Characteristic of nanoparticles generated from different nano-powders by using different dispersion methods

A standard rotating drum with a modified sampling train (RD), a vortex shaker (VS), and a SSPD (small-scale powder disperser) were used to investigate the emission characteristics of nano-powders, including nano-titanium dioxide (nano-TiO₂, primary diameter: 21 nm), nano-zinc oxide (nano-ZnO, primary diameter: 30–50 nm), and nano-silicon dioxide (nano-SiO₂, primary diameter: 10–30 nm). A TSI SMPS (scanning mobility particle sizer), a TSI APS (aerodynamic particle sizer), and a MSP MOUDI (micro-orifice uniform deposit impactor) were used to measure the number and mass distributions of generated particles. Significant differences in specific number and mass concentration or distributions were found among different methods and nano-powders with the most specific number and mass concentration and the smallest particles being generated by the most energetic SSPD, followed by VS and RD. Near uni-modal number or mass distributions were observed for the SSPD while bi-modal number or mass distributions existed for nano-powders except nano-SiO₂ which also exhibited bimodal mass distributions. The 30-min average results showed that the mass median aerodynamic diameter (MMAD) and number median diameter (NMD) of the SSPD ranged 1.1–2.1 μm and 166–261 nm, respectively, for all three nano-powders, which were smaller than those of the VS (MMAD: 3.3–6.0 μm and NMD: 156–462 nm), and the RD (MMAD: 5.2–11.2 μm and NMD: 198–479 nm). For nano-particles (electric mobility diameter < 100 nm), specific mass concentrations were nearly negligible for all three nano-powders and test methods. Specific number concentrations of nano-particles were low for the RD tester but were elevated when more energetic VS and SSPD testers were used. The quantitative size and concentration data obtained in this study is useful to elucidate the field emission and personal exposure data in the future provided that particle loss in the generation system is carefully assessed.     

A corrosion-resistance superhydrophobic TiO2 film

A superhydrophobic TiO₂ film with water contact angle greater than 170° on Hastelloy substrate was fabricated through simply dip-coating method from TiO₂ precursor solution containing TiO₂ nanoparticles with the average diameter 25 nm, followed by heat-treatment and modification with fluoroalkylsilane (FAS) molecules. The as-obtained sample was characterized by scanning electron microscopy (SEM), X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), and water contact angle measurement respectively. Moreover, the dynamic light scattering (DLS) size distribution of TiO₂ aggregated particles in the TiO₂ precursor solution containing P25 particles was evaluated by Laser Particle Sizer. It is found that the TiO₂ nanoparticles in TiO₂ precursor solution play a crucial role to form high superhydrophobicity. Simultaneously, the superhydrophobic TiO₂ film still showed great superhydrophobicity after corroded with strong acid or alkali solutions and protected the substrate from corrosion which should be critical to the potential application in industry.     

Dustiness behaviour of loose and compacted Bentonite and organoclay powders: What is the difference in exposure risk?

Single-drop and rotating drum dustiness testing was used to investigate the dustiness of loose and compacted montmorillonite (Bentonite) and an organoclay (Nanofil^®5), which had been modified from montmorillonite-rich Bentonite. The dustiness was analysed based on filter measurements as well as particle size distributions, the particle generation rate, and the total number of generated particles. Particle monitoring was completed using a TSI Fast Mobility Particle Sizer (FMPS) and a TSI Aerosol Particle Sizer (APS) at 1 s resolution. Low-pressure uniaxial powder compaction of the starting materials showed a logarithmic compaction curve and samples subjected to 3.5 kg/cm² were used for dustiness testing to evaluate the role of powder compaction, which could occur in powders from large shipments or high-volume storage facilities. The dustiness tests showed intermediate dustiness indices (1,077–2,077 mg/kg powder) in tests of Nanofil^®5, Bentonite, and compacted Bentonite, while a high-level dustiness index was found for compacted Nanofil^®5 (3,487 mg/kg powder). All powders produced multimodal particle size-distributions in the dust cloud with one mode around 300 nm (Bentonite) or 400 nm (Nanofil^®5) as well as one (Nanofil^®5) or two modes (Bentonite) with peaks between 1 and 2.5 μm. The dust release was found to occur either as a burst (loose Bentonite and Nanofil^®5), constant rate (compacted Nanofil^®5), or slowly increasing rate (compacted Bentonite). In rotating drum experiments, the number of particles generated in the FMPS and APS size-ranges were in general agreement with the mass-based dustiness index, but the same order was not observed in the single-drop tests. Compaction of Bentonite reduced the number of generated particles with app. 70 and 40% during single-drop and rotating drum dustiness tests, respectively. Compaction of Nanofil^®5 reduced the dustiness in the single-drop test, but it was more than doubled in the rotating drum test. Physically relevant low-pressure compaction may reduce the risk of particle exposure if powders are handled in operations with few agitations such as pouring or tapping. Repeated agitation, e.g., mixing, of these compacted powders, would result in reduced (app. 20% for Bentonite) or highly increased (app. 225% for Nanofil^®5) dustiness and thereby alter the exposure risk significantly.     

