Gold,silver, and palladium nanoparticle/nano-agglomerate generation,collection, and characterization

Generation, collection, and characterization of gold, silver, and palladium nanoparticles and nano-agglomerates (collectively “nanoparticles”) have been explored. The nanoparticles were generated with a spark aerosol generator (Palas GFG-1000). They were collected using a deposition cell under diffusion and thermophoresis. The shapes and sizes of the deposited particles were measured using transmission electron microscopy (TEM). TEM images showed that the particles were in the range of 8–100 nm in diameter, and their shapes varied from nearly spherical to highly non-spherical. Thermophoresis enhanced the deposition of nanoparticles (over the diffusive or the isothermal deposition) in all cases. Further, the size distributions of the nanoparticles generated in the gas phase (aerosol) were measured using a scanning mobility particle sizer (SMPS 3080, TSI) spectrometer. The SMPS results show that an increase in the spark frequency of the generator shifted the size distributions of the nanoparticles to larger diameters, and the total particle mass production rate increased linearly with increase in the spark frequency. The computational fluid dynamics code Fluent (Ansys) was used to model the flow in the deposition cell, and the computed results conform to the observations.     

Colloidal synthesis of BaF2 nanoparticles and their application as fillers in polymer nanocomposites

Nanoparticles of pure and Eu-doped BaF₂ have been prepared through sol-gel colloidal synthesis. In addition, BaF₂-filled PMMA polymer nanocomposites were fabricated and dielectric properties were measured. The as-synthesized pure and Eu-doped BaF₂ nanoparticles were analyzed by both X-ray diffraction and transmission electron microscopy and consisted of crystalline BaF₂ particles with an average diameter of 13.6 nm with a standard deviation of about ±2.4 nm. The photoluminescence properties of the pure and Eu-doped (2%, 4% and 8%) nanoparticles showed characteristic emission of Eu³⁺ (⁵D₀→⁷F _J (J=1–4) transitions). We also measured significantly enhanced dielectric breakdown strength of up to 30% for BaF₂ nanocomposites over the unfilled PMMA polymer. This study thus offers some promise of sol-gel synthesis of nanocomposite dielectrics with great potential for use as electrical insulation materials in cryogenic high-voltage applications.     

Sticking efficiency of nanoparticles in high-velocity collisions with various target materials

In order to find reliable collector surfaces for the Mesospheric Aerosol – Genesis, Interaction and Composition (MAGIC) sounding rocket experiment, intended to collect atmospheric nanoparticles, the sticking efficiency of nanoparticles was measured on several targets of different materials. The nanoparticles were generated by a molecular beam apparatus in Jena, Germany, by laser ablation (Al₂O₃ particles, diameter 5–50 nm) and by laser pyrolysis (carbon particles, diameter 10–20 nm). In a vacuum environment (>10⁻⁵ mbar) the particles condensed from the gas phase, formed a particle beam, and were accelerated to ∼ ∼1 km/s. The sticking efficiency on the target materials carbon, gold and grease was measured by a microbalance. Results demonstrate moderate to high sticking probabilities. Thus, the capture and retrieval of atmospheric nanoparticles was found to be quantitatively feasible.     

Effect of surrounding gas temperature on the morphological evolution of TiO2 nanoparticles generated by laser ablation in tubular furnace

Titanium oxide nanoparticles are synthesized by laser ablation of Ti target in oxygen atmosphere under well-controlled temperature profiles in a tubular furnace. The size and the shape of generated nanoparticles are varied by changing the temperature of furnace. The mobility-based size distributions of generated air-borne nanoparticles are measured using a scanning mobility particle sizer, and the size distributions of primary particles are analyzed by a scanning electron microscope. When the particles are generated by laser ablation at the room temperature, the particles are agglomerates in gas phase with the average mobility diameter of 117 nm and the mean diameter of primary particles of 11 nm. The primary particle diameter increases from 11 to 24 nm by raising the furnace temperature up to 800 °C. Since the mass of Ti vapor ablated from a target is found to be constant regardless of the furnace temperature, this particle growth may be attributed to the reduction in nuclei number as a result of mild quenching at higher temperatures. As the temperature reaches higher than 1,000 °C, the mobility diameter suddenly drops and the primary particle diameter increases due to sintering, and at 1,200 °C the mobility diameter coincides with the primary particle diameter. Since the laser oven method offers an independent control of vapor concentration and the temperature of surrounding atmosphere, it is an effective tool to study the formation process of nanoparticles from primary particles with a given size.     

