midcarpal (lunocapitate, hamatolunate) joint space widths, with and without traction, and assessed the amount of contrast material between the opposing cartilage surfaces using a three-point scale: 0 = absence, 1 = partial, 2 = complete. RESULTS: With traction, joint space width increased significantly at the radioscaphoid (Delta = 0.78 mm, P < 0.01), radiolunate (Delta = 0.18 mm, P < 0.01), and lunocapitate (Delta = 0.45 mm, P < 0.01) spaces, and both observers detected significantly more contrast material between the cartilage surfaces. At the hamatolunate space, the differences in joint space width (Delta = 0.14 mm, P = 0.54) and amount of contrast material were not significant. CONCLUSION: Direct wrist MR arthrography with axial traction of 3 kg increases joint space width at the radiocarpal and lunocapitate spaces, and prompts better coverage of the articular cartilage by the contrast material. J. Magn. Reson. Imaging 2011;. (c) 2011 Wiley-Liss, Inc.

Magnetic resonance-guided, real-time targeted delivery and imaging of magnetocapsules immunoprotecting pancreatic islet cells.

In type I diabetes mellitus, islet transplantation provides a moment-to-moment fine regulation of insulin. Success rates vary widely, however, necessitating suitable methods to monitor islet delivery, engraftment and survival. Here magnetic resonance-trackable magnetocapsules have been used simultaneously to immunoprotect pancreatic beta-cells and to monitor, non-invasively in real-time, hepatic delivery and engraftment by magnetic resonance imaging (MRI). Magnetocapsules were detected as single capsules with an altered magnetic resonance appearance on capsule rupture. Magnetocapsules were functional in vivo because mouse beta-cells restored normal glycemia in streptozotocin-induced diabetic mice and human islets induced sustained C-peptide levels in swine. In this large-animal model, magnetocapsules could be precisely targeted for infusion by using magnetic resonance fluoroscopy, whereas MRI facilitated monitoring of liver engraftment over time. These findings are directly applicable to ongoing improvements in islet cell transplantation for human diabetes, particularly because our magnetocapsules comprise clinically applicable materials.

High-field (3T) magnetic resonance defecography with functional assessment of the evacuation phase : a pictorial essay : P10

Purpose: Dynamic high-field magnetic resonance (MR) defecography including the evacuation phase is a promising tool for the assessment of functional pelvic disorders, nowadays seen with increasing frequency in elderly women in particular. Learning objectives: 1. To describe the adequate technique of dynamic high-field MRI (3T) in assessing pelvic floor disorders. 2. To provide an overview of the most common pathologies occurring during the evacuation phase, especially in comparison with results of conventional defecography. Methods and materials: After description of the ideal technical parameters of MR defecography performed in supine position after gel rectal filling with a 3 Tesla unit and including the evacuation phase we stress the importance of using a standardized evaluation system for the exact assessment of pelvic floor pathophysiology. Results: The typical pelvic floor disorders occurring before and/or during the evacuation phase, such as sphincter insufficiency, vaginal vault and/or uterine prolapse, cystourethrocele, peritoneo-/ entero-/ sigmoïdocele or rectal prolapse, are demonstrated. The difference between the terms "pelvic floor descent" and "pelvic floor relaxation" are pictorially outlined. MR results are compared with these of conventional defecography. Conclusion: Exact knowledge about the correct technique including the evacuation phase and the use of a standardized evaluation system in assessing pelvic floor disorders by dynamic high-field MRI is mandatory for accurate and reproducible diagnosis.

Optimization of spatial resolution for peripheral magnetic resonance angiography.

