Nanomaterial characterization: considerations and needs for hazard assessment and safety evaluation

Nanotechnology is a rapidly emerging field of great interest and promise. As new materials are developed and commercialized, hazard information also needs to be generated to reassure regulators, workers, and consumers that these materials can be used safely. The biological properties of nanomaterials are closely tied to the physical characteristics, including size, shape, dissolution rate, agglomeration state, and surface chemistry, to name a few. Furthermore, these properties can be altered by the medium used to suspend or disperse these water-insoluble particles. However, the current toxicology literature lacks much of the characterization information that allows toxicologists and regulators to develop “rules of thumb” that could be used to assess potential hazards. To effectively develop these rules, toxicologists need to know the characteristics of the particle that interacts with the biological system. This void leaves the scientific community with no options other than to evaluate all materials for all potential hazards. Lack of characterization could also lead to different laboratories reporting discordant results on seemingly the same test material because of subtle differences in the particle or differences in the dispersion medium used that resulted in altered properties and toxicity of the particle. For these reasons, good characterization using a minimal characterization data set should accompany and be required of all scientific publications on nanomaterials.     

含双噻唑基聚合物的合成及电流变性能研究

采用2，2’-二氨基-4，4’-双噻唑与联苯胺合成一种含有双噻唑基的共轭聚合物，通过红外、扫描电镜、热重分析等测试了该物质的结构及热稳定性等，并通过将聚合物分别分散在硅油和溴代二苯甲烷中制备电流变体，测试其电流变性能。结果表明：含双噻唑基的共轭聚合物作为电流变体的分散相表现出了良好的电流变性能，同时发现分散相和分散介质的密度相近时有利于电流变性能的提高。     

Fluidity and spreading of structured disperse systems

The regularities of flow and spreading of disperse systems as two interrelated processes are considered. Differences in the mechanisms of spreading of structured dispersions on solid surfaces are discussed in comparison with the processes of wetting and spreading of Newtonian and non-Newtonian unstructured liquids. It is shown that, for structured dispersions under consideration, their bulk structure-related rheological properties are of prime importance. Surface phenomena occurring at a boundary with a solid substrate affect the character of spreading of such dispersions to the same extent as the interaction of a structured disperse system with the surface affects variations in the properties of adjacent layers of the disperse system.     

Kinetics of Structurization Processes in Three-Phase Disperse Systems under the Dynamic Conditions (Vibration) during Mixing

Regularities of the formation kinetics of the three-phase disperse systems of the solid–liquid–gas type under dynamic conditions were considered. The mechanism of the action of continuous shear and vibration (with various frequencies and amplitudes) on the formation and breakage of dispersed structures in such systems was studied. The interrelation of contact interactions between the particles and particle aggregates with the bulk rheological properties of three-phase disperse systems during mixing of finely dispersed solid phases with liquid medium and consequent compaction of dispersions was established. The revealed regularities of the formation dynamics of three-phase disperse structures provide the basis for chemical technology of highly concentrated disperse systems and highly filled disperse composites.     

油溶性Ag纳米微粒的制备及表征

Surface modified silver nano particles were synthesized in a mixture solvent of water-alcohol with Pyridinium di-n-octadecyldithio phosphate(PyDDP) as a modification agent. Themorphology and structure of DDP-coated Ag (Ag-DDP) nanoparticles were characterized using X-ray powder diffraction(XRD), Transmission electron microscopy(TEM), Fourier transform infrared spectrum (FT-IR) and Thermo gravimetric analysis(TGA). Anti wear properties of Ag-DDP nano particles were tested using a four-ball tribological testing machine. The disperse properties of Ag-DDP nanoparticles were evaluated in solvents such as chloroform, benzen, toluene, liquid paraffin, distilled water and ethanol. The results show that Ag-DDP nanoparticles disperse in organic solvents, but they don’t disperse in water or ethanol. The good disperse properties in organic solvents enable Ag-DDP nanoparticles to be used as oil additives. The XRD pattern of Ag-DDP nanoparticles indicates that they have fcc crystal structure, and the modification layer can prevent the oxidation of Ag nanocores. TEM graphs show that Ag-DDP nanoparticles have a homogeneous grain distribution; the average diameter is about 15nm. FT-IR and TGA curves indicate that the existence of modification layer can prevent the adsorption of water on the surface of nanoparticles. Tribological tests show that Ag-DDP nanoparticles have good anti-wear properties in liquid paraffin, and they can improve the applied load of base oil.     