Improvement of photocatalytic behavior of chemical-vapor-synthesized TiO2 nanopowders by post-heat treatment

Anatase-type TiO₂ nanopowders less than 10 nm in average diameter were synthesized by a chemical vapor synthesis method. The TiO₂ nanopowders showed very poor photocatalytic properties, in spite of their large surface area. With subsequent heat treatment of the TiO₂ powders, their photocatalytic properties determined by measuring the degradation of 2-propanol were improved at temperatures up to 600 °C and then diminished along with formation of a rutile phase. This improvement in the photocatalytic properties of TiO₂ nanopowders was attributed to both a morphology change and a change in the electronic surface characteristics of TiO₂ particles during heat treatment.     

Surface-modified antibacterial TiO2/Ag nanoparticles: Preparation and properties

Studies were performed on surface modification of antibacterial TiO₂/Ag⁺ nanoparticles by grafting γ-aminopropyltriethoxysilane (APS). The interfacial structure of the modified particles was characterized by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis. The thickness of the surface layer was determined by using Auger electron spectroscopy (AES). The results show that APS is chemically bonded to the surface of antibacterial TiO₂/Ag⁺ nanoparticles. Furthermore, the modified particles were mixed in PVC to prepare composites whose antibacterial property was investigated. The results suggest that surface modification has no negative effect on antibacterial activity of TiO₂/Ag⁺ nanoparticles and PVC-TiO₂/Ag⁺ composites exhibits good antibacterial property.     

Influence of growth temperature of TiO2 buffer on structure and PL properties of ZnO films

A series of ZnO films with TiO₂ buffer on Si (1 0 0) substrates were prepared by DC reactive sputtering. Growth temperature of TiO₂ buffer changed from 100 °C to 400 °C, and the influence on the crystal structures and optical properties of ZnO films have been investigated. The XRD results show that the ZnO films with TiO₂ buffer have a hexagonal wurtzite structure with random orientation, and with the increase of growth temperature of TiO₂ buffer, the residual stresses were released gradually. Specially, the UV emission enhanced distinctly and FWHMs (full width half maximum) decreased linearly with the increasing TiO₂ growth temperature. The results all come from the improvement of crystal quality of ZnO films.     

Evaluation of nanoparticle emission for TiO<Subscript>2</Subscript> nanopowder coating materials

In this study, nanoparticle emission of TiO₂ nanopowder coated on different substrates including wood, polymer, and tile, was evaluated in a simulation box and measured with a Scanning Mobility Particle Sizer (SMPS) for the first time. The coating process for the substrate followed the instructions given by the supply company. In the simulation box, UV light, a fan, and a rubber knife were used to simulate the sun light, wind, and human contacting conditions. Among the three selected substrates, tile coated with TiO₂ nanopowder was found to have the highest particle emission (22 #/cm³ at 55 nm) due to nanopowder separation during the simulation process. The UV light was shown to increase the release of particle below 200 nm from TiO₂ nanopowder coating materials. The results show that, under the conditions of UV lamps, a fan and scraping motion, particle number concentration or average emission rate decreases significantly after 60 and 90 min for TiO₂/polymer and TiO₂/wood, respectively. However, the emission rate continued to increase after 2 h of testing for TiO₂/tile. It is suggested that nanoparticle emission evaluation is necessary for products with nanopowder coating.     

