Nanoscale Titanium Research Articles

Developmental toxicity studies with 6 forms of titanium dioxide test materials (3 pigment-different grade & 3 nanoscale) demonstrate an absence of effects in orally-exposed rats

Six different commercial forms and sizes of titanium dioxide particles were tested in separate developmental toxicity assays. The three pigment-grade (pg) or 3 ultrafine (uf)/nanoscale (anatase and/or rutile) titanium dioxide (TiO2) particle-types were evaluated for potential maternal and developmental toxicity in pregnant rats by two different laboratories. All studies were conducted according to OECD Guideline 414 (Prenatal Developmental Toxicity Study). In addition, all test materials were robustly characterized. The BET surface areas of the pg and uf samples ranged from 7 to 17 m2/g and 50–82 m2/g respectively (see Table 1). The test substances were formulated in sterile water. In all of the studies, the formulations were administered by oral gavage to time-mated rats daily beginning around the time of implantation and continuing until the day prior to expected parturition. In 3 of the studies (uf-1, uf-3, & pg-1), the formulations were administered to Crl:CD(SD) rats beginning on gestation day (GD) 6 through GD 20. In 3 additional studies (uf-2, and pg-2, pg-3 TiO2 particles), the formulations were administered to Wistar rats beginning on GD 5 through 19. The dose levels used in all studies were 0, 100, 300, or 1000 mg/kg/day; control group animals were administered the vehicle. During the in-life portions of the studies, body weights, food consumption, and clinical observations before and after dosing were collected on a daily basis. All dams were euthanized just prior to expected parturition (GD 21 for Crl:CD(SD) rats and GD 20 for Wistar rats). The gross necropsies included an examination and description of uterine contents including counts of corpora lutea, implantation sites, resorptions, and live and dead fetuses. All live fetuses were sexed, weighed, and examined externally and euthanized. Following euthanasia, fresh visceral and head examinations were performed on selected fetuses. The fetal carcasses were then processed and examined for skeletal alterations. There was no evidence of maternal or developmental toxicity at any dose level tested in any of the six studies. Based on these results, the no-observed-adverse-effect level (NOAEL) for titanium dioxide was 1000 mg/kg/day, the highest administered dose, in both the Sprague–Dawley (Crl:CD(SD) and Wistar rat strains.

Biological Effect of Ultraviolet Photocatalysis on Nanoscale Titanium with a Focus on Physicochemical Mechanism.

Physicochemical properties, regulated by various surface modifications, influence the biological performance of materials. The interaction between surface charge and biomolecules is key to understanding the mechanism of surface-tissue integration. The objective of this study was to evaluate the biological response to a nanoscale titanium surface after ultraviolet (UVC, λ = 250 ± 20 nm) irradiation and to analyze the effects via a physicochemical mechanism. The surface characteristics were evaluated by field-emission scanning electron microscopy, X-ray photoelectron spectroscopy, surface profilometry, and contact angle assay. In addition, we applied the zeta-potential, a direct method to measure the electrostatic charge on UV-treated and UV-untreated titanium nanotube surfaces. The effect of the Ti surface after UV treatment on the biological process was determined by analyzing bovine serum albumin (BSA) adsorption and osteoblast-like MG-63 early adhesion, morphology, cytoskeletal arrangement, proliferation, and focal adhesion. Compared to an anodized titanium nanotube coating, UV irradiation altered the contact angles on the control surface from 51.5° to 6.2° without changing the surface topography or roughness. Furthermore, titanium nanotubes after UV treatment showed a significant reduction in the content of acidic hydroxyl groups and held less negative charge than the anodized coating. With regard to the biological response, along with an enhanced capability to adsorb BSA, osteoblasts exhibited higher colonization and viability on the UV-treated material. The results suggest that UV treatment enhances the biocompatibility by reducing the electrostatic repulsion between biomaterials and biomolecules.