RATIONALE AND OBJECTIVES: To determine optimum spatial resolution when imaging peripheral arteries with magnetic resonance angiography (MRA). MATERIALS AND METHODS: Eight vessel diameters ranging from 1.0 to 8.0 mm were simulated in a vascular phantom. A total of 40 three-dimensional flash MRA sequences were acquired with incremental variations of fields of view, matrix size, and slice thickness. The accurately known eight diameters were combined pairwise to generate 22 "exact" degrees of stenosis ranging from 42% to 87%. Then, the diameters were measured in the MRA images by three independent observers and with quantitative angiography (QA) software and used to compute the degrees of stenosis corresponding to the 22 "exact" ones. The accuracy and reproducibility of vessel diameter measurements and stenosis calculations were assessed for vessel size ranging from 6 to 8 mm (iliac artery), 4 to 5 mm (femoro-popliteal arteries), and 1 to 3 mm (infrapopliteal arteries). Maximum pixel dimension and slice thickness to obtain a mean error in stenosis evaluation of less than 10% were determined by linear regression analysis. RESULTS: Mean errors on stenosis quantification were 8.8% +/- 6.3% for 6- to 8-mm vessels, 15.5% +/- 8.2% for 4- to 5-mm vessels, and 18.9% +/- 7.5% for 1- to 3-mm vessels. Mean errors on stenosis calculation were 12.3% +/- 8.2% for observers and 11.4% +/- 15.1% for QA software (P = .0342). To evaluate stenosis with a mean error of less than 10%, maximum pixel surface, the pixel size in the phase direction, and the slice thickness should be less than 1.56 mm2, 1.34 mm, 1.70 mm, respectively (voxel size 2.65 mm3) for 6- to 8-mm vessels; 1.31 mm2, 1.10 mm, 1.34 mm (voxel size 1.76 mm3), for 4- to 5-mm vessels; and 1.17 mm2, 0.90 mm, 0.9 mm (voxel size 1.05 mm3) for 1- to 3-mm vessels. CONCLUSION: Higher spatial resolution than currently used should be selected for imaging peripheral vessels.

Navigator-gated free-breathing three-dimensional balanced fast field echo (TrueFISP) coronary magnetic resonance angiography.

RATIONALE AND OBJECTIVES: Recent developments of MR imaging equipment enabled high-quality steady state-free-precession (Balanced FFE, True-FISP) MR-imaging with a substantial 'T2 like' contrast, resulting in a high signal intensity of the blood-pool without the application of exogenous contrast agents. It is hypothesized that Balanced-FFE may be valuable for contrast enhancement in 3D free-breathing coronary MRA. MATERIALS AND METHODS: Navigator-gated free-breathing cardiac triggered coronary MRA was performed in 10 healthy adult subjects and three patients with radiograph defined coronary artery disease using a segmented k-space 3D Balanced FFE imaging sequence. RESULTS: High contrast-to-noise ratio between the blood-pool and the myocardium (29 +/- 8) and long segment visualization of both coronary arteries could be obtained in about 5 minutes during free breathing using the present navigator-gated Balanced-FFE coronary MRA approach. First patient results demonstrated successful display of coronary artery stenoses. CONCLUSION: Balanced FFE offers a potential alternative for endogenous contrast enhancement in navigator-gated free-breathing 3D coronary MRA. The obtained results together with the relatively short scanning time warrant further studies in larger patient collectives.

High-resolution selective three-dimensional magnetic resonance coronary angiography with navigator-echo technique: segment-by-segment evaluation of coronary artery stenosis.

PURPOSE: To investigate the feasibility of high-resolution selective three-dimensional (3D) magnetic resonance coronary angiography (MRCA) in the evaluation of coronary artery stenoses. MATERIALS AND METHODS: In 12 patients with coronary artery stenoses, MRCA of the coronary artery groups, including the coronary segments with stenoses of 50% or greater based on conventional x-ray coronary angiography (CAG), was performed with double-oblique imaging planes by orienting the 3D slab along the major axis of each right coronary artery-left circumflex artery (RCA-LCX) group and each left main trunk-left anterior descending artery (LMT-LAD) group. Ten RCA-LCX and five LMT-LAD MR angiograms were obtained, and the results were compared with those of conventional x-ray angiography. RESULTS: Among 70 coronary artery segments expected to be covered, a total of 49 (70%) segments were fully demonstrated in diagnostic quality. The identification of segmental location of stenoses showed as high an accuracy as 96%. The retrospective analysis for stenosis of 50% or greater yielded the sensitivity, specificity, and accuracy of 80%, 85%, and 84%, respectively. CONCLUSION: Selective 3D MRCA has the potential for segment-by-segment evaluation of major portions of the right and left coronary arteries with high accuracy.