Aerosol characterization and lung deposition of synthesized TiO2 nanoparticles for murine inhalation studies

This study presents a novel exposure protocol for synthesized nanoparticles (NPs). NPs were synthesized in gas phase by thermal decomposition of metal alkoxide vapors in a laminar flow reactor. The exposure protocol was used to estimate the deposition fraction of titanium dioxide (TiO₂) NPs to mice lung. The experiments were conducted at aerosol mass concentrations of 0.8, 7.2, 10.0, and 28.5 mg m^?3. The means of aerosol geometric mobility diameter and aerodynamic diameter were 80 and 124 nm, and the geometric standard deviations were 1.8 and 1.7, respectively. The effective density of the particles was approximately from 1.5 to 1.7 g cm^?3. Particle concentration varied from 4 × 10⁵ cm^?3 at mass concentrations of 0.8 mg m^?3 to 12 × 10⁶ cm^?3 at 28.5 mg m^?3. Particle phase structures were 74% of anatase and 26% of brookite with respective crystallite sized of 41 and 6 nm. The brookite crystallites were approximately 100 times the size of the anatase crystallites. The TiO₂ particles were porous and highly agglomerated, with a mean primary particle size of 21 nm. The specific surface area of TiO₂ powder was 61 m² g^?1. We defined mice respiratory minute volume (RMV) value during exposure to TiO₂ aerosol. Both TiO₂ particulate matter and gaseous by-products affected respiratory parameters. The RMV values were used to quantify the deposition fraction of TiO₂ matter by using two different methods. According to individual samples, the deposition fraction was 8% on an average, and when defined from aerosol mass concentration series, it was 7%. These results show that the exposure protocol can be used to study toxicological effects of synthesized NPs.     

ZnO–TiO2 nanocomposites formed under submerged DC arc discharge: preparation,characterization and photocatalytic properties

A rutile TiO₂ (α-TiO₂) and hexagonal wurtzite ZnO nanocomposite was directly and synchronously synthesized via arc discharge method submerged in de-ionized water. In correlation with the detailed characterization of the morphology, and crystalline structure of the prepared ZnO–TiO₂ nanocomposites, the UV–visible and photoluminescence properties were studied. X-ray diffraction and transmission electron microscopy investigations revealed the co-existence of α-TiO₂ and hexagonal wurtzite ZnO phases with the ZnO and α-TiO₂ nanoparticles are in nanorod and nanospheres morphologies, respectively. The diameters of the synthesized nanocomposite particles are in the range of 5–70 nm. Interestingly, the as-prepared ZnO–TiO₂ nanocomposite shows better photocatalytic activity for photodegradation of the methylene blue dye than both of pure ZnO and TiO₂ nanocatalyts. This work would explore feasible routes to synthesize efficient metal or/and metal oxide nanocomposites for degrading organic pollutants, gas sensing or other related applications.     

Experimental evaluation of individual protection devices against different types of nanoaerosols: graphite,TiO<Subscript>2,</Subscript> and Pt

In this study different conventional individual protection devices, well-qualified for submicron particles were tested for different types of polydispersed nanoaerosols of TiO₂, Pt, and graphite. The electrical mobility diameters of the generated particles are ranging from 9 to 19 nm for Pt, 9 to 90 nm for TiO₂, and 15 to 90 nm for graphite. Toward this purpose, two specific test benches were used: one for the filter-based devices which are tested under a controlled air flow, and the other one for protective clothing and gloves under diffusion and without air flow. Different types of nanoaerosols, such as TiO₂, Pt, and graphite, were generated. Electrostatic and HEPA (High Efficiency Particle Air) filters have shown the highest efficiency for graphite nanoparticles. The main hypothesis for explaining this effect is that electrostatic forces could enhance the graphite nanoparticles capture. Air-tight fabrics made of non-woven textile seem much more efficient in protecting workers against Pt, and TiO₂ nanoparticles than cotton and polypropylene. With regard to protective clothing, no obvious effect linked to the aerosol type was observed. Gloves are found very efficient for TiO₂ and Pt nanoaerosols. Therefore, no effect of aerosol on the protection efficiency of gloves was evidenced.     