Acute and subchronic oral toxicity studies in rats with nanoscale and pigment grade titanium dioxide particles

Data generated using standardized testing protocols for toxicity studies generally provide reproducible and reliable results for establishing safe levels and formulating risk assessments. The findings of three OECD guideline-type oral toxicity studies of different duration in rats are summarized in this publication; each study evaluated different titanium dioxide (TiO2) particles of varying sizes and surface coatings. Moreover, each study finding demonstrated an absence of any TiO2 -related hazards. To briefly summarize the findings: 1) In a subchronic 90-day study (OECD TG 408), groups of young adult male and female rats were dosed with rutile-type, surface-coated pigment-grade TiO2 test particles (d50 = 145 nm − 21% nanoparticles by particle number criteria) by oral gavage for 90 days. The no-adverse-effect level (NOAEL) for both male and female rats in this study was 1000 mg/kg bw/day, the highest dose tested. The NOAEL was determined based on a lack of TiO2 particle-related adverse effects on any in-life, clinical pathology, or anatomic/microscopic pathology parameters; 2) In a 28-day repeated-dose oral toxicity study (OECD TG 407), groups of young adult male rats were administered daily doses of two rutile-type, uncoated, pigment-grade TiO2 test particles (d50 = 173 nm by number) by daily oral gavage at a dose of 24,000 mg/kg bw/day. There were no adverse effects measured during or following the end of the exposure period; and the NOAEL was determined to be 24,000 mg/kg bw/day; 3) In an acute oral toxicity study (OECD TG 425), female rats were administered a single oral exposure of surface-treated rutile/anatase nanoscale TiO2 particles (d50 = 73 nm by number) with doses up to 5000 mg/kg and evaluated over a 14-day post-exposure period. Under the conditions of this study, the oral LD50 for the test substance was >5000 mg/kg bw. In summary, the results from these three toxicity studies – each with different TiO2 particulate-types, demonstrated an absence of adverse toxicological effects. Apart from reporting the findings of these three studies, this publication also focuses on additional critical issues associated with particle and nanotoxicology studies. First, describing the detailed methodology requirements and rigor upon which the standardized OECD 408 guideline subchronic oral toxicity studies are conducted. Moreover, an attempt is made to reconcile the complex issue of particle size distribution as it relates to measurements of nanoscale and pigment-grade TiO2 particles. Clearly this has been a confusing issue and often misrepresented in the media and the scientific literature. It is clear that the particle-size distribution for pigment-grade TiO2, contains a small (“tail”) component of nanoscale particles (i.e., 21% by particle number and <1% by weight in the test material used in the 90-day study). However, this robust particle characterization finding should not be confused with mislabeling the test materials as exclusively in the nanoscale range. Moreover, based upon the findings presented herein, there appears to be no significant oral toxicity impact contributed by the nanoscale component of the TiO2 Test Material sample in the 90-day study. Finally, it seems reasonable to conclude that the study findings should be considered for read-across purposes to food-grade TiO2 particles (e.g., E171), as the physicochemical characteristics are quite similar.

Composites Based on Polystyrene Microspheres with Nano-Scaled Titanium Dioxide

This study produced for the first time composites based on polystyrene microspheres with nano-sized titania synthesized by sulfate and sol-gel methods, as well as commercial Hombifine N, Hombikat UV100, and Degussa P25. The starting samples and the composites were characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption capacity, and IR spectroscopy. The highest content of nano-titanium dioxide both in the bulk and on the surface of microspheres was obtained with the use of Hombikat UV100. This sample has the largest specific surface area and a high content of reactive OH groups. The adsorption properties of composites were investigated.

Synthesis and properties of nanoscale titanium boride

This work reports the scientific and technological grounds for plasma synthesis of titanium diboride, including thermodynamic and kinetic conditions of boride formation when titanium and titanium dioxide are interacting with products resulting from boron gasification in the nitrogen - hydrogen plasma flow, and two variations of its behavior using the powder mixtures: titanium - boron and titanium dioxide - boron. To study these technology variations, the mathematical models were derived, describing the relation between element contents in the synthesized products of titanium and free boron and basic parameters. The probable mechanism proposed for forming titanium diboride according to a "vapour - melt - crystal" pattern was examined, covering condensation of titanium vapour in the form of aerosol, boriding of nanoscale melt droplets by boron hydrides and crystallization of titanium - boron melt. The comprehensive physical - chemical certification of titanium diboride was carried out, including the study of its crystal structure, phase and chemical composition, dispersion, morphology and particle oxidation. Technological application prospects for use of titanium diboride nanoscale powder as constituent element in the wettable coating for carbon cathodes having excellent physical and mechanical performance and protective properties.

