Experimental study of the mechanical properties and durability of self-compacting mortars with nano materials (SiO2 and TiO2)

Resumo: Cement, as well as the remaining constituents of self-compacting mortars, must be carefully selected, in order to obtain an adequate composition with a granular mix as compact as possible and a good performance in the fresh state (self-compacting effect) and the hardened state (mechanical and durability-related behavior). Therefore in this work the possibility of incorporating nano particles in self-compacting mortars was studied. Nano materials are very reactive due mostly to their high specific surface and show a great potential to improve the properties of these mortars, both in mechanical and durability terms. In this work two nano materials were used, nano silica (nano SiO2) in colloidal state and nano titanium (nano TiO2) in amorphous state, in two types of self-compacting mortars (ratio binder:sand of 1:1 and 1:2). The self-compacting mortar mixes have the same water/cement ratio and 30% of replacement of cement with fly ashes. The influence of nano materials nano-SiO2 and nano-TiO2 on the fresh and hardened state properties of these self-compacting mortars was studied. The results show that the use of nano materials in repair and rehabilitation mortars has significant potential but still needs to be optimized. (C) 2015 Elsevier Ltd. All rights reserved.

Limitations and information needs for engineered nanomaterial-specific exposure estimation and scenarios: recommendations for improved reporting practices

The aim of this paper is to describe the process and challenges in building exposure scenarios for engineered nanomaterials (ENM), using an exposure scenario format similar to that used for the European Chemicals regulation (REACH). Over 60 exposure scenarios were developed based on information from publicly available sources (literature, books, and reports), publicly available exposure estimation models, occupational sampling campaign data from partnering institutions, and industrial partners regarding their own facilities. The primary focus was on carbon-based nanomaterials, nano-silver (nano-Ag) and nano-titanium dioxide (nano-TiO2), and included occupational and consumer uses of these materials with consideration of the associated environmental release. The process of building exposure scenarios illustrated the availability and limitations of existing information and exposure assessment tools for characterizing exposure to ENM, particularly as it relates to risk assessment. This article describes the gaps in the information reviewed, recommends future areas of ENM exposure research, and proposes types of information that should, at a minimum, be included when reporting the results of such research, so that the information is useful in a wider context.

Development of novel surface coatings based on acrylic copolymers

The present study describes the preparation of Vinyl acetate-Butyl acrylate copolymer lattices of varying compositions and solid contents by semicontinuous emulsion polymerization method. This copolymer lattices were used as binder to develop a new surface coating formulation. The properties of this surface coating were improved by using nano TiO2 colloidal sol as a pigment. Antimicrobial activity of surface coatings was improved by the addition of carboxymethyl chitosan as biocide. Uniformly dispersed tyre crumb was used to give a mat finish to the coating. The mechanical properties adhesive properties, thermal properties etc. of the coatings are presented in thesis.

Osteoblast differentiation is enhanced by a nano-to-micro hybrid titanium surface created by Yb:YAG laser irradiation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Titanium oxide adhesion layer for high temperature annealed Si/Si3N4/TiOx/Pt/LiCoO2 battery structures

This work describes the influence of a high annealing temperature of about 700C on the Si(substrate)/Si3N4/TiOx/Pt/LiCoO2 multilayer system for the fabrication of all-solid-state lithium ion thin film microbatteries. Such microbatteries typically utilize lithium cobalt oxide (LiCoO2) as cathode material with a platinum (Pt) current collector. Silicon nitride (Si3N4) is used to act as a barrier against Li diffusion into the substrate. For a good adherence between Si3N4 and Pt, commonly titanium (Ti) is used as intermediate layer. However, to achieve crystalline LiCoO2 the multilayer system has to be annealed at high temperature. This post-treatment initiates Ti diffusion into the Pt-collector and an oxidation to TiOx, leading to volume expansion and adhesion failures. To solve this adhesion problem, we introduce titanium oxide (TiOx) as an adhesion layer, avoiding the diffusion during the annealing process. LiCoO2, Pt and Si3N4 layers were deposited by magnetron sputtering and the TiOx layer by thermal oxidation of Ti layers deposited by e-beam technique. Asdeposited and annealed multilayer systems using various TiOx layer thicknesses were studied by scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) and x-ray photoelectron spectroscopy (XPS). The results revealed that an annealing process at temperature of 700C leads to different interactions of Ti atoms between the layers, for various TiOx layer thicknesses (25–45 nm).

