A rapid approach to urushiol–copper(I) coordination polymer under UV irradiation

Urushiol–metal polymers have attracted more and more attention in China because of their wide applications as a heavy anticorrosive coating in chemical industry. They could also offer many novel properties, including catalytic activity, magnetic property, semiconductive properties, flame retarding performance, etc., and significant progresses have been achieved in synthesis and study on the mechanism of these polymers. In this paper, a rapid method for fabrication of urushiol–copper(I) coordination polymer was developed under UV irradiation within 2 min. The formation and thermo-stability of the cured films were characterized by ESR, XPS, FT-IR, TGA, etc. The results suggested the coordination occurred between copper(I) ion and oxygen under UV irradiation. In the course of UV irradiation, the hydroxyl groups on the phenyl ring of urushiol were dissociated to urushiol semiquinone, and then coordinated with copper(I) ions generated by deoxidization of copper(II) ion. At the same time, crosslinking reaction on the long aliphatic unsaturated side chain occurred to form polymer. TG analysis showed that the polymer had excellent thermo-stability.     

Comparison between laser‐induced nucleation of ZnS and CdS nanocrystals directly into polymer matrices

The nucleation of two kinds of crystalline nanoparticles, zinc sulfide (ZnS), and cadmium sulfide (CdS), is achieved directly into specific sites of polymer matrices after their irradiation with UV laser pulses. The starting samples consist of polymers doped with precursors of Zn or Cd thiolate that are proved to decompose after the absorption of UV light, resulting into the nanoparticles formation. The growth of the crystalline nanostructures is followed throughout the irradiation of the samples with successive incident pulses, by different methods, such as transmission electron microscopy, atomic force microscopy, confocal microscopy, and X‐ray diffraction. Special attention is paid to the difference of the formation pathways of the two kinds of nanoparticles studied, because the Cd thiolate precursor exhibits much higher absorption efficiency than the Zn thiolate one, at the applied UV wavelength. Indeed, CdS nanoparticles become evident after the very first incident UV pulses, whereas the formation of ZnS nanocrystals requires rather prolonged irradiation, always through a macroscopically nondestructive procedure for the polymer matrix. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

In situ preparation of CdS/PVA nanocomposites using gamma radiation

Films of poly(vinyl alcohol)/cadmium sulphide (PVA/CdS) nanocomposite containing various concentrations of Cd²⁺ ions were prepared using gamma radiation at different doses from 50 up to 200 kGy. The UV/VIS spectra revealed that the CdS/PVA nanocomposites showed blue shift for the absorption peak as compared with bulk CdS. As the irradiation dose increased, a gradual red shift in the wavelength accompanying with broadening of the absorption peak was observed. The estimated optical band gap energies and the calculated CdS particle sizes of (PVA/CdS) showed correlation between their values and the variable parameters (irradiation dose and Cd⁺²:S^?2 molar ratio). Transmission electron microscopy images showed that the CdS/PVA nanocomposites were dispersed as spherical CdS nanoparticles with homogeneity at either lower concentration of CdCl₂ or irradiation dose. The nano‐rod structures of CdS was accompanied with small agglomeration at either higher CdCl₂ concentration or irradiation dose. A cubic phase and mixture of cubic and hexagonal phases of the prepared CdS nanoparticles were formed at lower and higher CdCl₂ concentrations, respectively. Fourier Transform Infrared spectra confirmed the coordination of CdS nanoparticles with the hydroxyl groups of PVA matrix. POLYM. ENG. SCI., 55:2583–2590, 2015. © 2015 Society of Plastics Engineers     

Suspension polymerization stabilized by triblock copolymer with CdS nanoparticles

In this paper, a new method to prepare polymer colloid particles stabilized by triblock copolymer with CdS nanoparticles was described. Poly(ethylene glycol-block-styrene-block-2-(dimethylamino) ethyl methacrylate) (PEG-b-PS-b-PDMAEMA) triblock copolymer was synthesized by sequential ATRP method. Micelles with CdS nanoparticles in the corona were prepared by “in situ” reaction of hydrogen sulfide with cadmium ion clusters in the corona of the micelles. The size of the CdS nanoparticles is affected by molar ratio of DMAEMA to cadmium ions and polymer concentration in the solution. When introduced into o/w emulsion the micelles reassemble on the surface of styrene oil droplets. PS colloid particles stabilized by triblock copolymer with CdS nanoparticles were achieved by suspension polymerization. TEM image indicates that CdS nanoparticles locate at the surface of the PS colloid particles.     

