Non-debye dielectric response in monolithic layers of silver stearate

This paper reports on the results of investigations of the electrophysical properties of silver stearate by the methods of dielectric spectroscopy and differential scanning calorimetry (DSC). The mechanisms of charge transfer and dielectric relaxation in silver stearate have been established. It has been found that there is a critical temperature T = 338 K, which is probably related to the low-temperature phase transition in the system under investigation.     

In Situ HREM observation of crystalline-to-gas transition in nanometer-sized Ag particles

Sublimation of silver atoms from a nanometer-sized silver particle, namely, the crystalline-to-gas transition, has been directly observed by high resolution electron microscopy. Remarkable sublimation of silver atoms took place at 950 K from an approximately 9-nm-sized crystalline silver particle on the graphite substrate. The sublimation continued until the whole silver particle disappeared. No melting of the particle occurred during this process. The height-to-width ratio of a nanometer-sized silver particle on graphite at 950 K was about 0.65, and the ratio did not change so much during the sublimation-induced shrinkage of the particle.     

From silver nanoparticles to thin films: Evolution of microstructure and electrical conduction on glass substrates

Silver nanoparticles embedded in a dielectric matrix are investigated for their potential as broadband-absorbing optical sensor materials. This contribution focuses on the electrical properties of silver nanoparticles on glass substrates at various morphological stages. The electrical current through thin films, consisting of silver nanoparticles, was characterized as a function of film thickness. Three distinct conductivity zones were observed. Two relatively flat zones (“dielectric” for very thin films and “metallic” for films thicker than 300-400 Å) are separated by a sharp transition zone where percolation dominates. The dielectric zone is characterized by isolated particle islands with the electrical conduction dominated by a thermally activated tunneling process. The transition zone is dominated by interconnected silver nanoclusters—a small increase of the film thickness results in a large increase of the electrical conductivity. The metallic conductivity zone dominates for thicknesses above 300-400 Å.     

Photoinduced formation and aggregation of silver nanoparticles at the surface of carboxymethylcellulose films

Formation and aggregation of photolytic silver nanoparticles at the surface of silver salt of carboxymethylcellulose films (CMCAg films) have been investigated. Detailed X-ray photoelectron spectroscopy (XPS) study and field emission type scanning electron microscopy (FE-SEM) observation have been carried out to characterize silver nanoparticles at the film surface. When the CMCAg films were irradiated with UV light in wet air at room temperature for 30–60 min, silver nanoparticles of ca. 10 nm size were formed at the irradiated surface. According to the FE-SEM observation, the growth of the particle diameter and aggregation of nanoparticles took place after prolonged irradiation, and finally, the irradiated side of the film surface was densely covered with the silver nanoparticles of ca. 35 nm size. Chemical composition analysis by the XPS measurements has confirmed the increase in the atomic concentration of silver with irradiation time. It is suggested that silver atoms and clusters can move in the film and precipitate at the irradiated surface.     

Phase transitions in BaCeO3: neutron diffraction and Raman studies

Polycrystalline samples and small single crystals of the perovskite BaCeO₃ were studied by neutron diffraction and Raman spectrometry between 300 and 1200 K. The controversy about the phase transitions originally deduced from our previous Raman study and those observed since by neutron diffraction by Knight has stimulated this work. Pretransitional effects which are detected by Raman much before long-range ordering takes place can partly explain the above disagreement. A continuous monitoring of the structural changes by neutron diffraction and by Raman spectroscopy including polarization analysis has allowed discussion of the transition mechanisms: The first transition Pnma–Imma takes place at 573 K and is of second order. Although some modes soften when the temperature is raised as in many of these perovskite compounds the transition is likely partly displacive partly order–disorder. The Raman modes which disappear transform in modes at the X point of the Brillouin zone of the Imma phase. The second transition Imma–R c takes place at 673 K and is first order. The last transition R c–Pm3m occurs above 1200 K and the transition temperature which can be deduced by extrapolation to zero Raman intensity is in good agreement with neutron results. This second order transition is progressive and begins at about 400 K, the intermediate R c structure appearing as an attempt for slowing down the structural evolution toward the cubic perovskite form.     

Preparation and properties of nano-sized Ag and Ag2S particles in biopolymer matrix

Silver (Ag) and silver sulfide (Ag₂S) nanoparticles were synthesized in a sago starch matrix. The resulting nanocomposites were investigated using structural, optical and thermal methods. XRD spectra of the nanocomposites confirmed the presence of nanostructured silver (cubic phase) and silver sulfide (monoclinic phase) in the matrix. TEM micrographs showed that the nanoparticles are mostly spherical in shape. Analyzes of the optical properties of the silver nanocomposite aqueous dispersions/solutions of various concentrations were carried out. The results and the theoretical considerations suggested that at high concentrations there is a release of silver nanoparticles from the composite in the water environment. Further dilution produces homogeneous solution in which silver nanoparticles are capped with starch macromolecules. TGA analysis revealed reduced thermal stability of the nanocomposites with respect to pure starch matrix.     