Research on titanium nitride thin films deposited by reactive magnetron sputtering for MEMS applications

Titanium nitride can be used among other materials as diffusion barrier for MEMS (microelectromechanical systems) applications. The aim of this study is to elaborate and to characterize at nanoscale titanium nitride thin films. The thin films were deposited by reactive magnetron sputtering on silicon substrates using a 99.99% purity titanium target. Different deposition parameters were employed. The deposition temperature, deposition time, substrate bias voltage and the presence/absence of a titanium buffer layer are the parameters that were modified. The so-obtained films were then investigated by atomic force microscopy. A significant impact of the deposition parameters on the determined mechanical and tribological characteristics was highlighted. The results showed that the titanium nitride thin films deposited for 20min at room temperature without the presence of a titanium buffer layer when a negative bias of −90V was applied to the substrate is characterized by the best tribological and mechanical behavior.

Photocatalytic Decomposition of Methylene Blue by Nanocomposite Fibers Containing TiO₂

This study investigated the incorporation of nanoscale titanium dioxide (TiO₂) particles, a well-known photocatalyst, into poly(vinyl alcohol) (PVA) nanofibers via electrospinning for the development of self-cleaning textile materials that can decompose organic contaminants and stains on the textile surface by light irradiation. TiO₂/PVA nanocomposite fiber webs were fabricated from a PVA solution containing 5wt% TiO₂ nanoparticles at a web area density of 3.0g/㎡. The morphology of electrospun nanocomposite fibers was examined using a field-emission scanning electron microscope and a transmission electron microscope. The photocatalytic decomposition efficiency of the nanocomposite fibers was examined by decomposition rates of methylene blue in aqueous solution under UV light irradiation. Also, the nanocomposite fibers were contaminated by methylene blue, and the color change of methylene blue on the fibers was assessed with time of light exposure. Methylene blue solution that contained TiO₂/PVA nanocomposite fibers exhibited much lower absorbance and thus gave a higher decomposition rate compared to that with pure PVA nanofiber webs after 12 hours of irradiation. TiO₂/PVA nanocomposite fibers contaminated by methylene blue also showed a photocatalytic property for the colorant after 24 hours of irradiation. The results indicate that TiO₂/PVA nanocomposite fiber webs have potential in medical textiles and automotive textiles that require self-cleaning properties.

Structure and properties of ultrathin poly-(3-hydroxybutirate) fibers modified by silicon and titanium dioxide particles

The influence of small concentrations of nanoscale silicon and titanium dioxide particles on the structure, physicomechanical and sorption properties, thermal destruction resistance, and thermal and photo oxidant destruction of unwoven ultrathin fibrous materials that are prepared via electrostatic solution spinning is studied. It is established that nanoscale particles favor the formation of thinner fibers with improved physical and mechanical parameters; good resistance to thermal, thermo- and photo oxidant destruction; and positive dynamics of mesenchymal stem cells.

Preparation and Photocatalytic Performance of Nano‐TiO2 Codoped with Iron III and Lanthanum III

Nanoscale titanium dioxide (nano‐TiO2) was modified via metal doping to improve its photocatalytic activity and utilization of visible light. Nano‐TiO2 doped with iron III (Fe3+) only, lanthanum III (La3+) only, and both Fe3+/La3+ was prepared using the sol‐gel method. The photocatalytic activities of the three forms of doped nano‐TiO2 were evaluated. Metal codoping limited crystal growth of crystal, and the sol‐gel method was shown to be an effective technique for doping the lattice of TiO2 with Fe3+ and La3+. Codoping of nano‐TiO2 with the tombarthite metal mixture had a synergistic effect of the photocatalytic performance, with the codoped nano‐TiO2 exhibiting a performance greater than the sum of those of the single‐doped nano‐TiO2 samples. Kinetic studies showed that the photodegradation reaction of methyl orange by nano‐TiO2 follows the Langmuir‐Hinshelwood first order mechanism.

Lung injury induced by TiO2 nanoparticles depends on their structural features: size, shape, crystal phases, and surface coating.