Dyes with high affinity for polylactide

Attempts were made to develop dyes with high affinity for polylactide as an alternative to the existent commercial disperse dyes. The dyes synthesized according to the affinity concept of dye to polylactide exhibited excellent dyeing properties on polylactide compared with the commercial disperse dyes.     

Naphthalimide based disperse dyes for nylon 6 and polyester (pet) fibers: Synthesis and evaluation of technical properties in the presence of urea

Technical properties of two naphthalimide based disperse dyes on nylon 6 and polyester fibers were investigated in the presence of urea.The two naphthalimide based disperse dyes were synthesized.The dyes were purified and then fully characterized using ~1H-NMR,FTIR and melting point analysis.Dispersion of the dyes was prepared in water and applied on nylon 6 and PET fibers.The dyes offered good build-up properties on the substrates.In order to increase dye adsorption of the substrates,urea was added into...     

Computer simulation of the structure formation and disruption processes in the solid-liquid disperse systems

Results of the computer simulation of solid-liquid disperse systems are reported. Main regularities of the formation and disruption of the internal structure of such systems are demonstrated under static and dynamic conditions (including the combination of shear and orthogonal vibrations). The effect of the character of the interaction of dispersed phase particles, as well as of a number of parameters concerning the type and intensity of external actions on the behavior of disperse systems is shown. The possibility of the regulation of the character of microstructure and rheological properties of disperse systems by the combination of shearing and orthogonal vibrations is illustrated.     

Luminescence investigations of the adsorption properties of disperse Al2O3 surfaces by means of selective laser excitation

A new method for the determination of the adsorption activity of disperse materials by means of inorganic luminescent probes under selective laser excitation has been developed and tested for the investigation of the adsorption properties of disperse Al(2)O(3) surfaces. Water-uranyl complexes have been used as luminescent probes for these experiments, and the photoluminescence spectra of UO(2)(2+) molecular ions adsorbed on the disperse Al(2)O(3) surfaces were investigated. The luminescence properties of this adsorption system, as in the previously studied case of SiO(2), were determined by the type and structure of the adsorption complexes (AC) formed. Different ACs cause many (7 observed) "elementary" luminescence spectra. The water-uranyl-complex adsorption binding energies were obtained. The values of the binding energies and the electric field strength of the surface active centers support the validity of the water-uranyl model of AC and the electrostatic consideration used.     

Thermophysical Properties of Granules of Instant Drinks in the Process of Structuring

In this article the research of the thermophysical properties of the material depending on its moisture content been represented. The interrelation of various physical properties with the content of moisture in the mass were detected. In addition, their dependence on the quantitative ratio and the properties of structural carcass and pore spaces were proved. The need to consider the volume phase composition of the mixture was justified. A formula to calculate the thermal conductivity coefficient of the product molded from disperse materials was obtained on the basis of Lykov criterion defining the property of drying material and volume phase concentrations. It is proved that the use of volume phase characteristics of disperse systems opens new possibilities for improving the methodologies for determining the those thermophysical properties of dry and wet dispersion materials, allows increasing the reliability results of these definitions, revealing the mechanism of anomalous heat conductivity of wet material.     

Concentration factor and rheology of aqueous titanium dioxide dispersions

The rheological properties of aqueous titanium dioxide dispersions have been studied by rotational viscometry. It has been established that the studied disperse systems are highly structured, and their degree of structuring dramatically increases with the volume fraction φ of the solid phase. At solid phase contents φ ≥ 0.164, the breakage of the disperse structure is accompanied by the appearance of local discontinuities and an abnormal dependence of viscosity on shear stress. The results obtained have been analyzed in terms of the Uriev theory of aggregated systems. The radii of aggregates and maximum solid phase content φ_m that corresponds to the formation of a continuous disperse structure under the conditions of dynamic impact have been calculated.     