Anatase TiO<Subscript>2</Subscript> nanoparticles for lithium-ion batteries

Anatase TiO₂ nanoparticles were prepared by a simple sol-gel method at moderate temperature. X-ray powder diffraction (XRD) and Raman spectroscopy revealed the exclusive presence of anatase TiO₂ without impurities such as rutile or brookite TiO₂. Thermogravimetric analysis confirmed the formation of TiO₂ at about 400 °C. Particle size of about 20 nm observed by transmission electron microscopy matches well with the dimension of crystallites calculated from XRD. The electrochemical tests of the sol-gel-prepared anatase TiO₂ show promising results as electrode for lithium-ion batteries with a stable specific capacity of 174 mAh g^?1 after 30 cycles at C/10 rate. The results show that improvement of the electrochemical properties of TiO₂ to reach the performance required for use as an electrode for lithium-ion batteries requires not only nanosized porous particles but also a morphology that prevents the self-aggregation of the particles during cycling.     

X-ray and AFM studies of polydisperse TiO2 (anatase) particles

Titanium dioxide (TiO₂) materials of a high chemical purity, as-prepared by the thermal hydrolysis, as well as subsequently modified by adsorption of different metal cations (Fe³⁺, Co²⁺, Cu²⁺), have been investigated by the X-ray diffraction, X-ray fluorescence and AFM microscopy methods. All TiO₂ powders have a fine-dispersated anatase structure and consist of grown together nanocrystallites of ∼8-17 nm. TiO₂ particles, usually ranging from 100 to 600 nm, show the ability to form large agglomerates, up to 2 μm in size. Contrary to the pure anatase, metal-modified TiO₂ particles possess a positive charge on their surface and can be lifted away by the AFM tip from the substrate surface during the scanning. This effect is mostly pronounced for the Fe-modified TiO₂ sample, where particles up to 250 nm are removed. The possible interaction mechanisms between different TiO₂ particles and the silicon tip are discussed. The electrostatic force has been found to play an essential role in the sample-tip interaction processes, and its value depends on the type of metal cation used.     

Light-induced antifungal activity of TiO2 nanoparticles/ZnO nanowires

Antifungal activity of TiO₂/ZnO nanostructures under visible light irradiation was investigated. A simple chemical method was used to synthesize ZnO nanowires. Zinc acetate dihydrate, Polyvinyl Pyrrolidone and deionized water were used as precursor, capping and solvent, respectively. TiO₂ nanoparticles were deposited on ZnO nanowires using an atmospheric pressure chemical vapor deposition system. X-ray diffraction pattern of TiO₂/ZnO nano-composite has represented the diffraction peaks relating to the crystal planes of the TiO₂ (anatase and rutile) and ZnO. TiO₂/ZnO nanostructure antifungal effect on Candida albicans biofilms was studied and compared with the activity of TiO₂ nanoparticles and ZnO nanowires. The high efficiency photocatalytic activity of TiO₂ nanoparticles leads to increased antifungal activity of ZnO nanowires. Scanning electron microscope was utilized to study the morphology of the as prepared nanostructures and the degradation of the yeast.     