Studies on Catalysis by Nano Titania Modified with Metals and Nonmetals

Semiconductor photocatalysis has received much attention during last three decades as a promising solution for both energy generation and environmental problems. Heterogeneous photocatalytic oxidation allows the degradation of organic compounds into carbon dioxide and water in the presence of a semiconductor catalyst and UV light source. The •OH radicals formed during the photocatalytic processes are powerful oxidizing agents and can mineralise a number of organic contaminants. Titanium dioxide (TiO2), due to its chemical stability, non-toxicity and low cost represents one of the most efficient photocatalyst. However, only the ultraviolet fraction of the solar radiation is active in the photoexcitation processes using pure TiO2 and although, TiO2 can treat a wide range of organic pollutants the effectiveness of the process for pollution abatement is still low. A more effective and efficient catalyst therefore must be formulated. Doping of TiO2 was considered with the aim of improving photocatalytic properties. In this study TiO2 catalyst was prepared using the sol-gel method. Metal and nonmetal doped TiO2 catalysts were prepared. The photoactivity of the catalyst was evaluated by the photodegradation of different dyes and pesticides in aqueous solution. High photocatalytic degradation of all the pollutants was observed with doped TiO2. Structural and optical properties of the catalysts were characterized using XRD, BET surface area, UV-Vis. DRS, CHNS analysis, SEM, EDX, TEM, XPS, FTIR and TG. All the catalysts showed the anatase phase. The presence of dopants shifts the absorption of TiO2 into the visible region indicating the possibility of using visible light for photocatalytic processes.

Ecotoxicology of Nano-TiO2 An Evaluation of its Toxicity to Organisms of Aquatic Ecosystems

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Growth of Calcium Phosphate Using Chemically Treated Titanium Oxide Nanotubes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Osteogenesis-inducing calcium phosphate nanoparticle precursors applied to titanium surfaces

This study investigated the effects of the morphology and physicochemical properties of calcium phosphate (CaP) nanoparticles on osteogenesis. Two types of CaP nanoparticles were compared, namely amorphous calcium phosphate (ACP) nano-spheres (diameter: 9-13 nm) and poorly crystalline apatite (PCA) nano-needles (30-50 nm x 2-4 nm) that closely resemble bone apatite. CaP particles were spin-coated onto titanium discs and implants; they were evaluated in cultured mouse calvarial osteoblasts, as well as after implantation in rabbit femurs. A significant dependence of CaP coatings was observed in osteoblast-related gene expression (Runx2, Col1a1 and Spp1). Specifically, the PCA group presented an up-regulation of the osteospecific genes, while the ACP group suppressed the Runx2 and Col1a1 expression when compared to blank titanium substrates. Both the ACP and PCA groups presented a more than three-fold increase of calcium deposition, as suggested by Alizarin red staining. The removal torque results implied a slight tendency in favour of the PCA group. Different forms of CaP nanostructures presented different biologic differences; the obtained information can be used to optimize surface coatings on biomaterials. © 2013 IOP Publishing Ltd.

Fish exposure to nano-TiO2 under different experimental conditions: Methodological aspects for nanoecotoxicology investigations

The ecotoxicology of nano-TiO2 has been extensively studied in recent years; however, few toxicological investigations have considered the photocatalytic properties of the substance, which can increase its toxicity to aquatic biota. The aim of this work was to evaluate the effects on fish exposed to different nano-TiO2 concentrations and illumination conditions. The interaction of these variables was investigated by observing the survival of the organisms, together with biomarkers of biochemical and genetic alterations. Fish (Piaractus mesopotamicus) were exposed for 96h to 0, 1, 10, and 100mg/L of nano-TiO2, under visible light, and visible light with ultraviolet (UV) light (22.47J/cm2/h). The following biomarkers of oxidative stress were monitored in the liver: concentrations of lipid hydroperoxide and carbonylated protein, and specific activities of superoxide dismutase, catalase, and glutathione S-transferase. Other biomarkers of physiological function were also studied: the specific activities of acid phosphatase and Na,K-ATPase were analyzed in the liver and brain, respectively, and the concentration of metallothionein was measured in the gills. In addition, micronucleus and comet assays were performed with blood as genotoxic biomarkers. Nano-TiO2 caused no mortality under any of the conditions tested, but induced sublethal effects that were influenced by illumination condition. Under both illumination conditions tested, exposure to 100mg/L showed an inhibition of acid phosphatase activity. Under visible light, there was an increase in metallothionein level in fish exposed to 1mg/L of nano-TiO2. Under UV light, protein carbonylation was reduced in groups exposed to 1 and 10mg/L, while nucleus alterations in erythrocytes were higher in fish exposed to 10mg/L. As well as improving the understanding of nano-TiO2 toxicity, the findings demonstrated the importance of considering the experimental conditions in nanoecotoxicological tests. This work provides information for the development of protocols to study substances whose toxicity is affected by illumination conditions. © 2013 Elsevier B.V..

Clareamento dental com perôxido de hidrogênio contendo nano partículas de óxido de titânio como semicondutor: efeito de concentrações, tempos e formas de ativação

Pós-graduação em Ciências Odontológicas - FOAR

Biomarker evaluation in fish after prolonged exposure to nano-TiO2: influence of illumination conditions and crystal phase

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

An alternative blocking layer for titanium dioxide (TiO 2) solar cell applications