With the rapid development of nanotechnology, a variety of engineered nanoparticles (NPs) are being produced. Nanotoxicology has become a hot topic in many fields, as researchers attempt to elucidate the potential adverse health effects of NPs. The biological activity of NPs strongly depends on physicochemical parameters but these are not routinely considered in toxicity screening, such as dose metrics. In this work, nanoscale titanium dioxide (TiO2), one of the most commonly produced and widely used NPs, is put forth as a representative. The correlation between the lung toxicity and pulmonary cell impairment related to TiO2 NPs and its unusual structural features, including size, shape, crystal phases, and surface coating, is reviewed in detail. The reactive oxygen species (ROS) production in pulmonary inflammation in response to the properties of TiO2 NPs is also briefly described. To fully understand the potential biological effects of NPs in toxicity screening, we highly recommend that the size, crystal phase, dispersion and agglomeration status, surface coating, and chemical composition should be most appropriately characterized.

Impact of particle size and light exposure on the effects of TiO2 nanoparticles on Caenorhabditis elegans.

The increasing use of engineered nanoparticles in industrial and consumer products leads to a release of the anthropogenic contaminants to the aquatic environment. To obtain a better understanding of the environmental effects of these particles, the nematode Caenorhabditis elegans was used to investigate the organism-level effects and in vivo molecular responses. Toxicity of bulk-scale (∼160 nm) and nanoscale (21 nm) titanium dioxide (TiO2 ) was tested under dark and light conditions, following ISO 10872. The expression of sod-3, a mitochondrial superoxide dismutase, was quantified as an indicator for oxidative stress induced by the photocatalytically active material. Particle sizes were estimated using dynamic light scattering and scanning electron microscopy. Although both materials agglomerated to a comparable secondary particle size of 300 nm to 1500 nm and were ingested into the intestine, only nanoscale-TiO2 significantly inhibited reproduction (lowest-observed-effect-concentration [LOEC]: 10 mg/L). Light exposure induced the production of reactive oxygen species (ROS) by nanoscale-TiO2 and increased toxicity of the nanomaterial from a median effect concentration of more than 100 mg/L to 53 mg/L. No evidence was found for inner cellular photocatalytic activity of nanoscale-TiO2 . Therefore, oxidative damage of the membranes of intestinal cells is suggested as a potential mode of action. Results highlight the importance of primary particle size and environmental parameters on the toxicity of TiO2 .

Transparent stakeholder engagement in practice: Lessons learned from applying comprehensive environmental assessment to research planning for nanomaterials.

As efforts to develop new applications of engineered nanoscale materials (ENMs) continue to grow, so too has interest in the environmental, health, and safety (EHS) implications of these materials. However, thorough evaluation and interpretation of such implications could require substantial resources (e.g., estimated as >$120 million per year in federal funding 2013-2017). A structured, strategic approach for transparently planning research would support improved linkages between ENM research and risk assessments, and thereby enhance the utility of financial and other resources for EHS studies of ENMs. For this reason, we applied Comprehensive Environmental Assessment (CEA) as an approach to provide transparent input into research planning for 2 types of ENMs: nanoscale titanium dioxide and nanoscale silver. For each of these CEA applications, we employed a collective judgment method known as Nominal Group Technique (NGT) in 2 workshops sponsored by the US Environmental Protection Agency (USEPA). The objective of this paper is to present the outcomes of these CEA applications in the context of how our methodology can inform future efforts to identify collective goals in science (e.g., research priorities) through structured decision support approaches. Outcomes include clear lists of research priorities for each ENM developed through transparently engaging stakeholders having diverse technical and sector perspectives. In addition, we identified several procedural aspects that could be refined, including emphasizing breakout group interactions, identifying broad information priorities before more detailed research questions, and using rating rather than ranking prioritization methods. Beyond the research directions identified for specific ENMs, lessons learned about engaging stakeholders in research planning are expected to inform future research planning efforts for ENMs and other emerging materials across the scientific community.

Food grade titanium dioxide disrupts intestinal brush border microvilli in vitro independent of sedimentation.