Inertial deposition of nanoparticle chain aggregates: Theory and comparison with impactor data for ultrafine atmospheric aerosols

Nanoparticle chain aggregates (NCAs) are often sized and collected using instruments that rely on inertial transport mechanisms. The instruments size segregate aggregates according to the diameter of a sphere with the same aerodynamic behavior in a mechanical force field. A new method of interpreting the aerodynamic diameter of NCAs is described. The method can be used to calculate aggregate surface area or volume. This is useful since inertial instruments are normally calibrated for spheres, and the calibrations cannot be directly used to calculate aggregate properties. A linear relationship between aggregate aerodynamic diameter and primary particle diameter based on published Monte-Carlo drag calculations is derived. The relationship shows that the aggregate aerodynamic diameter is independent of the number of primary particles that compose an aggregate, hence the aggregate mass. The analysis applies to aggregates with low fractal dimension and uniform primary particle diameter. This is often a reasonable approximation for the morphology of nanoparticles generated in high temperature gases. An analogy is the use of the sphere as an approximation for compact particles. The analysis is applied to the collection of NCAs by a low-pressure impactor. Our results indicate the low-pressure impactor collects aggregates with a known surface area per unit volume on each stage. Combustion processes often produce particles with aggregate structure. For diesel exhaust aggregates, the surface area per unit volume calculated by our method was about twice that of spheres with diameter equal to the aerodynamic diameter. Measurements of aggregates collected near a major freeway and at Los Angeles International Airport (LAX) were made for two aerodynamic cutoff diameter diameters (d _a,50), 50 and 75 nm. (Aerodynamic cutoff diameter refers to the diameter of particles collected with 50% efficiency on a low-pressure impactor stage.) Near-freeway aggregates were probably primarily a mixture of diesel and internal combustion engine emissions. Aggregates collected at LAX were most likely present as a result of aircraft emissions. In both measurements, the aggregate aerodynamic diameters calculated from the primary particle diameter were fairly close to the stage cutoff diameter. The number of primary particles per aggregate varied one order of magnitude for particles depositing on the same stage. The average aggregate surface area per unit volume was 2.41 × 10⁶ cm⁻¹ and 2.59 × 10⁶ cm⁻¹ (50 nm d _a,50) and 1.81 × 10⁶ cm⁻¹ and 1.68 × 10⁶ cm⁻¹ (75 nm d _a,50) for near-freeway and LAX measurements, respectively. These preliminary measurements are consistent with values calculated from theory.     

Generation of nanoparticles by spark discharge

The production of nanoparticles by microsecond spark discharge evaporation in inert gas is studied systematically applying transmission electron microscopy, mobility analysis and BET surface area measurement. The method of spark discharge is of special interest, because it is continuous, clean, extremely flexible with respect to material, and scale-up is possible. The particle size distributions are narrow and the mean primary particle size can be controlled via the energy per spark. Separated, unagglomerated particles, 3–12 nm in size, or agglomerates can be obtained depending on the flow rate. The nanoparticulate mass produced is typically 5 g/kWh. A formula is given, which estimates the mass production rate via thermal conductivity, evaporation enthalpy and the boiling point of the material used. We showed that with gas purified at the spot, the method produced gold particles that were so clean that sintering of agglomerated particles occurred at room temperature. The influence of a number of parameters on the primary particle size and mass production rate was studied and qualitatively understood with a model of Lehtinen and Zachariah (J Aerosol Sci 33:357–368, 2002). Surprisingly high charging probabilities for one polarity were obtained. Spark generation is therefore of special interest for producing monodisperse aerosols or particles of uniform size via electrical mobility analysis. Qualitative observations in the present study include the phenomenon of material exchange between the electrodes by the spark, which opens the possibility of producing arbitrary mixtures of materials on a nanoscale. If spark generation of nanoparticles is performed in a standing or almost standing gas, an aerogel of a web-like structure forms between surfaces of different electrical potential.     

