Rapid Synthesis of Silver Nanoparticles by Microwave-Polyol Method with the Assistance of Latex Copolymer

Highly stable and monodispersed silver nanoparticles with uniform morphology have been successfully prepared by microwave (MW) irradiation within a few seconds from the mixture of silver nitrate, ethanol and latex copolymer. The aqueous emulsion of latex copolymer acts as both reducing and stabilizing agent. To the best of our knowledge, it was the first time that the effect of MW irradiation time and latex concentration on the silver nanoparticle preparation and properties was analyzed. The formation of silver nanoparticles was confirmed by Ultraviolet–visible spectroscopy and transmission electron microscopy (TEM). The UV–Vis spectra are marked by the characteristic surface plasmon absorption band in the range 410–420 nm. From TEM images, silver nanoparticles were observed to be spherical with sizes ranging from 4 to 10 nm. Electron diffraction patterns on selected area, indicated that the silver nanoparticles are crystalline with face centered cubic structure.     

Preparation and the mechanisms of formation of silver particles of different morphologies in homogeneous solutions

Uniform, well-dispersed silver particles of various morphologies have been prepared by reducing highly acidic silver nitrate solutions with ascorbic acid in the presence of a sodium naphthalene sulfonate-formaldehyde copolymer as dispersing agent. By varying the temperature of the reaction, the free acid content, the addition rate of the reductant, and the aging time, both isometric and anisotropic silver particles could be obtained. It was found that the latter were formed by aggregation of nanosize subunits, which were identified by electron microscopy and X-ray diffractometry.     

Development of cellulose nanowhisker-polyacrylamide copolymer as a highly functional precursor in the synthesis of nanometal particles for conductive textiles

Herein we present extensive studies that were undertaken to develop a new copolymer with distinctive characteristics for utilization in different applications particularly in conductive textiles. The copolymer is based on graft polymerization of cellulose nanowhiskers (CNWs) with acrylamide and therefore nominated CNW-polyacrylamide (PAAm) copolymer. Development of this copolymer comprises preparation of CNWs from purified cotton sliver as per the acid hydrolysis method, followed by copolymerization of the freshly prepared CNWs with AAm at different feeding ratios for the sake of product optimization in the presence of K₂S₂O₈ as initiator. Thus, obtained CNW-PAAm copolymers were characterized by making use of the proper instruments and analysis facilities. Following this, the newly prepared and promising copolymer was selected and used as a precursor in the green synthesis of silver and copper nanoparticles. The crystal nature of CNWs as cellulose I remains unaltered after copolymerization, but the crystallinity decreases. According to thermal gravimetric analysis, the copolymer is much more thermally stable than CNWs. The CNW-PAAm copolymer can be used successfully as a highly functional, effective and adequate precursor for green synthesis of silver and copper nanoparticles as shown by UV-Vis spectral analysis and transmission electron microscopy micrographs. A multi-branched shape and hyperbranched shape-like tree involving silver nanoparticles and the PAAm graft of the copolymer are formed. Furthermore, Cu nanoparticles are chosen as a candidate for conductive fabrics application.     

Sorption of noble metal compounds by cross-linked copolymer of 1-vinyl-1,2,4-triazole with acrylic acid

Sorption properties with respect to noble metal compounds were examined for a new divinyl benzene cross-linked nitrogen-containing heterocyclic copolymer of 1-vinyl-1,2,4-triazole with acrylic acid. The sorption recovery of chloride complexes of Au(III), Pt(IV), Pd(II), and Ag(I), as well as of silver nitrate from acidic solutions was examined in relation to the nature and concentration of acids and the contact time between the phases.     

