Probing colloidal forces between a Si3N4 AFM tip and single nanoparticles of silica and alumina

The atomic force microscope (AFM) has been used to measure surface forces between silicon nitride AFM tips and individual nanoparticles deposited on substrates in 10(-4) and 10(-2) M KCl solutions. Silica nanoparticles (10 nm diameter) were deposited on an alumina substrate and alumina particles (5 to 80 nm diameter) were deposited on a mica substrate using aqueous suspensions. Ionic concentrations and pH were used to manage attractive substrate-particle electrostatic forces. The AFM tip was located on deposited nanoparticles using an operator controlled offset to achieve stepwise tip movements. Nanoparticles were found to have a negligible effect on long-range tip-substrate interactions, however, the forces between the tip and nanoparticle were detectable at small separations. Exponentially increasing short-range repulsive forces, attributed to the hydration forces, were observed for silica nanoparticles. The effective range of hydration forces was found to be 2-3 nm with the decay length of 0.8-1.3 nm. These parameters are in a good agreement with the results reported for macroscopic surfaces of silica obtained using the surface force apparatus suggesting that hydration forces for the silica nanoparticles are similar to those for flat silica surfaces. Hydration forces were not observed for either alumina substrates or alumina nanoparticles in both 10(-4) M KCl solution at pH 6.5 and 10(-2) M KCl at pH 10.2. Instead, strong attractive forces between the silicon nitride tip and the alumina (nanoparticles and substrate) were observed.     

AFM colloidal forces measured between microscopic probes and flat substrates in nanoparticle suspensions

Colloidal forces between atomic force microscopy probes of 0.12 and 0.58 N/m spring constant and flat substrates in nanoparticle suspensions were measured. Silicon nitride tips and glass spheres with a diameter of 5 and 15 mum were used as the probes whereas mica and silicon wafer were used as substrates. Aqueous suspensions were made of 5-80 nm alumina and 10 nm silica particles. Oscillatory force profiles were obtained using atomic force microscope. This finding indicates that the nanoparticles remain to be stratified in the intervening liquid films between the probe and substrate during the force measurements. Such structural effects were manifested for systems featuring attractive and weak repulsive interactions of nanoparticles with the probe and substrate. Oscillation of the structural forces shows a periodicity close to the size of nanoparticles in the suspension. When the nanoparticles are oppositely charged to the probes, they tend to coat the probes and hinder probe-substrate contact.     

The influence of alumina passivation on nano-Al/Teflon reactions

The reaction kinetics of aluminum (Al) and polytetrafluoroethylene (PTFE or Teflon) were recently examined using nanoparticles of both Al and Teflon. Results showed a unique pre-ignition reaction (PIR) associated with the nano-Al/Teflon mixture that was not significant in the micron-Al/Teflon mixture. The PIR is caused by fluorination of the alumina (Al₂O₃) shell passivating the Al particles and reduces the onset temperature of Al ignition for nano compared with micron particle mixtures. Because the alumina shell was found to play a key role in the reaction mechanism, this communication extends our understanding of the interaction between alumina and Teflon by examining the influence of alumina particle size, and therefore surface area, on the fluorination reaction with Teflon. Differential scanning calorimetry analysis show that reaction kinetics vary dramatically as the alumina particle size is reduced from 50 to 15 nm diameter. Specifically, for 15 nm diameter alumina, the first exotherm (corresponding to the PIR) exhibits three times more heat of reaction than for the 30, 40, or 50 nm alumina particles. These results show how particle size and specific surface area affect the Al–Teflon reaction mechanism.     

Heteroaggregation between Al2O3 submicrometer particles and SiO2 nanoparticles: experiment and simulation

The aggregation process of a two-component dilute system (3 vol %), made of alumina submicrometer particles and silica nanoparticles, is studied by Brownian dynamics simulations. Alumina and silica particles have very different sizes (diameters of 400 and 25 nm, respectively). The particle-particle interaction potential is of the DLVO form. The parameters of the potential are extracted from the experiments. The simulations show that the experimentally observed aggregation phenomena between alumina particles are due to the silica-alumina attraction that induces an effective driving force for alumina-alumina aggregation. The experimental data for silica adsorption on alumina are very well reproduced.     