Synthesis and gas sensing characteristic based on metal oxide modification multi wall carbon nanotube composites

A new type of gas sensing material based on metal oxide modification multi wall carbon nanotube (MO/MWCNT) composites is presented since the interface between the composites enhance the carrier density so as to improve the gas sensitivity. Three kinds of MO/MWCNT composite materials, such as ZnO/MWCNT, SnO₂/MWCNT and TiO₂/MWCNT, have been acquired in situ growth using catalytic pyrolysis method. The MO nano particles have decorated on side of MWCNTs, whereas the introduction of SnO₂ nano particles makes part of MWCNT showing two-dimensional form of carbon nano-wall structure. Among four kinds of cathode of ZnO/MWCNTs, SnO₂/MWCNTs, TiO₂/MWCNTs and pure MWCNT composite film, TiO₂/MWCNTs composite has the lowest threshold electric field required to draw current of 12 μA has been found to be ∼1.2 V/μm, and also TiO₂/MWCNTs composite has the highest sensitivity of 16% to ethanol. The TiO₂/MWCNTs composite is superior to the others both in vacuum electron transportation and gas sensitivity.     

超亲水性SiO2-TiO2纳米颗粒阵列结构的制备与性能研究

用分子自组装的方法在玻璃衬底上分别制备了TiO₂纳米颗粒层和SiO₂-TiO₂复合纳米颗粒阵列结构. 其中,SiO₂ 纳米颗粒层用旋涂法制备,得到密排阵列结构,而TiO₂纳米颗粒层则用浸渍提拉法制备. 文章分析了TiO₂纳米颗粒层和SiO₂-TiO₂复合纳米颗粒阵列结构的理论粗糙度,并通过扫描电子显微镜研究了它们的微观结构,用接触角 关键词： 自清洁 表面粗糙度 光催化 分子自组装     

Comparison of four mobility particle sizers with different time resolution for stationary exposure measurements

Exposure to airborne ultrafine and nanoparticles has raised increased interest over the recent years as they may cause adverse health effects. A common way to quantify exposure to airborne particles is to measure particle number size distributions through electrical mobility analysis. Four mobility particle sizers have been subject to a detailed intercomparison study, a TSI Fast Mobility Particle Sizer (FMPS), a Grimm Sequential Mobility Particle Sizer (SMPS+C), and two TSI Scanning Mobility Particle Sizers (SMPSs), equipped with two different condensation particle counters (CPC). The instruments were challenged with either NaCl or diesel soot particles. The results indicate that the sizing of all tested instrument was similar with only the FMPS size distributions consistently shifted toward smaller particle sizes. The Grimm SMPS generally measured higher concentrations and broader distributions than the TSI instruments. The two Grimm DMAs agreed well with each other; however, the TSI SMPS results showed a reproducible dependence on the flow rates. While TSI and Grimm SMPS delivered consistent results for sodium chloride (NaCl) and diesel soot, the FMPS seemed to react differently to the changing particle source than the SMPSs, which may be caused by either the different morphology or particle size dependent effects. For NaCl particles, the FMPS delivered the narrowest distributions and concentrations comparable with TSI SMPSs, whereas for diesel soot, it delivered the broadest distributions and higher concentrations than TSI SMPSs.     

Particle Sampling and Real Time Size Distribution Measurement in H2/O2/TEOS Diffusion Flame

Growth characteristics of silica particles have been studied experimentally using in situ particle sampling technique from H₂/O₂/Tetraethylorthosilicate (TEOS) diffusion flame with carefully devised sampling probe. The particle morphology and the size comparisons are made between the particles sampled by the local thermophoretic method from the inside of the flame and by the electrostatic collector sampling method after the dilution sampling probe. The Transmission Electron Microscope (TEM) image processed data of these two sampling techniques are compared with Scanning Mobility Particle Sizer (SMPS) measurement. TEM image analysis of two sampling methods showed a good agreement with SMPS measurement. The effects of flame conditions and TEOS flow rates on silica particle size distributions are also investigated using the new particle dilution sampling probe. It is found that the particle size distribution characteristics and morphology are mostly governed by the coagulation process and sintering process in the flame. As the flame temperature increases, the effect of coalescence or sintering becomes an important particle growth mechanism which reduces the coagulation process. However, if the flame temperature is not high enough to sinter the aggregated particles then the coagulation process is a dominant particle growth mechanism. In a certain flame condition a secondary particle formation is observed which results in a bimodal particle size distribution.     