Magnetic properties of nanoparticles of cobalt chromite

Magnetic properties of cobalt chromite nanoparticles of size 8-12 nm synthesized through conventional coprecipitation route are reported. Magnetization versus temperature measurement plot reveals a transition from paramagnetic to superparamagnetic (SPM) phase in contrast with the transition from paramagnetic to long-range ferrimagnetic phase at Curie temperature, T_c, reported in bulk. The blocking temperature, T_b, of SPM phase is found to be 50-60 K. On cooling in the presence of 10 kOe field these nanoparticles show an enhancement in coercivity and shifting of loop at 10 K, which is absent at 50 K. While the later observation supports the blocking temperature of the SPM phase, the former one is attributed to a disordered spin configuration at the surfaces and the distribution of nanoparticle sizes.     

Effect of Ag doping on the crystallization and phase transition of TiO2 nanoparticles

TiO₂ nanoparticles doped with different Ag contents were prepared by a modified sol–gel method, using titanium tetraisopropoxide and silver nitrate as precursors and 2-propanol as solvent. Silver was incorporated into the TiO₂ matrix via decomposition of AgNO₃ during thermal treatment in different atmospheres. Effects of Ag doping on the crystallization and phase transition of the TiO₂ nanoparticles were studied using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and Raman spectroscopy techniques. While air annealing incorporates silver into TiO₂ matrix in silver oxide form, annealing in nitrogen incorporates metallic silver into TiO₂. Formation of silver oxide increases the thermal stability of the TiO₂ particles. Silver oxide affects the crystallization process of TiO₂ particles and the temperature of transition form anatase to rutile. On the other hand, presence of metallic silver in the samples annealed in nitrogen atmosphere decreases the temperature of phase transition of TiO₂ nanoparticles.     

一种检测痕量IgG的免疫纳米银共振散射光谱探针

以柠檬酸三钠作还原剂,采用微波高压合成法制备了粒径约为20 nm的银纳米微粒。在pH 9.0条件下,用银纳米微粒标记羊抗人IgG制备了IgG的免疫纳米银探针(AgGIgG)。在pH为6.0的磷酸盐缓冲溶液及聚乙二醇(PEG)-6000和KCl存在下,IgG与AgGIgG发生免疫反应,裸露的银纳米颗粒在KCl和PEG-6000的作用下发生了聚集,导致体系在485 nm处的共振散射峰增强。考察了pH值、AgGIgG、PEG和KCl浓度,温育温度和时间及共存物质的影响。在最佳条件下,IgG浓度c_IgG在4.0～480 ng·mL-1范围内与485 nm处的共振散射光强度增加值ΔI_{485 nm}呈线性关系,回归方程为ΔI_{485 nm}=76.8c_IgG+4.7,方法检出限为2.4 ng·mL-1 IgG 。该法用于定量分析血清IgG,简便快速,本法结果与免疫比浊法结果一致。     

Significant modifications in the electrical properties of poly(methyl methacrylate) thin films upon dispersion of silver nanoparticles

Electrical conductivity of thin solid films of PMMA with dispersed silver nanoparticles, synthesized by a novel method, was studied in dark conditions by changing the applied voltage and temperature and also under photoexcitation (by a mercury lamp, 125 W) at room temperature. Anomalous hysteresis in current-temperature characteristics during heating and cooling cycles was observed. The hysteresis-like behaviour was explained on the basis of the movements of molecules associated with different parts of a PMMA matrix and diffusion of silver nanoparticles in the PMMA matrix. Dark current in the PMMA films with dispersed silver nanoparticles has been observed to be higher than the corresponding current in the PMMA films without silver nanoparticles due to the creation of conduction paths by the silver nanoparticles/nanoclusters. The photoresponse in the thin solid films of PMMA with dispersed silver nanoparticles was the reverse of that observed in thin solid films of PMMA without silver nanoparticles. A decrease in photocurrent under illumination of light was observed due to the destruction of conduction paths by the illumination of light.     

Solution calorimetric investigation of AgCl-AgI ionic conductor composites at 298 K: observation of metastable AgI modifications

The enthalpies of solution of pure silver halides AgCl and AgI and a composite material with molar composition 0.5 AgCl-0.5 AgI were measured at 298 K in a mixture of Na₂S₂O₃ (1 M) and NH₄OH (1 M). X-ray diffraction patterns showed that the composite material contained the metastable γ-AgI phase; different mechanisms for its stabilization were discussed. The phase transition enthalpies of AgI modifications and the enthalpy of formation of the composite material were deduced from the measurements. The latter could be related to a change of interfacial enthalpies.     