Synthesis of copper sulphide and copper nanoparticles with microemulsion method

The present work is focused on the synthesis of nanocopper and nanocopper sulphide metallic particles. The precise control of size and shape is best achievable with microemulsion technique, with in situ synthesis in microemulsion. The effect of most crucial operating parameter, water-to-surfactant molar ratio (w), on the product specification including size as well as size distribution and morphology were investigated. The variation of size was observed with variation in w for copper sulphide and copper. Product specifications were analyzed using transmission electron microscope imaging, dynamic light scattering with particle size analyzer and absorption spectra using UV-visible spectrophotometer. It was observed that bigger particles were achieved at higher water-to-surfactant ratio. From systematic study of effect of w on the size and size distribution of copper nanoparticles, the optimum value was chosen for preparation of in situ catalyst. As copper on alumina catalyst has wide catalytic applications of commercial importance, alumina was selected as support. A novel deposition method is developed successfully to deposit the copper nanoparticles from microemulsion on the support. Thus prepared catalyst was analyzed with UV-visible spectrophotometer and found to contain characteristic peak of copper at 655 nm, indicating proper copper deposition on support. XRD analysis of copper on alumina catalyst confirmed presence of metallic copper.     

Preparation of monodisperse SiO2 nanoparticles by membrane emulsification using ideally ordered anodic porous alumina

Monodisperse SiO2 particles of nanometer dimensions were fabricated by membrane emulsification using ideally ordered anodic porous alumina. For the preparation of monodisperse emulsion droplets, the dispersed phase was pressed through a porous alumina membrane into the continuous phase. After solidification treatment of the emulsion droplets, prepared spherical SiO2 nanoparticles with uniform sizes were obtained. From scanning electron microscope observation of the obtained particles, it was confirmed that the size distribution of SiO2 nanoparticles is relatively narrow.     

密堆积六方结构Ni纳米颗粒的制备与表征

采用溶胶-凝胶方法制备前驱体, 将前驱体进行热处理制得密堆积六方结构(hcp)的Ni纳米粉末. 利用TG-DTA, XRD和TEM等测试手段对材料的合成条件、结构、形貌以及结构演变过程进行了分析. 结果表明, 于300 ℃进行热处理所合成的样品为球形的具有密堆六方结构的Ni纳米颗粒, 晶胞参数a=0.2652 nm, c=0.4334 nm, 平均晶粒尺寸约为12 nm. 随着热处理温度的升高, 样品结构发生由密堆六方结构向面心立方结构的转变.     

Metallorganic routes to nanoscale iron and titanium oxide particles encapsulated in mesoporous alumina: formation, physical properties, and chemical reactivity

Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. M?ssbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the M?ssbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From M?ssbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active towards formation of carbon nanotubes by a CVD process. Depending on the reaction conditions, the formation of smaller carbon nanotubes inside the interior of larger carbon nanotubes within the alumina pores can be achieved. This behavior can be understood by means of selectively turning on and off the iron catalyst by adjusting the flow rate of the gaseous carbon precursor in the CVD process.     

Probing the effects of interfacial chemistry on the kinetics of phase transitions in amorphous and tetragonal zirconia nanocrystals

In this work, we examine the phase stability of both uncoated and alumina-coated zirconia nanoparticles using in-situ X-ray diffraction. By tracking structural changes in these particles, we seek to understand how changing interfacial bonding affects the kinetics of amorphous zirconia crystallization and the kinetics of grain growth in both initially amorphous and initially crystalline zirconia nanocrystals. Activation energies associated with crystallization are calculated using nonisothermal kinetic methods. The crystallization of the uncoated amorphous zirconia colloids has an activation energy of 117 +/- 13 kJ/mol, while that for the alumina-coated amorphous colloids is 185 +/- 28 kJ/mol. This increase in activation energy is attributed to inhibition of atomic rearrangement imparted by the alumina coating. The kinetics of grain growth are also studied with nonisothermal kinetic methods. The alumina coating again dramatically affects the activation energies. For colloids that were coated with alumina when they were in an amorphous structure, the coating imparts a 5x increase in the activation energy for grain growth (33 +/- 8 versus 150 +/- 30 kJ/mol). This increase shows that the alumina coating inhibits zirconia cores from coarsening. When the colloids are synthesized in the tetragonal phase and then coated with alumina, the effect of surface coating on coarsening kinetics is even more dramatic. In this case, a 10x increase in activation energies, from 28 +/- 3 kJ/mol for the uncoated particles to 300 +/- 25 kJ/mol for the alumina-coated crystallites, is found. The results show that one can alter phase stability in colloidal systems by using surface coatings and interfacial energy to dramatically change the kinetic barriers to structural rearrangement.     

