Risk-based classification system of nanomaterials

Various stakeholders are increasingly interested in the potential toxicity and other risks associated with nanomaterials throughout the different stages of a product’s life cycle (e.g., development, production, use, disposal). Risk assessment methods and tools developed and applied to chemical and biological materials may not be readily adaptable for nanomaterials because of the current uncertainty in identifying the relevant physico-chemical and biological properties that adequately describe the materials. Such uncertainty is further driven by the substantial variations in the properties of the original material due to variable manufacturing processes employed in nanomaterial production. To guide scientists and engineers in nanomaterial research and application as well as to promote the safe handling and use of these materials, we propose a decision support system for classifying nanomaterials into different risk categories. The classification system is based on a set of performance metrics that measure both the toxicity and physico-chemical characteristics of the original materials, as well as the expected environmental impacts through the product life cycle. Stochastic multicriteria acceptability analysis (SMAA-TRI), a formal decision analysis method, was used as the foundation for this task. This method allowed us to cluster various nanomaterials in different ecological risk categories based on our current knowledge of nanomaterial physico-chemical characteristics, variation in produced material, and best professional judgments. SMAA-TRI uses Monte Carlo simulations to explore all feasible values for weights, criteria measurements, and other model parameters to assess the robustness of nanomaterial grouping for risk management purposes.     

Horses for courses: risk information and decision making in the regulation of nanomaterials

Despite the widespread commercial use of nanomaterials, regulators currently have a limited ability to characterize and manage risks. There is a paucity of data available on the current production and use of nanomaterials and extreme scientific uncertainty on most aspects of the risk assessment “causal chain.” Regulatory decisions will need to be made in the near-term in the absence formal quantitative risk assessments. The article draws on examples from three different regulatory contexts—baseline data monitoring efforts of the U.S. Environmental Protection Agency and California Department of Toxic Substances Control, prioritization of risk information in the context of environmental releases, and mitigation of occupational risks—to argue for the use of decision-analytic tools in lieu of formal risk assessment to help regulatory bodies. We advocate a “horses for courses” approach whereby existing analytical tools (such as risk ranking, multi-criteria decision analysis, and “control banding” approaches) might be adapted to regulators’ goals in particular decision contexts. While efforts to build new and modify existing tools are underway, they need greater support from funding and regulatory agencies because innovative approaches are needed for the “extreme” uncertainty problems that nanomaterials pose.     

Micromechanics of the transition from intergrain to intragrain deformation in nanomaterials

A micromechanism of the transition from intergrain sliding to intragrain glide by nucleation and emission of lattice partial dislocations at grain-boundary dislocations is proposed and described theoretically. The energy characteristics of this process are calculated. It is shown that the nucleation of lattice partial dislocations is energetically efficient and can occur athermally (without the energy barrier) under conditions of the action of ultrahigh mechanical stresses. The critical stresses required for the athermal nucleation and emission of dislocations are calculated.     

Atomic-scale structure: From surfaces to nanomaterials

This brief overview is dedicated to Professor G. Ertl’s profound influence on shaping the field of surface science. I sketch recent accomplishments toward the determination and understanding of the atomic-scale structure of nanostructures. I argue that, to properly understand nanoscience and develop nanotechnology, there is a dire need to determine many more than the ～1,000 detailed surface structures known today. Techniques need to be adapted or invented to make this possible. As will be exhibited here, only two techniques are now essentially ready for this task: scanning tunneling microscopy, if interpreted by theory, and, to a lesser extent, x-ray diffraction. I also describe how low-energy electron diffraction is currently being developed for the same purpose.     