Combined synthesis and in situ coating of nanoparticles in the gas phase

Ga₂O₃ was-synthesized by doping a premixed H₂/O₂/Ar flat flame with diluted trimethyl gallium Ga(CH₃)₃ in a low-pressure reactor. The mean particle diameter d _p of the resulting metal oxide was characterized in-situ with a particle mass spectrometer (PMS), and was observed to range between 2.5 nm ≤ d _p ≤ 6.5 nm. XRD results show that the as-synthesized Ga₂O₃ nanoparticles are mostly amorphous, although, a few broad reflexes were observed that indicate the presence of some degree of crystallinity. Thermal annealing of the as-synthesized material at 1000 °C for 5 min yielded β-Ga₂O₃ with a monoclinic structure. UV–VIS measurements indicate strong absorption in the UV range (4.8 eV), which corresponds quite well to the direct band gap of bulk Ga₂O₃. Photoluminescence (PL) measurements of the as-synthesized metal oxide show a broad emission ranging from 350 nm to 600 nm with a maximum at 460 nm. Crystalline β-Ga₂O₃ exhibited stronger luminescence than as-synthesized particles.     

Size dependence of complex refractive index function of growing nanoparticles

The evidence of the change of the complex refractive index function E(m) of carbon and iron nanoparticles as a function of their size was found from two-color time-resolved laser-induced incandescence (TiRe-LII) measurements. Growing carbon particles were observed from acetylene pyrolysis behind a shock wave and iron particles were synthesized by pulse Kr–F excimer laser photo-dissociation of Fe(CO)₅. The magnitudes of refractive index function were found through the fitting of two independently measured values of particle heat up temperature, determined by two-color pyrometry and from the known energy of the laser pulse and the E(m) variation. Small carbon particles of about 1–14 nm in diameter had a low value of E(m)∼0.05–0.07, which tends to increase up to a value of 0.2–0.25 during particle growth up to 20 nm. Similar behavior for iron particles resulted in E(m) rise from ∼0.1 for particles 1–3 nm in diameter up to ∼0.2 for particles >12 nm in diameter.     

Exposure assessment of nano-sized and respirable particles at different workplaces

In this study, nanoparticle (NP, diameter < 100 nm) and respirable particles measurements were conducted at three different nanopowder workplaces, including the mixing area of a nano-SiO₂-epoxy molding compound plant (primary diameter: 15 nm), bagging areas of a nano-carbon black (nano-CB) (primary diameter: 32 nm) and a nano-CaCO₃ (primary diameter: 94 nm) manufacturing plant. Chemical analysis of respirable particle mass (RPM) and NPs was performed to quantify the content of manufactured nanoparticles in the collected samples. Nanopowder products obtained from the plants were used in the laboratory dustiness testing using a rotating drum tester to obtain particle mass and number distributions. The obtained laboratory data were then used to elucidate the field data. Both field and laboratory data showed that NP number and mass concentrations of manufactured materials were close to the background level. Number concentration was elevated only for particles with the electrical mobility diameter >100 nm during bagging or feeding processes, unless there were combustion-related incidental sources existed. Large fraction of nanomaterials was found in the RPM due to agglomeration of nanomaterials or attachment of nanomaterials to the larger particles. From this study, it is concluded that RPM concentration measurements are necessary for the exposure assessment of nanoparticles in workplaces.     

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.     

Structural properties of silver nanoparticle agglomerates based on transmission electron microscopy: relationship to particle mobility analysis

In this work, the structural properties of silver nanoparticle agglomerates generated using condensation and evaporation method in an electric tube furnace followed by a coagulation process are analyzed using Transmission Electron Microscopy (TEM). Agglomerates with mobility diameters of 80, 120, and 150 nm are sampled using the electrostatic method and then imaged by TEM. The primary particle diameter of silver agglomerates was 13.8 nm with a standard deviation of 2.5 nm. We obtained the relationship between the projected area equivalent diameter (d _pa) and the mobility diameter (d _m), i.e., d _pa = 0.92 ± 0.03 d _m for particles from 80 to 150 nm. We obtained fractal dimensions of silver agglomerates using three different methods: (1) D _f = 1.84 ± 0.03, 1.75 ± 0.06, and 1.74 ± 0.03 for d _m = 80, 120, and 150 nm, respectively from projected TEM images using a box counting algorithm; (2) fractal dimension (D _fL) = 1.47 based on maximum projected length from projected TEM images using an empirical equation proposed by Koylu et al. (1995) Combust Flame 100:621–633; and (3) mass fractal-like dimension (D _fm) = 1.71 theoretically derived from the mobility analysis proposed by Lall and Friedlander (2006) J Aerosol Sci 37:260–271. We also compared the number of primary particles in agglomerate and found that the number of primary particles obtained from the projected surface area using an empirical equation proposed by Koylu et al. (1995) Combust Flame 100:621–633 is larger than that from using the relationship, d _pa = 0.92 ± 0.03 d _m or from using the mobility analysis.     