Bulk- and nano-scale titanium dioxide (TiO2) has found use in human food products for controlling color, texture, and moisture. Once ingested, and because of their small size, nano-scale TiO2 can interact with a number of epithelia that line the human gastrointestinal tract. One such epithelium responsible for nutrient absorption is the small intestine, whose constituent cells contain microvilli to increase the total surface area of the gut. Using a combination of scanning and transmission electron microscopy it was found that food grade TiO2 (E171 food additive coded) included ∼25% of the TiO2 as nanoparticles (NPs; <100 nm), and disrupted the normal organization of the microvilli as a consequence of TiO2 sedimentation. It was found that TiO2 isolated from the candy coating of chewing gum and a commercially available TiO2 food grade additive samples were of the anatase crystal structure. Exposure to food grade TiO2 additives, containing nanoparticles, at the lowest concentration tested within this experimental paradigm to date at 350 ng/mL (i.e., 100 ng/cm(2) cell surface area) resulted in disruption of the brush border. Through the use of two independent techniques to remove the effects of gravity, and subsequent TiO2 sedimentation, it was found that disruption of the microvilli was independent of sedimentation. These data indicate that food grade TiO2 exposure resulted in the loss of microvilli from the Caco-2BBe1 cell system due to a biological response, and not simply a physical artifact of in vitro exposure.

Preparation and ageing-resistant properties of polyester composites modified with functional nanoscale additives.

This study investigated ageing-resistant properties of carboxyl-terminated polyester (polyethylene glycol terephthalate) composites modified with nanoscale titanium dioxide particles (nano-TiO2). The nano-TiO2 was pretreated by a dry coating method, with aluminate coupling agent as a functional grafting additive. The agglomeration resistance was evaluated, which exhibited significant improvement for the modified nanoparticles. Then, the effects of the modified nano-TiO2 on the crosslinking and ageing-resistant properties of the composites were studied. With a real-time Fourier transform infrared (FT-IR) measurement, the nano-TiO2 displayed promoting effect on the crosslinking of polyester resin with triglycidyl isocyanurate (TGIC) as crosslinking agent. Moreover, the gloss retention, colour aberration and the surface morphologies of the composites during accelerated UV ageing (1500 hours) were investigated. The results demonstrated much less degree of ageing degradation for the nanocomposites, indicating an important role of the nano-TiO2 in improving the ageing-resistant properties of synthetic polymer composites.

Rapid reduction of titanium dioxide nano-particles by reduction with a calcium reductant

Micro-, submicron-, and nano-scale titanium dioxide particles were reduced by reduction with a metallic calcium reductant in calcium chloride molten salt at 1173K, and the reduction mechanism of the oxides by the calcium reductant was explored. These oxide particles, metallic calcium as a reducing agent, and calcium chloride as a molten salt were placed in a titanium crucible and heated under an argon atmosphere. Titanium dioxide was reduced to metallic titanium through a calcium titanate and lower titanium oxide, and the materials were sintered together to form a micro-porous titanium structure in molten salt at high temperature. The reduction rate of titanium dioxide was observed to increase with decreasing particle size; accordingly, the residual oxygen content in the reduced titanium decreases. The obtained micro-porous titanium appeared dark gray in color because of its low surface reflection. Micro-porous metallic titanium with a low oxygen content (0.42wt%) and a large surface area (1.794m2g−1) can be successfully obtained by reduction under optimal conditions.

Using ICP-qMS to trace the uptake of nanoscale titanium dioxide by microalgae–potential disadvantages of vegetable reference material

As nanoscale materials have gained in economic importance over recent years, concerns about accumulation in the environment and, consequently, analysis of nanoparticles in biological material have increasingly become the focus of scientific research. A nanomaterial used in a wide range of food, consumer and household products is titanium dioxide (nTiO2). Monitoring of nTiO2 via determination of elemental titanium (Ti) can be very challenging because of a variety of possible interferences. This work describes problems during the development of a quantification method for titanium dioxide (TiO2) using inductively coupled plasma-quadrupole mass spectrometry (ICP-qMS). To evaluate the analytical method, certified vegetable reference material NCS DC 73349 was used. Interestingly, measurements of NCS DC 73349 seemed to result in acceptable recovery values-however, this was without considering interferences or conceivable differences in the natural isotopic abundance of the certified titanium calibration solution and NCS DC 73349. Actually, recoveries were lower than initially assumed. The potential interferences causing augmented recovery could be attributed to the presence of the elements sulfur (S) and phosphorus (P), which were able to form oxide ions and nitrogen-interfering species. The effect of such interfering cluster ions could be prevented by dry ashing as a sample preparation step, to evaporate S and P, before digestion with aqua regia in a high-pressure asher (HPA). Final practicability of the analysis method was proved by monitoring the uptake of nTiO2 by the microalgae Scenedesmus acutus in an environmental exposure study.