Occupational exposure limits for nanomaterials: state of the art

Assessing the need for and effectiveness of controlling airborne exposures to engineered nanomaterials in the workplace is difficult in the absence of occupational exposure limits (OELs). At present, there are practically no OELs specific to nanomaterials that have been adopted or promulgated by authoritative standards and guidance organizations. The vast heterogeneity of nanomaterials limits the number of specific OELs that are likely to be developed in the near future, but OELs could be developed more expeditiously for nanomaterials by applying dose–response data generated from animal studies for specific nanoparticles across categories of nanomaterials with similar properties and modes of action. This article reviews the history, context, and approaches for developing OELs for particles in general and nanoparticles in particular. Examples of approaches for developing OELs for titanium dioxide and carbon nanotubes are presented and interim OELs from various organizations for some nanomaterials are discussed. When adequate dose–response data are available in animals or humans, quantitative risk assessment methods can provide estimates of adverse health risk of nanomaterials in workers and, in conjunction with workplace exposure and control data, provide a basis for determining appropriate exposure limits. In the absence of adequate quantitative data, qualitative approaches to hazard assessment, exposure control, and safe work practices are prudent measures to reduce hazards in workers.     

Validity of the Darwin and Ewald reflectivity functions in the range of the far wings: Neutron diffraction study

Using the neutron time-of-flight (TOF) technique, we have examined the reason for the dramatic departure of experimental results from the Darwin and Ewald reflectivity functions in the far wings. The scattering from Si(111) single- and triple-bounce crystals set up at the Bragg angle θB=24.4° was dispersed in time-of-flight in the wavelength range 0.3<λ<3.0 Å. The experiment reveals admixture of the single-scattered Bragg peaks and thermal diffuse scattering (TDS) originating at λ<0.6 Å in the spectrum registered from a triple-bounce crystal. Our study explains the discrepancy between the theory and the experimental results reported in many neutron studies and proves the validity of the Darwin and Ewald theories in the far wings.     

Relaxation of quasi-stationary states in long range interacting systems and a classification of the range of pair interactions

Systems of particles interacting with long range interactions present generically ”quasi-stationary states” (QSS), which are approximately time-independent out of equilibrium states. In this proceedings, we explore the generalization of the formation of such QSS and their relaxation from the much studied case of gravity to a generic pair interaction with the asymptotic form of the potential v(r) ∼ 1/r ^γ with γ > 0 in d dimensions. We compute analytic estimations of the relaxation time calculating the rate of two body collisionality in a virialized system approximated as homogeneous. We show that for γ < (d − 1/2), the collision integral is dominated by the size of the system, while for γ > (d − 1/2), it is dominated by small impact parameters. In addition, the lifetime of QSS increases with the number of particles if γ < d − 1 (i.e. the force is not integrable) and decreases if γ > d − 1. Using numerical simulations we confirm our analytic results. A corollary of our work gives a ”dynamical” classification of interactions: the dynamical properties of the system depend on whether the pair force is integrable or not.     

Using sonochemistry for the fabrication of nanomaterials

One of the reasons for the huge interest in nanomaterials originated because of the prohibitive price that commercial companies have to pay for introducing new materials into the market. Nanotechnology enables these companies to obtain new properties using old and recognized materials by just reducing their particle size. For these known materials no government approval has to be obtained. Thus, the interest in nanomaterials has led to the development of many synthetic methods for their fabrication. Sonochemistry is one of the earliest techniques used to prepare nanosized compounds. Suslick, in his original work, sonicated Fe(CO)5 either as a neat liquid or in a decalin solution and obtained 10-20 nm size amorphous iron nanoparticles. A literature search that was conducted by crossing Sono* and Nanop* has found that this area is expanding almost exponentially. It started with two papers published in 1994, two in 1995, and increased to 59 papers in 2002. A few authors have already reviewed the fields of Sono and Nano. It should be mentioned that in 1996, Suslick et al. published an early review on the nanostructured materials generated by ultrasound radiation. Suslick and Price have also reviewed the application of ultrasound to materials science. This review dealt with nanomaterials, but was not directed specifically to this topic. The review concentrated only on the sonochemistry of transition metal carbonyls and catalytic reactions that involve the nanoparticles resulting from their sonochemical decomposition. Grieser and Ashokkumar have also written a review on a similar topic. A former coworker, Zhu, has recently submitted for publication a review article entitled "Novel Methods for Chemical Preparation of Metal Chalcogenide Nanoparticles" in which he reviews three synthetic methods (sonochemistry, sonoelectrochemistry, and microwave heating) and their application in the synthesis of nanosized metal chalcogenides. Although still unpublished, I myself have recently written a review discussing novel methods (sonochemistry, microwave heating, and sonoelectrochemistry) for making nanosized materials. The current review will: (1) Present the four main advantages that sonochemistry has over other methods related to materials science and nanochemistry; (2) concentrate on the more recent (2003) literature that was not reviewed in the previously-mentioned reviews, and (3) focus on a specific question, such as what is the typical shape of products obtained in sonochemistry? This review will not survey the literature related to sonoelectrochemistry.     