Stabilization of silver nanoparticles with copolymers of maleic acid

Silver nanoparticles are obtained by reducing AgNO₃ with sodium borohydride in an aqueous solution in the presence of maleic acid copolymers with ethylene, N-vinylpyrrolidone, or styrene, as well as their octadecylamide group-containing hydrophobized derivatives, as dispersants. The influence of the structural features of the dicarboxylic acid copolymers on the silver nanoparticle formation process and the conditions for producing sols containing spherical nanoparticles with sizes of 1.5–3.5 nm (according to the data of transmission electron microscopy) are determined. It is shown that, at the equimolar copolymer/silver cation ratio, the morphology of resulting silver nanoparticles weakly depends on the nature of comonomers of maleic acid and the presence of hydrophobic fragments, which play an auxiliary role in the stabilization of dispersions of nanoparticles by increasing their stability with respect to ionic strength and oxidation. Evolution of the particle sizes in the system is monitored beginning with copolymer solutions to silver sols by the methods of light scattering, transmission electron microscopy, and atomic force microscopy. According to the light scattering data, copolymers and their complexes with silver ions in solutions are partly aggregated at concentrations corresponding to the conditions of nanosilver synthesis. Silver sols are shown to contain stabilized nanoparticles, which represent core-polyelectrolyte corona-type micelles and micellar clusters with polyelectrolyte coronas.     

Regulation of the sizes of silver nanoparticles stabilized with a maleic acid copolymer and the prospect of their biotechnological use

Methods of synthesizing silver nanoparticles (SNP) of various sizes stabilized with a maleic acid copolymer are proposed. The colloidal solutions of SNP are characterized by electron spectroscopy, static and dynamic light scattering, transmission electron microscopy. The stability of the obtained SNP in solutions of hydrogen peroxide and a hydrochloric acid salt is studied, their efficiency in antimicrobial activity tests is assessed.     

Synthesis of copolymer-stabilized silver nanoparticles for coating materials

Silver ions being less toxic than silver nanoparticles, a more safe material can be obtained to be used as antimicrobial coating. This can be achieved by using thiol chemistry and covalently attach the silver nanoparticles in the coating. Our aim is to produce a coating having antimicrobial properties of silver ions but with the silver nanoparticles firmly attached in the coating. Here, we present a way to produce silver nanoparticles that can be used as a component in a coating or as such to produce an antimicrobial coating. The silver nanoparticles presented here are stabilized by a copolymer (poly(butyl acrylate–methyl methacrylate)) that is soft and has well-known good film-producing properties. The reversible addition-fragmentation chain transfer radical polymerization technique used to prepare the polymers provides conveniently a thiol group for effective binding of the silver nanoparticles to the polymers and thus to the coating.     

Silver Metallic Nanoparticles with Surface Plasmon Resonance: Synthesis and Characterizations

Silver nanoparticles were synthesized by the reduction of the silver nitrate (AgNO₃) using the latex copolymer in ethanol solution under microwave (MW) heating. The reaction parameters such as silver precursor concentration (from 0.005 to 0.1 g/l) and MW power (200–800 W) significantly affect the formation rate, shape, size and distribution of the silver nanoparticles. A significant reduction of irradiation time was observed when the MW energy is compared to conventional thermal reduction processes. The prepared silver nanoparticles show uniform and stable sizes from 5 to 11 nm, which can be stored at room temperature for approximately 12 months without any visible change. These peculiarities indicate that the latex copolymer is a good stabilizer for the silver nanoparticles. The optical properties, morphology, and crystalline structure of the silver-latex copolymer nanocomposites were characterized by the Ultraviolet–Visible spectroscopy, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The study of the TEM images at high magnifications identified the silver nanoparticles as face-centered cubic (fcc) structure with spherical and hexagonal shapes.     

Synthesis and characterization of silver polymer nanocomposites of 1-vinyl-1,2,4-triazole with acrylonitrile

Novel organic-inorganic nanocomposites were synthesized by chemical reduction of silver ions from silver acetate in DMSO and DMF solutions in the presence of the stabilizing copolymer of 1-vinyl-1,2,4-triazole-acrylonitrile. The solvents DMSO and DMF can act as efficient reducing agents for silver ions, which makes it possible to carry out the reaction under mild conditions and simplify procedures of nanocomposite isolation. The structure and properties of the starting copolymer and related nanocomposites were characterized by UV, IR, and ¹H and ¹³C NMR spectroscopy, as well as transmission electron microscopy and thermogravimetry. The prepared polymer nanocomposites contain 6.8–7.2% silver in the form of nanoparticles with a size of 2–20 nm uniformly dispersed in the polymer matrix. The nanocomposites are readily soluble in DMSO and DMF and do not decompose on heating to 260 °C.     

