Effect of temperature on ring-shaped-deposit formated at evaporation of droplets of silver-nanoparticle dispersions

The effect of temperature is studied on the geometric parameters and conductivity of ring-shaped deposits formed at evaporation of droplets of dispersions of silver nanoparticles on hydrophilic (glass) and hydrophobic (copper) substrates. It has been shown that increasing temperature leads to substantial changes in the deposit profile. Therewith, the effects of temperature on droplet evaporation on glass and copper substrates are different. It has been found that the lateral conductivity of a ring-shaped deposit formed on a glass substrate increases stepwise similarly to a percolation transition at a droplet-evaporation temperature of 58°C. It has been suggested that the reason for the temperature effect is related to a change in the ratio between the rates of physicochemical processes occurring at different stages of droplet evaporation.     

The influence of the concentration and size of silver nanoparticles on the conductivity of ring-shaped deposits resulting from evaporation of colloidal solution droplets

The conductivity of ring-shaped deposits formed at the periphery of evaporating droplets of silver nanoparticle colloidal solutions has been studied. The dependence of the resistance of the ring-shaped deposits on nanoparticle size has been shown to exhibit a percolation transition. The specific conductivity of the deposits has been estimated in relation to their geometric shapes. The conductivity has been established to nonmonotonically depend on nanoparticle sizes. It has been noted that, in rather strong fields, the conductivity of the composite layers dramatically increases after some induction period. The X-ray spectra of silver have been revealed to alter for samples the conductivity of which has increased under the action of an external electric field.     

The structure and conductivity of thin composite films formed from nanodispersions of silver particles by the moving meniscus method

The formation processes, structure, geometric parameters, and conductivity are studied for thin composite films prepared from nanodispersions of silver particles with diameters smaller than 10 nm by the moving meniscus method. The thickness and conductivity of the films are determined as functions of the mass concentration of a precursor (AgNO₃) and the concentration (size) of silver nanoparticles. Some of these functions are nonmonotonic. The dependences of the conductivity on these parameters are found to have the character of a percolation transition. Heterogeneous crystallization of soluble components of the colloidal solutions on silver nanoparticles plays an essential role in the formation of the films.     

Electroless deposition of metallic silver from a choline chloride-based ionic liquid: a study using acoustic impedance spectroscopy, SEM and atomic force microscopy

In this paper, we describe the first example of a sustained galvanic coating deposited on a surface from a non-aqueous liquid. We present the surface characterization of electroless silver deposits on copper substrates from a solution of Ag(+) ions in an ionic liquid based on a choline chloride (ChCl) eutectic. Through a study of these deposits and the mechanism of formation using acoustic impedance spectroscopy (QCM), probe microscopy (AFM) and electron microscopy (SEM/EDX), we demonstrate that sustained growth of the silver deposit is facilitated by the porous nature of the silver. This is in contrast to the dip-coating reaction of silver ions in aqueous media, where the reaction stops when surface coverage is reached. Electroless silver deposits of up to several microns have been obtained by dip coating in ionic liquids without the use of catalysts of strong inorganic acids.     

Structural Peculiarities of Anomalous Electrolytic Palladium Deposits Prepared under Hydride Formation Conditions

The peculiarities of bulk and surface structures of electrolytic palladium deposits formed under hydride formation conditions are studied by x-ray diffraction (XRD) and x-ray photoelectron spectroscopy techniques. For anomalous deposits with high hydrogen capacities, the evolution of the XRD behavior is traced as a function of thermal treatment. The material is shown to comprise two cubic phases with different lattice parameters.     

硬脂酸单分子膜上电沉积Ag膜的研究

通过电沉积方法,以气/液界面上形成的硬脂酸单分子膜为模板诱导沉积金属银膜.考察了镀液pH值、单分子膜表面压及沉积电位对银膜形貌及结构的影响.实验发现,酸性镀液的气/液界面上形成的单分子膜不能诱导沉积银,而在中性和碱性镀液的气/液界面上可以诱导银膜的生长.当单分子膜处于液态或固态时,气/液界面有银膜形成;液态单分子膜上的银膜生长速度较快,且银膜的结构一致.随着电极电位的升高,银膜沉积的速度加快,呈环状向外生长的圆形银膜逐渐变得不规则.将不同实验条件下的银膜转移出来,采用扫描电镜(SEM)、透射电镜(TEM)对银膜的结构与形貌进行了表征.研究表明,银首先在单分子膜上异相成核,由八面体构型逐渐发展成星型,最终在气/液界面形成具有松枝状微观结构的光亮银膜.     