ZnO/TiO2 core–shell heterojunction for CdS and PbS quantum dot-cosensitized solar cells

ZnO nanorods (NRs) with regular morphology were prepared through hydrothermal method, and the TiO₂ shell was assembled onto the surface of ZnO NRs by spin coating to the ZnO/TiO₂ core–shell heterojunction. CdS and PbS quantum dots (QDs) were used to cosensitize the ZnO/TiO₂ nanostructure by direct adsorption (DA) and successive ionic layer adsorption and reaction, respectively. SEM, TEM, and HRTEM images show that the samples possessed a rough surface and four lattice fringes indicating the successful synthesis of the ZnO/TiO₂/CdS/PbS composite structure. The ZnO/TiO₂(10T)/CdS/PbS sample showed a high absorption intensity at a broad range of wavelength to visible light region. The ZnO/TiO₂(10T)/CdS/PbS photoelectrode with QDSSCs showed the highest IPCE of 36.04% and photoelectric efficiency (η) of 1.59%; these values increased by approximately 550% and 150% compared with those of unsensitized ZnO (0.29%) and ZnO/TiO₂(10T) (1.04%) and about 146% and 120% compared with those of ZnO/TiO₂(10T)/CdS and ZnO/TiO₂(10T)/PbS, respectively. The fill factor was 0.36, and the photocurrent density (J_sc) and open circuit voltage (V_oc) reached the maximum values of 9.73 mA cm⁻² and 0.46 V, respectively.     

Synthesis of TiO2 nanorods by oriented attachment using EDTA modifier: a novel approach towards 1D nanostructure development

The synthesis of TiO₂ nanorods with anatase structure has been achieved from the necking of truncated nanoparticles by oriented attachment using titanium ethylenediaminetetraacetic acid (EDTA) chelated complex as a molecular precursor. The preparation was carried out under mild conditions using a simple solvothermal process. The influence of EDTA over the growth of nanocrystallites and the various other factors which contribute to the development of 1D TiO₂ nanostructure are investigated. At a relatively lower temperature, titania nanopowders are obtained, and the anatase phase crystallization is verified by wide angle X-ray diffraction. The evolution of rod-shaped TiO₂ with tapered edges has been confirmed by transmission electron micrographs. The well aligned lattice fringes of TiO₂ nanorod towards [001] direction is investigated by HRTEM. The SEM images show the surface configuration of overall aggregates of titania crystallites consisted of primary particles which are densely packed in an orderly texture. The moderate shift in the absorption band towards higher energy region of the absorption spectrum confirms the weak carrier confinement effect in the sample.     

Comparison of nanoparticle measurement instruments for occupational health applications

Nanoparticles are used in many applications because of their novel properties compared to bulk material. A growing number of employees are working with nanomaterials and their exposure to nanoparticles trough inhalation must be evaluated and monitored continuously. However, there is an ongoing debate in the scientific literature about what are the relevant parameters to measure to evaluate exposure to level. In this study, three types of nanoparticles (ammonium sulphate, synthesised TiO₂ agglomerates and aerosolised TiO₂ powder, modes in a range of 30–140 nm mobility size) were measured with commonly used aerosol measurement instruments: scanning and fast mobility particle sizers (SMPS, FMPS), electrical low pressure impactor (ELPI), condensation particle counter (CPC) together with nanoparticle surface area monitor (NSAM) to achieve information about the interrelations of the outputs of the instruments. In addition, the ease of use of these instruments was evaluated. Differences between the results of different instruments can mainly be attributed to the nature of test particles. For spherical ammonium sulphate nanoparticles, the data from the instruments were in good agreement while larger differences were observed for particles with more complex morphology, the TiO₂ agglomerates and powder. For instance, the FMPS showed a smaller particle size, a higher number concentration and a narrower size distribution compared with the SMPS for TiO₂ particles. Thus, the type of the nanoparticle was observed to influence the data obtained from these different instruments. Therefore, care and expertise are essential when interpreting results from aerosol measurement instruments to estimate nanoparticle concentrations and properties.