载银离子PLGA-PEG-PLGA温度敏感水凝胶的制备及体外抗菌性能

利用聚乙二醇(PEG 1000)引发乙交酯和 D,L-丙交酯开环共聚合, 制备了聚丙交酯乙交酯(PLGA)三嵌段共聚物(PLGA-PEG-PLGA)温敏水凝胶材料; 利用核磁共振氢谱( ¹H NMR)确定了产物的结构及组成. 通过还原硝酸银的方法制备银纳米粒子(AgNPs), 并将其与PLGA-PEG-PLGA三嵌段共聚物水凝胶混合, 制得新型AgNPs/PLGA-PEG-PLGA复合水凝胶; 对该复合水凝胶的相关性能进行了表征. AgNPs/PLGA-PEG-PLGA复合水凝胶仍然具有温敏性能, 随着温度升高可发生溶胶-凝胶的相转变; 还可以持续释放银纳米粒子, 从而发挥抗菌性能. 体外细胞实验结果表明, AgNPs/PLGA-PEG-PLGA复合水凝胶具有良好的生物相容性, 未见明显细胞毒性, 是具有应用前景的新型复合水凝胶.     

Electrical transport properties of poly(aniline-co-p-phenylenediamine) and its composites with incorporated silver particles

Statistical copolymers of aniline and p-phenylenediamine, poly(aniline-co-p-phenylenediamine)s, were synthesised by oxidative polymerisation using various oxidants, ammonium peroxydisulphate or silver nitrate. Depending on the choice of oxidant, copolymers or composites with silver particles were obtained. Different molar concentrations of p-phenylenediamine in the reaction mixture provided materials of different conductivities. The influence of both the copolymer composition and the presence of discrete silver particles on the electric and dielectric properties of the system was studied. The results showed a decrease in the conductivity of copolymers and their composites with the silver content compared with the content of standard polyaniline salt. The reduction in conductivity was described in terms of the decreased density of hopping centres due to defects in the copolymer structure. The dielectric relaxations observed were described in terms of their activation energies and were linked to the corresponding conduction mechanism.     

A novel route to in‐situ incorporation of silver nanoparticles into supramolecular hydrogel networks

A novel strategy was developed for the in situ incorporation of silver nanoparticles into the supramolecular hydrogel networks, in which colloidally stable silver hydrosols were firstly prepared in the presence of an amphiphilic block copolymer of poly(oxyethylene)‐poly(oxypropylene)‐poly(oxyethylene) and then mixed with aqueous solution of α‐cyclodextrin. The analyses from rheology, X‐ray diffraction, and scanning electron microscopy confirmed the formation of the supramolecular‐structured hydrogels hybridized with silver nanoparticles. In particular, the colloidal stability of the resultant silver hydrosol and its gelation kinetics in the presence of α‐cyclodextrin as well as the viscoelastic properties of the resultant hybrid hydrogel were investigated under various concentrations of the used block copolymer. It was found that the used block copolymer could act not only as the effective reducing and stabilizing agents for the preparation of the silver hydrosol but also as the effective guest molecule for the supramolecular self‐assembly with α‐cyclodextrin. In addition, the effects of silver nanoparticles on the gelation process and the hydrogel strength were also studied. Such a hybrid hydrogel material could show a good catalytic activity for the reduction of methylene blue dye by sodium borohydride. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 740–749, 2009     

A facile and simple method for the preparation of copoly(TEAMPS/VP)/silver nanocomposites for the humidity-sensing membranes

We developed a simple method for the preparation of polyelectrolyte/silver nanocomposites, where silver nanoparticles were dispersed in a polyelectrolyte. Copoly(TEAMPS/VP)/silver (w/w=100/0, 100/1, 100/2, 100/3 and 100/4) nanocomposites were obtained by a thermal decomposition reaction of silver carbamate complex at 130 degrees C, and well-dispersed silver colloids were stabilized by copolymer of tetraethylammonium 2-acrylamido-2-methyl-1-propanesulfonate (TEAMPS) and N-vinylpyrrolidone (VP). A dark brown solution in its UV-vis absorption spectrum showed surface plasmon resonance absorption bands at 420 nm in solution. The silver precursor and the resulting polyelectrolyte/Ag nanocomposite was characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), infrared (IR), transmission electron microscopy (TEM). In addition the humidity-sensing properties using copoly(TEAMPS/VP)/Ag nanocomposite films were examined.     