Characterization of the Nanoscale Microstructure of an Immersion Silver on Sputtered Copper

1 INTRODUCTION Silver and its compounds have received much attention due to their current and potential applica- tions in many areas[1, 2]. As a metal with the highest electrical and thermal conductivities, silver was one of the most important noble metals used in electrical industries in the last century. Several decades ago, however, the development of silver application in electronic area seemed not so quick. The fear for some undesirable phenomena involving silver, like “electrochemi…     

Photopolymerized silver-containing conducting polymer films. Part I. An electronic conductivity and cyclic voltammetric investigation

A photopolymerization process that simultaneously deposits electronically conducting polymer films and incorporates nanophase silver grains within the films, the silver grains having been formed in situ on irradiating cast, photopolymerizable formulations containing silver salts, was developed. Polymer films produced from formulations containing large organic anions were very flexible and strongly adherent to substrates. Polypyrrole films containing silver grains were characterized electronically on measuring their electronic conductivities and electrochemically on recording their cyclic voltammetric profiles. Conductivities were affected by the chemical identity and concentration of components added to photopolymerizable formulations. The best photopolymerized films had a conductivity of the order of 1 S cm⁻¹. Electronically conducting films derived from formulations consisting of a monomer, an electron acceptor/“dopant,” and a photoinitiator were electrochemically active. They possessed long-term stability under extended electrode potential cycling conditions, acceptable charge storage capacity, and the ability to oxidize or reduce redox couples in solution. Paper submitted for inclusion in the special issue of the Journal of Solid State Electrochemistry honouring the 85th birthday of Professor John O’M. Bockris.     

Mechanisms of pinning accompanying evaporation of colloidal dispersion droplets

Experiments have been performed to clarify the mechanism of pinning, i.e., the phenomenon of fixing menisci of evaporating dispersion droplets, related to the formation of ring-shaped deposits (coffee ring effect). The influence of particle concentration in dispersions and the degree of hydrophilicity (hydrophobicity) of substrates on pinning has been studied. It has been shown that there are three main mechanisms of pinning, with the first one being due to the hysteresis of droplet contact angle, the second mechanism resulting from the adhesion of particles to substrates, and the third one being caused by the formation of a dense adsorption layer on a substrate. A relation has been revealed between the pinning mechanism that occurs and the degree of substrate hydrophilicity.     

Preparation and Characterization of a Composite of Silver Iodide and Synthetic Mordenite

A composite material made up of AgI and the potassium form of mordenite has been prepared by treating the silver form of synthetic mordenite with potassium iodide. The composite as well as the silver and potassium forms of mordenite have been characterised by X-ray powder diffractometry, X-ray photoelectron spectroscopy, EDS analyses and ac conductivity measurements. It has been inferred that, in the composite material, AgI grows at the entrance of the zeolite channels without forming a continuous conducting phase. The silver form of mordenite has been proved to be a silver ion conductor by dc conductivity measurements.     

Specific features of polyol synthesis of silver nanoparticles with the use of solid carboxylates as precursors

Electron microscopy, X-ray diffraction, and chromatography-mass spectrometry have been employed to investigate the reduction of solid silver caprylate in ethylene glycol with the formation of silver nanoparticles. The structural characteristics of silver nanoparticles have been studied as depending on the conditions of their synthesis, including temperature, reduction time, and silver salt concentration. It has been found that, in the studied range of parameters under the conditions, when solid silver caprylate is dispersed in ethylene glycol, the characteristics of resulting nanoparticles are almost independent of the synthesis temperature. This peculiarity is related to the fact that the formation and growth of nanoparticles occur on the surface of silver salt crystals and are accompanied by gradual dissolution thereof. In this system, ethylene glycol plays the roles of a reductant and a solvent for liquid reaction products.     

Label‐Free Electrochemical Imaging of Latent Fingerprints on Metal Surfaces

A label‐free electrochemical method based on scanning electrochemical microscopy (SECM) has been developed to image latent fingerprints with high resolution on five kinds of metal surfaces (platinum, gold, silver, copper and stainless steel), as it could measure the minor conductivity differences of the substrate surface and avoid the interference of the background‐color. The images of sebaceous fingerprints on clean metals were revealed by SECM with ferrocene methanol acting as a redox mediator to detect the topology of the fingerprint deposits in constant‐height feedback mode. Inhibition of electrochemical processes on areas of the surface masked by the insulating fingerprint residues generated a negative image of the fingerprint.     