Magnetism of gadolinium nanoparticles near <Emphasis Type="Italic">T</Emphasis><Subscript><Emphasis Type="Italic">c</Emphasis></Subscript>

Influence of temperature and magnetic field H on magnetism of spherical Gd nanoparticles of different sizes (89, 63, 47, 28, and 18 nm) was studied in the temperature range 250 K < T < 325 K. The particles were obtained by metal vapor condensation in the flow of helium. The particles with d = 18 nm did not show a magnetic transition; their structure is a combination of two cubic phases (FCC1 and FCC2). Large particles remained in the HCP phase and had an admixture of the FCC1 phase, the amount of which decreased as the particle sizes increased; magnetic transition took place at T _c = 293 K. The admixture of O₂ did not alter the structure but decreased the magnetization σ and magnetic permeability μ. An orientation transition in polycrystalline gadolinium initiated by the magnetic field H was proved in an experiment. The orientation transition in Gd particles smaller than 63 nm, the magnetic structure of which is close to the single-domain structure, occurred near T _c without the influence of H.     

An evidence for a microscopic phase separation in AsSeAg glasses revealed by thermal and structural investigations

Alternating Differential Scanning Calorimetric (ADSC) studies show that Se rich As₂₀Se_80-xAg_x (0 ≤ x ≤ 15) glasses exhibit two endothermic glass transitions and two exothermic crystallization peaks; the observed thermal behavior has been understood on the basis that As₂₀Se_80-xAg_x glasses are microscopically phase separated, containing Ag₂Se phases embedded in an As-Se backbone. With increasing silver concentration, the Ag₂Se phase percolates in the As-Se matrix, with a well-defined percolation threshold at x = 8. A signature of this percolation transition is shown up in the thermal behavior, as sudden jumps in the composition dependence of non-reversing enthalpy, ΔH_nr obtained at the second glass transition reaction. Scanning Electron Microscopic (SEM) studies also confirm the microscopic phase separation in these glasses. The super-ionic conduction observed earlier in these glasses at higher silver proportions, is likely to be associated with the silver phase percolation.     

Influence of silver nanoparticles on neurons and blood-brain barrier via subcutaneous injection in rats

Nanosilver has been widely used in medical biology; however, the distribution and interaction of nanosilver with cells is still unclear. There have been some reports demonstrating that nanoparticles can cross the blood-brain barrier (BBB). The present study investigated the accumulation of silver nanoparticles in the brain, and the effects of silver nanoparticles on BBB. Nanosilver and microsilver (62.8 mg/kg) particles were subcutaneously injected into rats. The rats were sacrificed at predetermined time points and the brains were obtained for ultrastructural observation and silver level detection. The results showed that silver nanoparticles could traverse the BBB and move into the brain in the form of particle. The silver nanoparticles can induce neuronal degeneration and necrosis by accumulating in the brain over a long period of time.     

TEM monitoring of silver nanoparticles formation on the surface of lead crystal glass

Silver nanoparticles have been formed on the surface of lead crystal glass by means of (i) ion-exchange of alkaline ions from the glass by Ag⁺ ions from a molten salts bath, and (ii) silica based sol-gel coatings containing silver. All experimental variables concerning both ion-exchange process and sol-gel coatings application were combined and studied as main parameters governing the reduction of Ag⁺ ions to Ag⁰ atoms and further aggregation to form nanosized colloids. The content of thermoreducing agents (arsenic or antimony oxides) in the lead crystal glass was essential to favour the reduction of silver ions to form nanoparticles. Optimal experimental conditions to be used for the obtaining of surface silver nanoparticles were determined. TEM was used as the principal characterisation technique for direct observation of the nanoparticles generated. The size of silver colloids varied in the 20-300 nm range for ion-exchanged samples and in the 10-80 nm range for sol-gel coated samples.     

Colossal magnetostriction effect in HoMn2O5

We have investigated the detailed field and temperature dependence of the dielectric constant, electric polarization, magnetization and magnetostriction in orthorhombic HoMn₂O₅ single crystals. HoMn₂O₅ displays incommensurate antiferromagnetic ordering below 39 K, becoming commensurate on further cooling. The commensurate-incommensurate transition takes place at low temperatures. The inherent magnetic frustration in this material is lifted by a small lattice distortion, primarily involving shifts of the Mn³⁺ cations and giving rise to a canted antiferroelectric phase. Colossal magnetostriction effect was observed and a novel phase transition diagram was build.     