Interfacial band alignment and structural properties of nanoscale TiO2 thin films for integration with epitaxial crystallographic oriented germanium

We have investigated the structural and band alignment properties of nanoscale titanium dioxide (TiO2) thin films deposited on epitaxial crystallographic oriented Ge layers grown on (100), (110), and (111)A GaAs substrates by molecular beam epitaxy. The TiO2 thin films deposited at low temperature by physical vapor deposition were found to be amorphous in nature, and high-resolution transmission electron microscopy confirmed a sharp heterointerface between the TiO2 thin film and the epitaxially grown Ge with no traceable interfacial layer. A comprehensive assessment on the effect of substrate orientation on the band alignment at the TiO2/Ge heterointerface is presented by utilizing x-ray photoelectron spectroscopy and spectroscopic ellipsometry. A band-gap of 3.33 ± 0.02 eV was determined for the amorphous TiO2 thin film from the Tauc plot. Irrespective of the crystallographic orientation of the epitaxial Ge layer, a sufficient valence band-offset of greater than 2 eV was obtained at the TiO2/Ge heterointerface while the corresponding conduction band-offsets for the aforementioned TiO2/Ge system were found to be smaller than 1 eV. A comparative assessment on the effect of Ge substrate orientation revealed a valence band-offset relation of ΔEV(100) &amp;gt; ΔEV(111) &amp;gt; ΔEV(110) and a conduction band-offset relation of ΔEC(110) &amp;gt; ΔEC(111) &amp;gt; ΔEC(100). These band-offset parameters are of critical importance and will provide key insight for the design and performance analysis of TiO2 for potential high-κ dielectric integration and for future metal-insulator-semiconductor contact applications with next generation of Ge based metal-oxide field-effect transistors.

Influence of temperature change on conductive characteristics of titanium oxide memristor

Nano-scaled titanium oxide memristors exhibit unstable conductive characteristics under the same test condition: restricting the possibility to have accurate reading and control of the transient resistance of the device. Moreover, the reliability and stability of memristor-based circuits cannot be guaranteed. Coexistence of dopant drift and tunnel barrier is one of possible origins which causes undesirable instability, and the ambient temperature has a close relationship with dopant drift. However, there have been no detailed researches which may improve the stability of memristors by controlling temperatures. Based on the coexistence of dopant drift and tunnel barrier, the connections between temperature and memristor conductive characteristics are analyzed, and the influences of changes of active area width and initially doped layer width on the critical temperature are studied. Simulations are performed in SPICE and the results are given in this paper. In conclusion, methods are proposed for enhancing the conductive stability of memristors, which include increasing the active area width, decreasing the initially doped layer width, keeping the temperature to be under the critical value, and stability. Our work may provide a basis for manufacturing memristors with stable performance and promoting the practical circuit in applications.

Influence of the cross section area on the conductive characteristics of titanium oxide memristor

The conduction of nano-scale titanium oxide memristor exhibits complex characteristics, owing to the change of self-parameters and the coexistence of different conductive mechanisms. However, there has been no detailed discussion about the influence of the cross section area change on the conductive characteristics of memristor. Based on dopant drift and tunnel barrier mechanisms, the conductive process of memristor is analysed, and the relevance between cross section area and key physical factors of the conductive process is studied, then the influences of the changes of titanium oxide and tunnel barrier cross section area on conductive characteristics of memristors are studied, respectively. The differences and connections between the two cases are analysed. In the case of the coexistence of those two mechanisms, compared with the change of titanium oxide cross section area, the change of tunnel barrier cross section area is proved to be the chief factor which causes changes of memristor conductive characteristics, it is also a possible factor causing the change of non-ideal conductive characteristics of memristor. The research results contribute to further explaining the complexity of memristor conductions and providing basis for optimizing memristor modeling.

XPS study of MxTi0.91V0.09O2 + δ nH2O (M = Co, Fe) nanoscale oxides

A strong correlation was found between the ionic state of magnetic Ti, V, Co and Fe ions in doped nanoscale titanium–vanadium oxides synthesized by a sol-gel method, the annealing conditions of the samples and the dopant ions.