Quantum Gravitational Corrections to the Real Klein-Gordon Field in the Presence of a Minimal Length

The (D+1)-dimensional (β,β′)-two-parameter Lorentz-covariant deformed algebra introduced by Quesne and Tkachuk (J. Phys., A Math. Gen. 39, 10909, 2006), leads to a nonzero minimal uncertainty in position (minimal length). The Klein-Gordon equation in a (3+1)-dimensional space-time described by Quesne-Tkachuk Lorentz-covariant deformed algebra is studied in the case where β′=2β up to first order over deformation parameter β. It is shown that the modified Klein-Gordon equation which contains fourth-order derivative of the wave function describes two massive particles with different masses. We have shown that physically acceptable mass states can only exist for b < \frac18m²c²\beta<\frac{1}{8m^{2}c^{2}} which leads to an isotropic minimal length in the interval 10⁻¹⁷ m<(ΔX ⁱ )₀<10⁻¹⁵ m. Finally, we have shown that the above estimation of minimal length is in good agreement with the results obtained in previous investigations.     

Measurement of electric field strengths in a waveguide by means of the dynamic Stark effect in hydrogen and neutral helium spectral lines

The dynamic Stark effect of the spectral lines H_β and of the neutral helium lines λ=402.6 nm (2³ P ⁰−5³ D) and λ=438.8 nm (2¹ P ⁰−5¹ D) emitted from a discharge tube was used for probing rf electric fields in a transverse waveguide. Calculations accounting for the pertubation of the atomic states by strong unidirectional fields prove to be suitable in order to interprete the main experimental results. If the waveguide is terminated with a metallic reflector and the plasma in the discharge tube becomes overdense—then representing a slightly permeable mirror—a resonant enhancement of the electric field strength may be achieved by tuning. This enhancement is well recognizable in the spectral line contours.     

Silicon nanoparticles produced by spark discharge

On the example of silicon, the production of nanoparticles using spark discharge is shown to be feasible for semiconductors. The discharge circuit is modelled as a damped oscillator circuit. This analysis reveals that the electrode resistance should be kept low enough to limit energy loss by Joule heating and to enable effective nanoparticle production. The use of doped electrodes results in a thousand-fold increase in the mass production rate as compared to intrinsic silicon. Pure and oxidised uniformly sized silicon nanoparticles with a primary particle diameter of 3–5 nm are produced. It is shown that the colour of the particles can be used as a good indicator of the oxidation state. If oxygen and water are banned from the spark generation system by (a) gas purification, (b) outgassing and (c) by initially using the particles produced as getters, unoxidised Si particles are obtained. They exhibit pyrophoric behaviour. This continuous nanoparticle preparation method can be combined with other processing techniques, including surface functionalization or the immediate impaction of freshly prepared nanoparticles onto a substrate for applications in the field of batteries, hydrogen storage or sensors.     

Optical properties of pyridine funtionalized TbF<Subscript>3</Subscript> nanoparticles

The preparation of pyridine functionalized TbF₃ nanoparticles are described in this report. Synthesized nanoparticles were characterized using the TEM, UV/Vis, FTIR and photoluminescence spectroscopy. TEM micrograph reveals the nanorod shaped, uniform in size with a particles size in the range of 20–30 nm. FTIR spectrum shown characteristic absorption bands of pyridine and a small intensity band at 411 cm⁻¹ corresponding metal nitrogen ν(Tb–N) bonding. Uv-vis spectrum shown the characteristic absorption transitions of Tb³⁺ ion. A strong emission transition at 540 nm (⁵D₄ → ⁷F₅) was observed on excite by visible light at 414 nm.     