Experimental constraints on the phase diagram of elemental zirconium

The phase diagram of zirconium metal has been studied using synchrotron X-ray diffraction and time-of-flight neutron scattering at temperatures and pressures up to 1273 K and 17 GPa. The equilibrium phase boundary of the α-ω transition has a dT/dP slope of 473 K/GPa, and the extrapolated transition pressure at ambient temperature is located at 3.4 GPa. For the ω-β transition, the phase boundary has a negative dT/dP slope of 15.5 K/GPa between 6.4 and 15.3 GPa, which is substantially smaller than a previously reported value of −39±5 K/GPa in the pressure range of 32-35 GPa. This difference indicates a significant curvature of the phase boundary between 15.3 and 35 GPa. The α-ω-β triple point was estimated to be at 4.9 GPa and 953 K, which is comparable to previous results obtained from a differential thermal analysis. Except for the three known crystalline forms, the β phase of zirconium metal was found to possess an extraordinary glass forming ability at pressures between 6.4 and 8.6 GPa. This transformation leads to a limited stability field for the β phase in the pressure range of 6-16 GPa and to complications of high-temperature portion of phase diagram for zirconium metal.     

Model for UV induced formation of gold nanoparticles in solid polymeric matrices

UV irradiation of polymeric PMMA films containing HAuCl₄ followed by annealing at 60-80 °C forms gold nanoparticles directly within the bulk material. The kinetics of nanoparticle formation was traced by extinction spectra of nanocomposite film changes vs annealing time. We propose that UV irradiation causes HAuCl₄ dissociation and thus provides a polymeric matrix with atomic gold. The presence of an oversaturated solid solution of atomic gold in the polymeric matrix leads to Au nanoparticle formation during annealing. This process can be understood as a phase transition of the first order. In this paper we apply several common kinetic models of the phase transition for describing Au nanoparticle formation inside the solid polymer matrix. We compare predictions of these models with the experimental data and show that these models cannot describe the process. We propose that the stabilization effect of the matrix on the growing gold nanoparticles is important. The simplest model introducing some probability for the transition from growing nanoparticle to the non-growing, stabilized form is suggested. It is shown that this model satisfactorily describes the experimentally observed evolution of the extinction spectrum of Au nanoparticles forming in a polymer matrix.     

Phase transition and magnetic properties of Mg-doped hexagonal close-packed Ni nanoparticles

Mg-doped Ni nanoparticles with the hexagonal close-packed (hcp) and face-centered cubic (fcc) structure have been synthesized by sol-gel method sintered at different temperatures in argon atmosphere. The sintering temperature played an important role in the control of the crystalline phase and the particle size. The pure hcp Mg-doped Ni nanoparticles with average particle size of 6.0 nm were obtained at 320 °C. The results indicated that the transition from the hcp to the fcc phase occurred in the temperature range between 320 °C and 450 °C. Moreover, the VSM results showed that the hcp Mg-doped Ni nanoparticles had unique ferromagnetic and superparamagnetic behavior. The unsaturation even at 5000 Oe is one of the superparamagnetic characteristics due to the small particle size. From the ZFC and FC curves, the blocking temperature T_B of the hcp sample (6.0 nm) was estimated to be 10 K. The blocking temperature was related to the size of the magnetic particles and the magnetocrystalline anisotropy constant. By theoretical calculation, the deduced particle size was 6.59 nm for hcp Mg-doped Ni nanoparticles which was in agreement with the results of XRD and TEM.     

Role of dislocation loops on the elastic constants of lyotropic lamellar phases

We study the role of dislocation loops defects on the elasticity of lamellar phases by investigating the variation of the lamellar elastic constants, ˉ and K, induced by the proliferation of these defects. We focus our interest on one particular lamellar phase made up of a mixture of C₁₂E₅ and DMPC in water, which is already well-characterised. This lamellar phase undergoes a second-order (or weakly first-order) lamellar-to-nematic phase transition at about 19^°C and dislocation loops are seen to proliferate within the lamellar structure when temperature is decreased below 30^°C. The values of both elastic constants of this given lamellar phase are measured as a function of temperature, approaching the lamellar-to-nematic transition, with the help of Quasi-Elastic Light Scattering (QELS) on oriented lamellar phases. Very surprisingly we observe a strong and rapid increase in both ˉ and K as the lamellar-to-nematic transition temperature is approached. These increases are seen to start as soon as dislocation loops can be observed in the lamellar phase. We interpret our results as being the consequence of the appearance and proliferation of dislocation loops within the lamellar structure. According to a simple model we developped we show that ˉ and K are proportional to the density of dislocation loops in the lamellar phase.