Aqueous Systems Based on Metaphos in Low Concentration: The Relationship between Self-Assembly,Physico-Chemical,and Biological Properties

It has been shown for the first time that aqueous solutions of metaphos pesticide (1×10^–4–1×10^–17 mol/L) are disperse systems, the disperse phase undergoing rearrangement upon dilution. The relationship between nonmonotonic concentration dependences of the nanoassociate size, physico-chemical properties of the systems, and their action on higher plants and hydrocoles has been found.     

Chemical Graft of Cellulose with the Ion-Pair Emulsion Containing the Reactive Groups and Its Dyeing Properties

Chemical graft of cellulose with ion-pair disperse emulsion containing the reactive groups was investigated. The ion-pair disperse systems were consisted of a 1,3,5-triazine derivative containing the reactive groups, 2,4,6-tri[(2-hydroxy-3-trimethyl-ammonium)propyl]-1,3,5-triazine chloride (Tri-HTAC) and 2,4,-bichloro[(6-sulfanilic acid)-1,3,5-triazine (Bi-CSAT). Compared with unmodified cellulose, the modified cotton exhibited different behavior towards dyeing. The modified cotton could be dyed with reactive dyes without the addition of salt. The color yield was higher than that on untreated cotton, despite of the addition of large amounts of salt in the latter case. Cotton fabric modified with ion-pair disperse emulsion was imparted good level dyeing properties. The dyeing rate was slower in the presence of the ion-pair compounds than that in the present of the only cationic compounds.     

Synthesis and dyeing performance of some novel thiazole azo disperse dyes

The synthesis of some novel monoazo disperse dyes derived from 5-acetyl-2-amino-4-methylthiazole using various N-alkyl derivatives of aniline and their dyeing performance as disperse dyes have been assessed on cellulose triacetate fabric. The spectral properties of these dyes were also measured. The dyed fabric show good light fastness, very good rubbing, perspiration, washing fastness and excellent sublimation fastness. These dyes have been found to give bright yellow to maroon color shade with very good depth and levelness on fabric. The dyebath exhaustion and fixation on fabric has been found to be very good.     

Effect of the nature of carbonaceous supports on the bioelectrocatalytic activity of peroxidase, immobilized on the supports, in the hydrogen peroxide reduction reaction

Electrochemical properties of such disperse carbonaceous materials as acetylene black AD-100, finely divided colloidal graphite (FCG), ultradisperse diamond (UDD), and carbon nanotubes (CNT) are examined. Effect of the nature of disperse carbonaceous supports on bioelectrocatalytic activity of adsorbed peroxidase (POD) in the hydrogen peroxide reduction reaction is investigated. It is shown that the hydrogen peroxide reduction on the biocatalysts studied proceeds in conditions of direct bioelectrocatalysis independently of the disperse-support type. It is also demonstrated that the biocatalysts’ activity depends on the structure and properties of the surface of the supports defining the magnitude of the POD adsorption in an orientation favorable for direct bioelectrocatalysis. Maximum activity is inherent in the catalysts manufactured on the basis of materials with moderate hydrophobic and hydrophilic properties. By the magnitude of the activity in the hydrogen peroxide reduction reaction, depending on the nature of the carbonaceous support, the fabricated catalysts (carbonaceous material with adsorbed POD) form the series AD-100, CNT > FCG > UDD.     

Dynamics simulation of disperse systems in the presence of a structure-related mechanical barrier resulting from surfactant adsorption

A computer model has been developed to refine the notions of the kinetics of structural transformations in surfactant-modified disperse systems, the mechanism of the influence of adsorption layers on viscosity, conditions of aggregation, and evolution of nonuniformities in microstructures. Classical concepts of the structure-related mechanical barrier providing disperse systems with stability to aggregation, as well as the criterion of adsorption-layer breakdown upon interparticle collisions under dynamic conditions, have been used. It has been shown that adsorption-layer breakdown under dynamic conditions may lead to the appearance of an extreme in the viscosity curve of a disperse system. The combined effect of additives of surfactants with different molecular masses successively added to the systems has been studied via taking into account the influence of surfactant adsorption layers on the dynamics of contact interactions. The simulation results make it possible to optimize the regulation of structure-related rheological properties of dispersions so as to decrease their apparent viscosity with a simultaneous increase in the uniformity of the structure.     