Novel Bottom‐Up SERS Substrates for Quantitative and Parallelized Analytics

Surface‐enhanced Raman spectroscopy (SERS) is an emerging technology in the field of analytics. Due to the high sensitivity in connection with specific Raman molecular fingerprint information SERS can be used in a variety of analytical, bioanalytical, and biosensing applications. However, for the SERS effect substrates with metal nanostructures are needed. The broad application of this technology is greatly hampered by the lack of reliable and reproducible substrates. Usually the activity of a given substrate has to be determined by time‐consuming experiments such as calibration or ultramicroscopic studies. To use SERS as a standard analytical tool, cheap and reproducible substrates are required, preferably with a characterization technique that does not interfere with the subsequent measurements. Herein we introduce an innovative approach to produce low‐cost and large‐scale reproducible substrates for SERS applications, which allows easy and economical production of micropatterned SERS active surfaces on a large scale. This approach is based on an enzyme‐induced growth of silver nanostructures. The special structural feature of the enzymatically deposited silver nanoparticles prevents the breakdown of SERS activity even at high particle densities (particle density >60 %) that lead to a conductive layer. In contrast to other approaches, this substrate exhibits a relationship between electrical conductivity and the resulting SERS activity of a given spot. This enables the prediction of the SERS activity of the nanostructure ensemble and therewith the controllable and reproducible production of SERS substrates of enzymatic silver nanoparticles on a large scale, utilizing a simple measurement of the electrical conductivity. Furthermore, through a correlation between the conductivity and the SERS activity of the substrates it is possible to quantify SERS measurements with these substrates.     

Radiation-chemical decomposition of heavy metal azides—III. The role of two-valence impurity cations in radiation-stimulated processes in silver azide

Ion and electron transfer in the irradiation field as well as silver azide radiolysis doped with Cu²⁺, Pb²⁺, Cd²⁺ cations topography and kinetics have been studied. A certain part of impurity cations appeared to enter the crystal lattice to form solid solutions, they being chemisorbed partially on the surface to form complexes with low mobility. Ion transfer parameters change greatly due to interstitial silver ions concentration decrease, cation vacancy concentration increase and because of doped cations participating in the transfer in doped systems. Impurity cations being electron traps and recommendation centers influence the radiation conductivity value. In addition, Cu²⁺ ions lose their mobility caused by their transition into the atomic state.In fact, during silver azide radiation-chemical decomposition bivalent impurity cations become radiolytic metal particle formation centers. This has been inferred from the fact that the radiolytic metal contains as much as 30% of dopants at the initial stages, which has experimentally been proved. This results in kinetic curve change and general radiolysis acceleration at the initial stage with decomposition proceeding under nonstationary conditions. The impurity cation effect seemed insignificant for larger degrees of radiolysis with decomposition proceeding under stationary conditions.The scheme of silver azide radiolysis with no radiolytic particle metal participating in the growth process during thermo-activated stages has been proposed, accounting for the results obtained.     

Formation of silver nanoparticles in deoxyribonucleic acid-poly(o-methoxyaniline) hybrid: a novel nano-biocomposite

A novel nano-biocomposite of silver and poly(o-methoxy aniline) (POMA)/DNA hybrid has been prepared by adding DNA solution to an aqueous solution of POMA (emeraldine base, EB) and AgNO(3) mixture. The mixture was aged for 10 days and was freeze-dried to form the hybrid nanocomposite (weight fraction of DNA = 0.75). FESEM pictures show a fibrillar network morphology of the biomolecular hybrid with silver nanoparticles on its surface. The TEM picture also corroborates silver nanoparticle formation in the biomolecular hybrid, and the denser population of nanoparticles in the TEM micrograph as compared to that in the SEM micrograph indicates that the nanoparticles are present inside the fibrils in greater proportion. The dc conductivity value of the hybrid indicates that POMA (EB) is doped by silver ion and the doped POMA form complexes with DNA through electrostatic interaction of the radical cation of POMA (emeraldine salt form, ES) and the DNA anion. During the doping process and Ag nanoparticle formation, a fluctuation of the pi band to polaron band transition peak occurs together with a complementary fluctuation of the polaron band to pi* band transition peak. After 53 h of aging, the former shows a slow but continuous red shift with aging time. This has been attributed to the slow uncoiling of POMA on the DNA surface. The conformation and crystal structure of DNA remain intact during the nano-biocomposite formation. The dc conductivity value of the nano-biocomposite is almost the same as that of the pure POMA-DNA hybrid at the same composition, but the I-V characteristic curve of the nano-biocomposite is somewhat different showing an insulating region on low applied voltage. At higher applied voltage, it shows a semiconducting property characterizing the large band gap semiconducting behavior of the nano-biocomposite.     