Attachment of nanoparticles to the AFM tips for direct measurements of interaction between a single nanoparticle and surfaces

Here we report a universal method of attachment/functionalization of tips for atomic force microscope (AFM) with nanoparticles. The particles of interest are glued to the AFM tip with epoxy. While the gluing of micron size particles with epoxy has been known, attachment of nanoparticles was a problem. The suggested method can be used for attachment of virtually any solid nanoparticles. Approximately every other tip prepared with this method has a single nanoparticle terminated apex. We demonstrate the force measurements between a single approximately 50 nm ceria nanoparticle and flat silica surface in aqueous media of different acidity (pH 4-9). Comparing forces measured with larger ceria particles ( approximately 500 nm), we show that the interaction with nanoparticles is qualitatively different from the interaction with larger particles.     

Initial stages of self-organization of silica-alumina gels in zeolite synthesis

We report the effect of aluminum on the formation and structure of silica nanoparticles formed in basic solutions of small organic and inorganic cations using a combination of small-angle X-ray scattering, conductivity, pH, and 27Al NMR spectroscopy methods. At low silica concentrations, our observations agree with previous reports and show the formation of small oligomers ((HO)4-nAl(OSi(OH)3)n)- that can be modeled qualitatively using a simple aqueous speciation model. We also find that aluminum drastically reduces the concentration of silica at which nanoparticles are formed. Using organic cations, the particles are smaller than the ones observed in pure silica systems (1.5 nm vs approximately 3 nm diameter), but in the case of sodium cations, larger particles are detected ( approximately 10 nm in diameter). The data suggests that sodium cations are incorporated within the inorganic silica/alumina core, as opposed to organic cations that appear to be excluded from such clusters. Important insights are gained by making analogies to the behavior of mixed surfactant systems using regular solution theory and noting that the formation of Si-O-Al bonds (as measured by the DeltaGdegrees(rxn) of condensation) is much more favorable than the formation of Si-O-Si bonds.     

FTIR and XPS study of Pt nanoparticle functionalization and interaction with alumina

Platinum nanoparticles with a mean size of 1.7 nm were synthesized by reduction in sodium acetate solution in 1,2-ethanediol. The particles were then functionalized with dodecylamine, dodecanethiol, and omega-mercapto-undecanoic acid (MUDA). Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) showed important variations of the particle surface state with functionalization whereas their structure differs only slightly. Platinum-to-sulfur charge transfer inferred from XPS of thiol-coated particles enabled the identification of the formation of Pt (delta+)-S (delta-) bonds. The native carbon monoxide (CO) at the surface of the particles was a very efficient probe for following the functionalization of the particles by FTIR. The red shift of nu(CO) accounts for the nature of the ligands at the surface of the particles and also for their degree of functionalization. Immobilization on alumina substrates of particles functionalized with MUDA was realized by immersion in colloidal solutions. Free molecules, isolated particles, and aggregates of particles interconnected by hydrogen bonds at the surface of alumina were evidenced by FTIR. With successive washings, the energy variation of the CO stretch of carbon monoxide and of carboxylic acid groups and the relative intensity nu(CH2)/nu(CO) showed that the free molecules are eliminated first, followed by aggregates and less-functionalized particles. Particles presenting a high degree of functionalization by MUDA remain and interact strongly with alumina.     