Aqueous dispersions of C60 fullerene by use of amphiphilic block copolymers: preparation and nonlinear optical properties

The dispersion of the otherwise insoluble C60 fullerene in water is discussed. Amphiphilic block copolymers, namely, polystyrene-b-polyethylene oxide (PS-PEO), were found to be able to disperse C60 in aqueous solutions, where the polymer forms micelles with a hydrophobic PS core. The preparation protocol of the final solutions was found to play a crucial role in the ability of the block copolymer to disperse the C60 molecules. The C60 containing aggregates were studied using optical spectroscopy, light scattering, and scanning electron microscopy. In addition, their optical limiting action and nonlinear optical properties under visible nanosecond laser excitation were studied and compared with that of C60-toluene solutions.     

Synthesis and application of some novel fluorescent heterocyclic disperse dyestuffs based on phenothiazine on polyester

A series of novel heterocyclic disperse dyestuffs derived from phenothiazine were prepared by standard reactions from phenothiazine as the starting material. Phenothiazine was nitrated and oxidized then reduced to obtain synthesized disperse dyestuffs. The reaction conditions were varied in order to obtain optimal yields for each stage of the preparation to obtain the corresponding derivative and final disperse dyestuffs. All intermediates and disperse dyestuffs were purified and characterized by DSC, FTIR, ¹H NMR, ¹³C NMR, elemental analysis and UV–Visible spectroscopic techniques. The molar extinction coefficients (ε), wavelengths of maximum absorption (λ_max) and solvatochromism effects were studied in solvents as toluene, acetone and N,N-dimethylformamide (DMF). Results represented that the dyestuffs had extinction coefficients of 2011–28189 L mol⁻¹ cm⁻¹, wavelengths of maximum absorption of 448–475 nm in acetone and positive solvatochromism by changing solvent from toluene to DMF. The disperse dyestuffs were applied to locally manufactured polyester fibers and their dyeing properties were investigated. Results showed that the buildup of dyestuffs was acceptable and dyed fibers had very good heat and wash fastness and medium light fastness on polyester fibers.     

Control of microstructure and properties of filled polymer compositions

The problem of controlling the structure and properties of filled polymer compositions based on epoxy materials and various fibrous and disperse fillers is investigated. Four scale levels of the filled polymer materials are considered, and examples of their structure at different stages of the fracture process are given.     

Variation of anions in layered double hydroxides: Effects on dispersion and fire properties

Layered double hydroxides (LDHs) are interesting materials for nanocomposite formation because one can vary the identity of the metals, the anions and the stoichiometry to see the effect of these on the ability of the nano-material to disperse in a polymer and to see what effect dispersion has on the properties of the polymer. In this study, the anions 2-ethylhexyl sulfate (SEHS), bis(2-ethylhexyl) phosphate (HDEHP) and dodecyl benzenesulfonate (SDBS) have been utilized as the charge balancing anions to synthesize organo-LDHs. Nanocomposites of poly(methyl methacrylate) (PMMA) and polystyrene (PS) with organo-LDHs were prepared both by melt blending and bulk polymerization. X-ray diffraction and transmission electron microscopy were used to characterize the morphology of the nanocomposites while the thermal stability and fire properties of nanocomposites were studied by thermogravimetric analysis and cone calorimetry; the mechanical properties are also investigated. In general, it is easier to disperse these organo-LDHs in PMMA than in PS, but the sulfate cannot be dispersed at the nanometer level in either material. The addition of these organo-LDHs does not affect the mechanical properties. The best fire properties are obtained with the sulfonate LDH, SDBS; the reduction in the peak heat release rate is almost 50% for both polymers.