Application of a voltammetric method for investigation the formation mechanisms of silver nanoparticles in multicomponent solutions

A voltammetric method has been tested for the investigation of the kinetics of formation of silver nanoparticles in two systems: (a) silver(I) triflourineacetate, methylcellosolve, butyl acetate, toluene and methyl methacrylate with methacrylic acid copolymer; and (b) silver nitrate, sodium citrate, poly-N-vinyl-2-pirrolydone, sodium borohydride. It could be established for the first system that the formation rate of metal nanoparticles from silver triflourineacetate solutions depends on the dielectric constant and complexing ability of the solvent. The formation of silver particles proceeds faster in methylcellosolve than in other solvents. The butyl acetate addition to the solution contributes to the complex stability of methylcellosolve with silver triflourineacetate and decelerates the formation process of particles. It could be shown that nitrogen purging of solutions containing poly-N-vinyl-2-pirrolydone affects the silver-ion concentration in the first stage of synthesis and accelerates the formation process of nanoparticles for the second system. The spherical silver nanoparticles which are formed at the first stage of the synthesis are destroyed after starting the UV–irradiation. Then new silver nanoparticles (triangular prisms) are formed.     

Studies of difurylmethane‐maleic anhydride copolymer as an ion‐responsive membrane for the determination of mono‐, di‐ and tri‐valent cations

The synthesis of the difurylmethane‐maleicanhydride(DFM‐MAH) copolymer was done by reacting difurylmethane with maleic acid followed by hydrolysis with sodium hydroxide to produce the anhydride sodium salt. Construction of a sensor with the copolymer as the ion‐exchanger material was done by mixing the copolymer with poly(vinylchloride), PVC, plastic matrix and dibutylphthalate (DBP) plasticizer in tetrahydrofuran (THF) solvent to form a paste. The paste was coated on a piece of silver wire to produce a coated wire electrode (CWE). The response characteristics of the copolymer‐CWE, in potentiometric analysis, were studied for mono‐, di‐ and tri‐valent cations. All the cations studied showed a near‐Nernstian response for concentrations ranging from 5 x 10⁻⁸ M to 1 x 10⁰M in triethanolamine buffer in aqueous media (0.5 M, pH 10.5). The membrane had a composition of 20:20:60 for the copolymer, PVC and DBP.     

Redox-mediated synthesis and encapsulation of inorganic nanoparticles in shell-cross-linked cylindrical polyferrocenylsilane block copolymer micelles

Detailed studies of a new approach to the synthesis and encapsulation of silver and silver halide nanoparticles inside shell-cross-linked cylindrical block copolymer polyisoprene-block-polyferrocenyldimethylsilane (PI-b-PFS) micelles (1) through in situ redox reactions are reported. The cylindrical nanostructures 1 were prepared by the solution self-assembly of the PI-b-PFS diblock copolymer in the PI-selective solvent hexane followed by Pt(0)-catalyzed PI shell-cross-linking hydrosilylation reactions. The partial preoxidation of the swollen PFS core using tris(4-bromophenyl)aminium hexachloroantimonate [p-BrC6H4)3N][SbCl6] (2, Magic Blue) followed by redox reaction between the remaining Fe(II) centers in the PFS core and Ag(+) cations led to the formation of silver nanoparticles. High-resolution scanning transmission electron microscopy images of the resulting peapod structures provided a clear indication that the nanoparticles were encapsulated inside the micelles. The composition of the nanoparticles was analyzed by energy-dispersive X-ray spectroscopy (EDX). By combining the evolution of the UV-vis spectra of the reaction mixture and EDX measurements, we surprisingly found that silver halide seed particles were formed through a precipitation reaction at an early stage of the encapsulation process. The size of the silver nanoparticles varied with different amounts of silver ions added to the micelle solution. When I2 was used as the preoxidant, AgI nanoparticles were formed and encapsulated inside the cylinders through the precipitation reaction between iodide anions and silver ions. The packing density of the resulting AgI nanoparticles was increased by an iterative addition method, which utilizes the reversible redox properties of PFS. The small encapsulated AgI nanoparticles were also shown to serve as seeds for the formation of larger Ag nanoparticles when a silver salt was subsequently added.     