Characterization and surface reactivity of ferrihydrite nanoparticles assembled in ferritin

Ferrihydrite nanoparticles with nominal sizes of 3 and 6 nm were assembled within ferritin, an iron storage protein. The crystallinity and structure of the nanoparticles (after removal of the protein shell) were evaluated by high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), and scanning tunneling microscopy (STM). HRTEM showed that amorphous and crystalline nanoparticles were copresent, and the degree of crystallinity improved with increasing size of the particles. The dominant phase of the crystalline nanoparticles was ferrihydrite. Morphology and electronic structure of the nanoparticles were characterized by AFM and STM. Scanning tunneling spectroscopy (STS) measurements suggested that the band gap associated with the 6 nm particles was larger than the band gap associated with the 3 nm particles. Interaction of SO2(g) with the nanoparticles was investigated by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and results were interpreted with the aid of molecular orbital/density functional theory (MO/DFT) frequency calculations. Reaction of SO2(g) with the nanoparticles resulted primarily in SO(3)2- surface species. The concentration of SO3(2-) appeared to be dependent on the ferrihydrite particle size (or differences in structural properties).     

Colloid stability of thymine-functionalized gold nanoparticles

Gold nanoparticles surface-coated with thyminethiol derivatives containing long hydrocarbon chains have been prepared. The diameter of the particles is 2.2 and 7.0 nm, respectively, with a relatively narrow size distribution. Thyminethiol derivatives are attached to the gold particle surfaces with thymine moieties as the end groups. The colloid stability of the gold nanoparticles as a function of the type and concentration of monovalent salt, pH, and particle size was investigated in alkaline, aqueous solutions. The gold particles are stable in concentrated NaCl and KCl solutions, but are unstable in concentrated LiCl and CsCl solutions. The larger gold particles are more sensitive to salt concentration and aggregate at lower salt concentrations. The reversible aggregation and dispersion of the gold particles can be controlled by changing the solution pH. The larger gold particles can be dispersed at higher pH and aggregate faster than the smaller particles, due to stronger van der Waals forces between the larger particles. Hydration forces play an important role in stabilizing the particles under conditions where electrostatic forces are negligible. The coagulation of the gold nanoparticles is attributed to van der Waals attraction and reduced hydration repulsion in the presence of LiCl and CsCl.     

Permittivity and electric conductivity of aqueous alumina (40 nm) nanofluids at different temperatures

Aiming to study the effect of nanoparticle size on electric properties, the effective relative permittivity and electric conductivity of suspensions of 40 nm particles of aluminium oxide (alumina) in base Milli-Q and Milli-Ro water were determined at six different temperatures in the range (298.15 to 348.15) K, and at eight different concentrations up to 7% mass (2% volume). Present results are compared with previously published values for the same colloids containing 15 nm particles. Empirical equations for describing the experimental data are given. This study demonstrates the importance of the particle size, volume fraction of nanoparticles, temperature and water purity on the effective relative permittivity and electric conductivity of alumina nanoparticles suspensions. Trends for changes in permittivity enhancement and in electric conductivity enhancement with temperature and concentration are examined and discussed. Classical theoretical models in the study of permittivity and conductivity are applied. A summary is given for the effect of size ((15 and 40) nm), concentration (0.25 to 2)% volume and temperature (298.15 to 348.15) K on the behavior of these nanofluids.     

Solvent-dependent permeability in asymmetric ceramic membranes with tortuous or non-tortuous mesopores

Solvent-dependent transport and the role of surface interactions were examined in commercial mesoporous ceramic membranes using permeability and thermoporometry measurements. The membranes chosen were titania (TiO₂) with tortuous interconnected pores (1, 5, and 50 kDa, corresponding to pore diameters of ca. 8.2, 18.3, and 33.2 nm, respectively) and alumina (Al₂O₃) with non-tortuous 20 nm cylindrical pores. A pre-water/solvent/post-water permeability cycle was employed to account for structural differences between membranes and to gauge the effect of residual solvent on water permeability at different temperatures. Our results suggest that in both types of membranes, restricted permeability of 1-butanol and cyclohexane was due to a combination of surface sorption and an increase in disjoining pressure due to solvation forces. Sorption and solvation forces were prevalent as their length scales were on the same order of magnitude as the pore radii. For 1-butanol, chemisorption changed the surfaces from hydrophilic to hydrophobic, and led to a significant decrease in post-water permeability. While Darcy's law could not describe 1-butanol and cyclohexane permeability, it did apply to water and 1,4-dioxane in the 20 nm alumina membranes. Thermoporometry, coupled with permeability, was further used to evaluate surface wetting within the mesopores.     