Seed-mediated shape evolution of gold nanomaterials: from spherical nanoparticles to polycrystalline nanochains and single-crystalline nanowires

We studied the kinetics of the reduction of a gold precursor (HAuCl₄) and the effect of the molar ratio (R) of sodium citrate, which was introduced from a seed solution, and the gold precursor on the shape evolution of gold nanomaterials in the presence of preformed 13 nm gold nanoparticles as seeds. The reduction of the gold precursor by sodium citrate was accelerated due to the presence of gold seeds. Nearly single-crystalline gold nanowires were formed at a very low R value (R = 0.16) in the presence of the seeds as a result of the oriented attachment of the growing gold nanoparticles. At a higher R value (R = 0.33), gold nanochains were formed due to the non-oriented attachment of gold nanoparticles. At a much higher R value (R = 1.32), only larger spherical gold nanoparticles grown from the seeds were found. In the absence of gold seeds, no single-crystalline nanowires were formed at the same R value. Our results indicate that the formation of the 1D nanostructures (nanochains and nanowires) at low R values is due to the attachment of gold nanoparticles along one direction, which is driven by the surface energy reduction, nanoparticle attraction, and dipole–dipole interaction between adjacent nanoparticles.     

Differential cross sections for in the CM energy range from 2.0 to 3.1 GeV

Exclusive production of proton-antiproton pairs by two photon scattering at CM energies between 2.0 GeV and 3.1 GeV has been measured with the TASSO detector at the e⁺e⁻ storage ring PETRA. The angular distribution is flat within the accepted CM angular range |cos Θ^*|0.7. The integrated cross section (|cos Θ^*|0.6) drops from about 4 nb at 2 GeV to less than 0.5 nb above 3 GeV. For the two-photon production of the η_c(2984) and its subsequent decay into proton-antiproton the upper limit

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(95% CL) is found.     

Germanium lasers in the range from far-infra red to millimetre waves

Recent experimental and theoretical achievements are reviewed on three types of laser oscillation inp-type germanium; the intervalence band (IVB) laser oscillation due to transitions between the light-hole band and the heavy-hole band, the light-hole cyclotron resonance (LHCR) laser oscillation, and the heavy hole cyclotron resonance (HHCR) maser oscillation. Described for the IVB oscillation are fundamental characteristics (such as the wavelength range of oscillation and the cooperation with higherharmonic cyclotron resonances), the polarization characteristics of radiation and influence of uniaxial stress on the oscillation. The present status of the attempt at single line oscillation is also described. As for the LHCR oscillation, the formation of population inversion and the amplification are explained on the basis of quantum mechanical calculations of the valence bands in crossed electric and magnetic fields.     

Analysis of equation of state for nanomaterials

An equation of state (EOS) recently proposed for nanomaterials is discussed critically. Different possible forms of the EOS are discussed with their correlations. We have considered 20 nanomaterials for this purpose, viz. CdSe, Rb₃C₆₀, carbon nanotube, γ-Fe₂O₃, ε-Fe (hexagonal iron), MgO, γ-Al₂O₃ (67 nm), α-Fe₂O₃, α-Fe (filled nanotube), TiO₂ (anatase ), 3C-SiC (30 nm), TiO₂ (rutile phase), Zr_0.1Ti_0.9O₂, γ-Si₃N₄, Ni-filled MWCNT, Fe-filled MWCNT, CeO₂ (cubic fluorite phase and orthorhombic phase), germanium (49 nm), GaN (wurtzite phase) and SnO₂ (rutile phase) (14 nm). It is found that the change in the form of EOS does not improve the results. This demonstrates the validity of the EOS proposed for nanomaterials. The EOS is also used to study the effect of temperature on compression of Ni (20 nm). It is found that there is small shift in isotherm due to increase in the temperature. The results have been found to present a good agreement with the available experimental data.     