AA-AM-AN三元共聚物的合成及其溶液性能的研究

采用自由基水溶液共聚法制备了水溶性丙烯酸－丙烯酰胺－丙烯腈共聚物。对聚合反应温度、引发剂用量、尿素用量、聚合物浓度、电解质浓度、剪切速率、温度等因素对聚合物溶液性能的影响进行了研究。结果表明,合成的水溶性聚合物具有良好的增稠作用及耐温抗盐抗剪切等性能。     

Nanoscale patterning of two metals on silicon surfaces using an ABC triblock copolymer template

Patterning technologically important semiconductor interfaces with nanoscale metal films is important for applications such as metallic interconnects and sensing applications. Self-assembling block copolymer templates are utilized to pattern an aqueous metal reduction reaction, galvanic displacement, on silicon surfaces. Utilization of a triblock copolymer monolayer film, polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO), with two blocks capable of selective transport of different metal complexes to the surface (PEO and P2VP), allows for chemical discrimination and nanoscale patterning. Different regions of the self-assembled structure discriminate between metal complexes at the silicon surface, at which time they undergo the spontaneous reaction at the interface. Gold deposition from gold(III) compounds such as HAuCl4(aq) in the presence of hydrofluoric acid mirrors the parent block copolymer core structure, whereas silver deposition from Ag(I) salts such as AgNO3(aq) does the opposite, localizing exclusively under the corona. By carrying out gold deposition first and silver second, sub-100-nm gold features surrounded by silver films can be produced. The chemical selectivity was extended to other metals, including copper, palladium, and platinum. The interfaces were characterized by a variety of methods, including scanning electron microscopy, scanning Auger microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy.     

Selective olefin permeation through Ag(I) contained silicone rubber-graft-poly(acrylic acid) membranes

The silicone rubber (SR) based graft copolymer, SR-graft-poly(acrylic acid) (SR-g-AA), was modified by incorporating silver ion (SR-g-AA-Ag⁺) for C₄ olefin/paraffin gases separation. Olefin could be transported across the complex membrane by the silver ion facilitated transport. The permeation properties, as measured by gas chromatography equipped with a gas permeability analyzer, implied a facilitating effect for olefin. Typical trans-2-butene/n-butane selectivity in the 95.6% grafted complex membrane at 25°C is 4.0. Also, the influences of AA% grafting, measuring temperature and pressure to the permeation properties of C₄ gases were studied. In addition, the sorption behaviors of C₄ gases in SR based membranes are presented and discussed by the Flory-Huggins equation. Finally, the selectivity of solubility and diffusivity in these SR based membranes are also discussed.     

Photochemical modification of polymer surface by the pendant photobase generator containing oxime‐urethane groups and its application to an image‐recording material

Copolymers containing oxime‐urethane groups were prepared by the copolymerization of methyl methacrylate and benzophenoneoximinocarbonylaminoethyl methacrylate (BCM), and their photochemical properties were examined from the UV and IR absorption spectral changes. The decomposed fraction of oxime‐urethane groups in the copolymer increased with irradiation time, but it decreased with the content of BCM units in the copolymer. Changes of the surface properties of the copolymer film on irradiation were studied by measurements of the contact angle and dyeing with an acid dye. The surface of the copolymer film changed to become more hydrophilic upon irradiation with 254 nm of UV light. After the irradiated copolymer films were treated with HCl or methanol, changes of the contact angle of water on irradiation were compared. The copolymer film was dyed by acid dyes after treatment of the irradiated film with HCl. The degree of dyeing increased with irradiation time and BCM units in the copolymer, but it was unaffected by the film thickness. Various colors were developed on the irradiated area depending on the acid dye as the developer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1200–1207, 2002