Structural and optical investigations of SiO2-CdS core-shell particles

Cadmium sulfide nanoparticles (approximately 5 nm), chemically capped using thioglycerol molecules, have been anchored onto silica particles (approximately 80 nm) functionalized with 3-aminopropyltrimethoxysilane. Transmission electron microscopy clearly showed that at a low concentration of cadmium sulfide, nanoparticles were discretely and more or less uniformly attached onto the silica particles. At a high concentration of cadmium sulfide nanoparticles, an approximately 6-nm-thick compact shell of cadmium sulfide was formed on the silica particles. In both cases the nanocrystalline nature of cadmium sulfide particles was preserved, as is evident from X-ray diffraction and optical absorption spectra.     

Displacement of hexanol by the hexanoic acid overoxidation product in alcohol oxidation on a model supported palladium nanoparticle catalyst

This work characterizes the adsorption, structure, and binding mechanism of oxygenated organic species from cyclohexane solution at the liquid/solid interface of optically flat alumina-supported palladium nanoparticle surfaces prepared by atomic layer deposition (ALD). The surface-specific nonlinear optical vibrational spectroscopy, sum-frequency generation (SFG), was used as a probe for adsorption and interfacial molecular structure. 1-Hexanoic acid is an overoxidation product and possible catalyst poison for the aerobic heterogeneous oxidation of 1-hexanol at the liquid/solid interface of Pd/Al(2)O(3) catalysts. Single component and competitive adsorption experiments show that 1-hexanoic acid adsorbs to both ALD-prepared alumina surfaces and alumina surfaces with palladium nanoparticles, that were also prepared by ALD, more strongly than does 1-hexanol. Furthermore, 1-hexanoic acid adsorbs with conformational order on ALD-prepared alumina surfaces, but on surfaces with palladium particles the adsorbates exhibit relative disorder at low surface coverage and become more ordered, on average, at higher surface coverage. Although significant differences in binding constant were not observed between surfaces with and without palladium nanoparticles, the palladium particles play an apparent role in controlling adsorbate structures. The disordered adsorption of 1-hexanoic acid most likely occurs on the alumina support, and probably results from modification of binding sites on the alumina, adjacent to the particles. In addition to providing insight on the possibility of catalyst poisoning by the overoxidation product and characterizing changes in its structure that result in only small adsorption energy changes, this work represents a step toward using surface science techniques that bridge the complexity gap between fundamental studies and realistic catalyst models.     

Composite Au/TiO(2) Nanoparticles: Synthesis, Characterization, and Assembly by Using Potentiostatic Technique

Composite Au/TiO(2) nanoparticles were synthesized using TiO(2) nanoparticles as nuclei. The particles were characterized by UV-vis spectroscopy, zeta potential, EDS, and TEM. The mean diameter of the particles is about 23.6 nm, and the position of the surface plasma absorption band peak is at 533 nm, with a red shift of 15 nm compared with that of Au sol. The zeta potential is +31.3 mV. Monolayers of composite Au/TiO(2) nanoparticles were obtained using the potentiostatic technique. Copyright 2000 Academic Press.     

Evidence for patchy lipid layers on gold nanoparticle surfaces

Gold nanoparticles bearing multiple surface ligands are becoming favored candidates as multifunctional targeting, imaging, and therapeutic vehicles for biomedicine. The question of spatial location of different ligands on nanoparticle surfaces, especially with those of diameters less than 100 nm, is an important one that is difficult to quantitatively address. Here we functionalize the surface of 20, 50, and 90 nm gold nanoparticles with two different lipids, both single and mixed, using two different surface chemical procedures. Mass spectrometry supports the presence of both lipids in the mixed-lipid systems on nanoparticles, while electron microscopy evidence shows domain sizes for one lipid apparently a quarter to a half the projected diameter for 50 and 90 nm particles; but for 20 nm particles, there is no evidence for the existence of patches of the two lipids. Larger gold nanoparticles (90 nm) can be decorated with an array of 12 nm gold nanoparticles by use of a third lipid and antibody-antigen connectors; the display of the 12 nm particles about the 90 nm particles can be controlled to some extent by the initial surface chemistry and is quantified via a new angle analysis procedure.