Surfing and generation of cosmic rays in relativistic shock waves

We consider the problem of cosmic-ray generation through the surfing acceleration of charged particles in relativistic magnetosonic shock waves (the branch of fast magnetic sound) propagating in magnetized space plasmas. The dependence of the particle surfing acceleration efficiency on the angle θ _Bn between the normal to the shock front plane and the magnetic field vector in the plasma upstream of the shock is analyzed in detail. We show that for angles satisfying the condition χ = βΓ tan θ _Bn ⩾ 1, where β = U/c, Γ = (1 − β)^{2 −1/2}, U is the shock velocity, and c is the speed of light, the particles can theoretically be accelerated through surfing for an unlimited time and can gain an unlimited energy. For angles satisfying the condition χ < 1, the kinetic energy ℰ of the particles is limited by ℰ = 2mc ²χ²/(1 − χ²) (m is the particle rest mass). Our main conclusion is that the generation of cosmic rays through the surfing acceleration of particles in the front of a relativistic shock wave for Γ ≫ 1 is also efficient when the angle θ _Bn is very small, i.e., it differs significantly from a right angle. Estimates for the energies of particles accelerated through surfing in relativistic jets are provided.     

Nonlinear optical absorption and refraction in Ru, Pd, and Au nanoparticle suspensions

We present the results of studies of the nonlinear optical properties of Pd, Ru, and Au nanoparticles. We studied the nonlinear refraction and nonlinear absorption of suspensions of these nanoparticles at 1064-nm wavelength. A relatively strong nonlinear absorption of the Pd nanoparticles was observed in the case of 1064-nm, 50-ps pulses (β=2×10⁻⁹ m W⁻¹). The Ru and Pd nanoparticles showed weak negative nonlinear refraction (γ∼−(6–8)×10⁻¹⁶ m² W⁻¹) in this spectral range. In the case of the Au nanoparticles, a saturated absorption at 532 nm dominated over other nonlinear optical processes.     

Development of three-dimensional turbulent separation in the neighborhood of incident crossing shock waves

The results are presented for experimental investigation of the peculiarities of the development of three-dimensional turbulent separated flows on a flat surface for the Mach number M_∞ = 4 and the Reynolds number Re₁ ∼ 55·10⁶ m⁻¹ under the conditions of the flow around two identical cylindrical bodies of revolution of diameter D = 50 mm and the body aspect ratio L _b/D = 5 with conical forebodies with semi-apex angles β_c = 30, 20, 15, and 10° located above plate in parallel to one another and to the flow. The typical stages of the three-dimensional separation development are considered under the reducing distance between the axes of the bodies within the range of Z = Δz/D = 1.06–3.0 at their fixed distance from the surface (Y = Δy/D = 0.96). The topology of limiting streamlines and the peculiarities of pressure fields on the surface as well as the gasdynamic structure of separated flows arising at the interaction of crossing bow shocks propagating from the bodies and at the interaction of secondary disturbances with the boundary layer are analysed.     

Arrays of magnetic nanoparticles capped with alkylamines

Magnetic metal and metal oxide nanoparticles capped with alkylamines have been synthesized and characterized by transmission electron microscopy. X-ray diffraction, energy dispersive X-ray analysis and magnetization measurements. Core-shell Pd-Ni particles with composition, Pd₅₆₁Ni₃₀₀₀, (diameter ∼3.3 nm) are superparamagnetic at 5 K and organize themselves into two-dimensional crystalline arrays. Similar arrays are obtained with Pd₅₆₁Ni₃₀₀₀Pd₁₅₀₀ nanoparticles containing an additional Pd shell. Magnetic spinel particles of γ-Fe₂O₃, Fe₃O₄ and CoFe₂O₄ of average diameters in the 4–6 nm range coated with octylamine are all supermagnetic at room temperature and yield close-packed disordered arrays. Relatively regular arrays are formed by dodecylaminecapped Fe₃O₄ nanoparticles (∼8.6 nm diameter) while well-ordered hexagonal arrays were obtained with octylamine-covered Co₃O₄ nanoparticles (∼4.2 nm diameter).     

Synthesis and characterization of indium–tin oxide (ITO) nanoparticles

Synthesis and characterization of ITO nanoparticles were investigated in the present study. To synthesize the ITO nanoparticles flame spray pyrolysis was introduced. The average particle diameter increased with an increase in the molar concentration of the precursor. Raising the maximum flame temperature by controlling the gas flow rates also led to an increase in the average diameter of the particles. The crystalline ITO nanoparticles were synthesized, and their average primary particle diameters ranged from 11 to 20 nm. ITO thin films were prepared with a sol consisted of the ITO nanoparticles and a polymer binder. Effect of average particle diameter of the ITO nanoparticles on the transparency and the surface resistance of the ITO thin films were measured. As the average particle diameter increased, the transparency and the surface resistance decreased from 92 to 83% and from 1.0 × 10⁴ to 0.8 × 10⁴Ω/□, respectively.