Reversible pattern formation through photolysis

We report a photolytic method to induce spatial and temporal patterning/deposition of particles at the micron scale on a time scale of seconds. Reversible pattern formation by negatively charged particles occur around micron-sized silver features on different substrates when exposed to UV light in the presence of aqueous hydrogen peroxide. Diffusiophoretic motion due to a spatially defined ion gradient accounts for our observations. Atomic force and optical microscopy, as well as conductivity measurements, support this hypothesis.     

Hydrothermal-induced assembly of colloidal silver spheres into various nanoparticles on the basis of HTAB-modified silver mirror reaction

Small colloidal silver spheres (diameter < 10 nm) were found to assemble into various silver nanoparticles including cubes, triangles, wires, and rods in water in the presence of HTAB (n-hexadecyltrimethylammonium bromide) at 120 degrees C, while the colloids were generated in situ on the basis of a HTAB-modified silver mirror reaction during the synthesis process. Adjustment of the synthesis parameters, in particular the concentrations of HTAB and [Ag(NH3)2]+, led to an obvious shape evolution of silver nanoparticles, thus resulting in the shape-selective formation of the silver nanoparticles. The monodisperse nanocubes with a well-defined crystallographical structure (a single crystal bounded by six {200} facets) have a strong tendency to assemble into two-dimensional arrays on substrates. The nanowires with uniform diameter usually existed in the form of two-dimensional alignments. The findings suggested that hydrothermal-induced assembly of small silver colloidal particles should be a convenient and effective approach to the preparation of various silver nanoparticles.     

The formation of mono- and bimetallic silver-containing seed nanoparticles

The regularities of the formation of mono- and bimetallic seed particles used for subsequent synthesis of anisotropic silver nanoparticles in micellar media has been studied. It has been found that the formation of nanosized silver seed particles is influenced by the synthesis parameters, such as the presence of oxygen and gold in the reaction system. Based on characteristics of the surface plasmon resonance band of nanoparticles, a simple and efficient method has been proposed for controlling the degree of monodispersity of the seed particles.     

Synthesis and Heterogeneous Structure of Anionic Networks of Oligoester Acrylates

Anionic polymerization has been used for the synthesis of polymeric networks based on α,ω-dimethacrylbis(triethylene glycol) phthalate, α,ω-dimethacrylbis(diethylene glycol) phthalate, and α,ω-dimethacrylbis(ethylene glycol) phthalate. The dependence of network polymer yields on catalyst concentration has a maximum. The correlation between the value and position of maxima and the length of the initial oligomeric chain has been established. The network polymers were studied by use of small-angle x-ray scattering. The parameters of heterogeneous structure and their relation to the peculiarities of the polymerization process have been established. It was established that the microheterogeneous structure of the networks is determined by the geometric characteristics of the initial oligomeric chains and the conditions of synthesis.     

Mössbauer and XRD investigation of electrodeposited Fe,Co and Fe-Co alloys using a gluconate plating process

Summary A fundamental requirement for electrodeposition systems of the 21st century is that the processes involved should be environmentally safe, as well as they should be suited to replace hazardous conventional processes thereby supporting global sustainability. Conventional plating baths contain hazardous components and facilitate the generation of non-desirable compounds. The subject of the present article is the electrodeposition of Fe, Co, and Fe-Co alloys from an electrolyte based on gluconate. Preliminary studies showed that good quality iron-cobalt alloy coatings could be obtained on copper substrates from an environmentally acceptable gluconate plating system. The gluconate bath is inexpensive, non-toxic and easily disposed of. We report the successful deposition of Fe, Co and Fe-Co alloys from a modified gluconate based electrolyte which has not been used previously to deposit these materials. The effect of process parameters, such as current density, pH and deposition time were investigated using the gluconate electrolyte at a temperature of 60 °C and a pH of 7. The phase composition, crystal structure and magnetic anisotropy of the obtained alloy deposits are correlated with the applied process parameters. The structural analysis of the deposits is mainly based on ⁵⁷Fe CEMS and XRD measurements. α-Fe and Co-Fe were identified as dominant phases in Fe and Co/Fe deposits, respectively. The magnetic anisotropy of the Fe-containing deposits was found to correlate with the current density applied during deposition. The time of electrodeposition, at the same time, had little if any effect on the magnetic anisotropy of the obtained deposits. The mechanism and formation of the electrodeposits are discussed on the basis of the obtained results.