Selection maps for quantum logics: applications to the classification of elementary particles

The observed properties of certain groups of elementary particle states are used to construct quantum logics whose pure states correspond to those of the given particles. The pure states can be made into an orthogonality space and the observed properties are representable as frame functions on this structure.This technique generalizes aspects of the existing methods of classification and provides examples of nonstandard logics in physics.     

X-filtering for a range of coupling constants: application to the detection of intermolecular NOEs

A new method for heteronuclear X-filtering is presented, which relies on repetitive applications of 90 degrees (1H)-tau(1/41J(HC))-180 degrees (1H,13C)-tau(1/41J(HC))-90 degrees (1H,13C)-PFG building blocks employing gradient-mediated suppression of magnetization built up for directly heteronuclear coupled protons. Thereby, a range of heteronuclear coupling constants can be suppressed by varying the delays of scalar coupling evolution both within and between individual transients. To achieve efficient destruction of 13C-coupled protons in macromolecular systems, the scalar coupling evolution delays were optimized using simulated annealing by including transverse relaxation effects. With a combination of regular hard pulses, delays and pulsed field gradients only, this method yields sufficient X-filtering to allow the observation of intermolecular nuclear overhauser effects in a molecular complex consisting of a 13C, 15N double-labeled, and an unlabeled protein. This is achieved by exciting magnetization of 12C- and 14N-bound protons and detecting 13C-bound 1H magnetization in a 3D 13C-filtered, 13C-edited NOESY-HSQC experiment. The method is tested on the 18 kDa homodimeric bacterial antidote ParD.     

Electrodynamic properties of nanoporous silicon in the range from terahertz to infrared frequencies

The dielectric response (conductivity and permittivity) spectra of a series of nanoporous silicon samples prepared by anodization of low-resistivity single-crystal silicon are measured, for the first time, using terahertz and IR spectroscopy in the frequency range 7–4000 cm^?1 at room temperature. The spectra obtained are analyzed in terms of the effective medium theory with a size-dependent dielectric response function of nanoinclusions and averaged dielectric characteristics of the surrounding medium. The geometric and dielectric characteristics of silicon nanoinclusions are determined. The dielectric properties of inclusions are found to be affected by nanosize effects, namely, carrier scattering at crystallite boundaries and a broadening of the band gap due to quantum confinement. The spectra of the samples prepared by adding iodine to the electrolyte exhibit a resonance at frequencies of 150–300 cm^?1. The nature of the resonance can be associated with the presence of chemisorbed iodine on the surface of porous silicon. Possible mechanisms responsible for the changes in broadband conductivity and permittivity spectra of single-crystal silicon upon transformation into a nanoporous structure are discussed.     

An overview of thermoelectric films:Fabrication techniques,classification,and regulation methods

Thermoelectric materials have aroused widespread concern due to their unique ability to directly convert heat to electricity without any moving parts or noxious emissions.Taking advantages of two-dimensional structures of thermoelectric films,the potential applications of thermoelectric materials are diversified,particularly in microdevices.Well-controlled nanostructures in thermoelectric films are effective to optimize the electrical and thermal transport,which can significantly improve the performance of thermoelectric materials.In this paper,various physical and chemical approaches to fabricate thermoelectric films,including inorganic,organic,and inorganic–organic composites,are summarized,where more attentions are paid on the inorganic thermoelectric films for their excellent thermoelectric responses.Additionally,strategies for enhancing the performance of thermoelectric films are also discussed.