In hybrid organic solar cells a blocking layer between transparent electrode and nanocrystalline titania particles is essential to prevent short-circuiting and current loss through recombination at the electrode interface. Here the preparation of a uniform hybrid blocking layer which is composed of conducting titania nanoparticles embedded in an insulating polymer derived ceramic is presented. This blocking layer is prepared by sol-gel chemistry where an amphiphilic block copolymer is used as a templating agent. A novel poly(dimethylsiloxane) containing amphiphilic block copolymer poly(ethyleneglycol)methylethermethacrylate-block-poly(dimethylsiloxane)-block-poly(ethyleneglycol)methylethermethacrylate has been synthesized to act as the templating agent. Plasma treatment uncovered titania surface from any polymer. Annealing at 450°C under nitrogen resulted in anatase titania with polymer derived silicon oxycarbide ceramic. Electrical characterization by conductive scanning probe microscopy experiments revealed a percolating titania network separated by an insulating ceramic matrix. Scanning Kelvin probe force microscopy showed predominant presence of titania particles on the surface creating a large surface area for dye absorption. The uniformity of the percolating structures was proven by microbeam grazing incidence small angle x-ray scattering. First applications in hybrid organic solar cells in comparison with conventional titanium dioxide blocking layer containing devices revealed 15 fold increases in corresponding efficiencies. Poly(dimethylsiloxane)-block-poly(ethyleneglycol)methylethermethacrylate and poly(ethyleneoxide)-poly(dimethylsiloxane)methylmethacrylate diblock copolymers were also synthesized. Their titania nanocomposite films were compared with the integrated blocking layer. Liner poly(ethyleneoxide) containing diblock copolymer resulted in highly ordered foam like structures. The effect of heating temperature rise to 600°C and 1000°C on titania morphology was investigated by scanning electron and force microscopy and x-ray scattering. Sol-gel contents, hydrochloric acid, titania precursor and amphiphilic triblock copolymer were altered to see their effect on titania morphology. Increase in block copolymer content resulted in titania particles of diameter 15-20 nm.

Generation and characterization of stable, highly concentrated titanium dioxide nanoparticle aerosols for rodent inhalation studies

The intensive use of nano-sized titanium dioxide (TiO2) particles in many different applications necessitates studies on their risk assessment as there are still open questions on their safe handling and utilization. For reliable risk assessment, the interaction of TiO2 nanoparticles (NP) with biological systems ideally needs to be investigated using physico-chemically uniform and well-characterized NP. In this article, we describe the reproducible production of TiO2 NP aerosols using spark ignition technology. Because currently no data are available on inhaled NP in the 10–50 nm diameter range, the emphasis was to generate NP as small as 20 nm for inhalation studies in rodents. For anticipated in vivo dosimetry analyses, TiO2 NP were radiolabeled with 48V by proton irradiation of the titanium electrodes of the spark generator. The dissolution rate of the 48V label was about 1% within the first day. The highly concentrated, polydisperse TiO2 NP aerosol (3–6 × 106 cm−3) proved to be constant over several hours in terms of its count median mobility diameter, its geometric standard deviation, and number concentration. Extensive characterization of NP chemical composition, physical structure, morphology, and specific surface area was performed. The originally generated amorphous TiO2 NP were converted into crystalline anatase TiO2 NP by thermal annealing at 950 °C. Both crystalline and amorphous 20-nm TiO2 NP were chain agglomerated/aggregated, consisting of primary particles in the range of 5 nm. Disintegration of the deposited TiO2 NP in lung tissue was not detectable within 24 h.

Structural and surface property characterization of titanium dioxide nanotubes for orthopedic implants

This research focused on the to modification of the surface structure of titanium implants with nanostructured morphology of TiO2 nanotubes and studied the interaction of nanotubes with osteoblast cells to understand the parameters that affect the cell growth. The electrical, mechanical, and structural properties of TiO2 nanotubes were characterized to establish a better understanding on the properties of such nanoscale morphological structures. To achieve the objectives of this research work I transformed the titanium and its alloys, either in bulk sheet form, bulk machined form, or thin film deposited on another substrate into a surface of titania nanotubes using a low cost and environmentally friendly process. The process requires only a simple electrolyte, low cost electrode, and a DC power supply. With this simple approach of scalable nanofabrication, a typical result is nanotubes that are each approximately 100nm in diameter and have a wall thickness of about 20nm. By changing the fabrication parameters, independent nanotubes can be fabricated with open volume between them. Titanium in this form is termed onedimensional since electron transport is narrowly confined along the length of the nanotube. My Ph.D. accomplishments have successfully shown that osteoblast cells, the cells that are the precursors to bone, have a strong tendency to attach to the inside and outside of the titanium nanotubes onto which they are grown using their filopodia – cell’s foot used for locomotion – anchored to titanium nanotubes. In fact it was shown that the cell prefers to find many anchoring sites. These sites are critical for cell locomotion during the first several weeks of maturity and upon calcification as a strongly anchored bone cell. In addition I have shown that such a surface has a greater cell density than a smooth titanium surface. My work also developed a process that uses a focused and controllably rastered ion beam as a nano-scalpel to cut away sections of the osteoblast cells to probe the attachment beneath the main cell body. Ultimately the more rapid growth of osteoblasts, coupled with a stronger cell-surface interface, could provide cost reduction, shorter rehabilitation, and fewer follow-on surgeries due to implant loosening.