Phase Controlled Monodispersed CdS Nanocrystals Synthesized in Polymer Solution Using Microwave Irradiation

Cadmium sulfide (CdS) nanocrystals were synthesized in aqueous solution of polyvinyl pyrrolidone (PVP) via the simple and rapid microwave irradiation method. It is revealed that sulfur source is a key factor in controlling the phase formation of the resulting nanocrystals. The hexagonal and cubic structure of CdS nanocrystals could be obtained with varying sulfur sources of thioacetamide and sodium sulphide respectively. The interaction mechanism of PVP with precursor ions of cadmium and sulfur sources in the preparation process was proposed. It is found that PVP compounded the CdS nanoparticles and protected them from agglomerating. With increasing of PVP concentration, the average particle size of CdS nanocrystals increased and subsequently their optical band gap decreased. At the appropriate dosage of PVP, well isolated nanoparticles with relatively narrow size distribution were obtained for both sulfur sources. Moreover the stability of CdS nanoparticles enhanced after coating with polymer.     

Characterization and conductive property of polyurushiol/silver conductive coatings prepared under UV irradiation

Polyurushiol/silver (PU/Ag) composite conductive coatings were prepared from urushiol and AgNO₃ under UV irradiation by using in situ radical reduction approach. The effects of the silver nitrate loading and the irradiation time on the surface resistivity of polyurushiol/silver (PU/Ag) composite films were investigated. The result from XRD analysis showed that the formation of Ag particles, and the surface resistivity of polyurushiol/silver (PU/Ag) composite films reached the value of 0.26 Ω cm, when the content of Ag particles in composite films was 23.8 wt%, and the irradiation time 90 s. Additionally, Ag particles were well dispersed in the composite films. And the films had good thermo-stability.     

Synthesis of CdS nanoparticles dispersed within solutions and polymer films using amphiphilic urethane acrylate chains

In this study, a new process for preparation of CdS/polymer nanocomposite films using a new amphiphilic oligomer chain (Urethane Acrylate Nonionomer: UAN) is presented. UAN chains have hydrophilic polyethylene oxide segments and polypropylene oxide-based hydrophobic segments as part of the same backbone. In addition, these chains also have reactive vinyl groups at their hydrophobic segments. For the preparation of CdS nano-colloid solutions, UAN chains acted as a stabilizer for CdS nanoparticles dispersed in a solvent. For the fabrication of CdS/polymer nanocomposite films, UAN chains in CdS nano-colloid solutions were polymerized through reactions between their vinyl groups, resulting in the formation of CdS nanoparticle dispersed films swollen by the solvent. The nature of the solvent used strongly influenced the size of the CdS nanoparticles, which was confirmed by UV absorption spectra, PL emission spectra and TEM images. Smaller sized CdS nanoparticles were formed in higher polar solvents such as DMAc and methanol, which can be explained by the higher solubility of UAN chains and the more effective dissociation and stabilization of cadmium salts and CdS nanoparticles by UAN chains in the polar solvent.     

Synthesis of CdS‐ and ZnS‐modified bentonite nanoparticles and their applications to the degradation of eosin B

BACKGROUND: In the present study, nanocomposites of cadmium sulphide (CdS) and zinc sulphide (ZnS) on a bentonite have been prepared via an in‐situ precipitation route and their catalytic behaviour was evaluated in the degradation of eosin B. RESULTS: It was found that the basal space of bentonite increased from 1.23 to 1.49 nm after CdS or ZnS nanoparticles were deposited on layers of the bentonite. The resulting CdS–bentonite and ZnS–bentonite nanocomposites can degrade eosin B from aqueous solution after 2 h under UV irradiation. CONCLUSION: A soft method for in situ synthesis of monodispersed, CdS and ZnS nanoparticles, using a reverse micelle type procedure, is reported. The synthesized CdS‐ and ZnS–bentonite composites combined the adsorptive ability of bentonite and the catalytic degradation ability of CdS and ZnS to remove eosin B from its aqueous solution efficiently. Copyright © 2009 Society of Chemical Industry     

Synthesis of metal–cadmium sulfide nanocomposites using jingle-bell-shaped core-shell photocatalyst particles

Photocatalytic deposition of gold (Au) and silver (Ag) nanoparticles was investigated using jingle-bell-shaped silica (SiO₂)-coated cadmium sulfide (CdS) nanoparticles (SiO₂/CdS), which each had a void space between the CdS core and SiO₂ shell, as a photocatalyst. A size-selective photoetching technique was used to prepare the jingle bell nanostructure of SiO₂/CdS. Nanoparticles of Au and Ag were deposited by irradiation of the photoetched SiO₂/CdS in the presence of the corresponding metal complexes under deaerated conditions. Chemical etching of Au-deposited particles enabled the selective removal of CdS without any influence on the surface-plasmon absorption of Au. TEM analyses of the resulting particles suggested that some particles were encapsulated in hollow SiO₂ particles, while other Au particles were deposited on the outer surface of the SiO₂ shell. Emission spectra of the photoetched SiO₂/CdS showed that the metal deposition developed a broad emission with a peak around 650 nm originating from surface defect sites, the degree being dependent on the kind of metal nanoparticles and their amount of deposition. This fact can be explained by the formation of metal–CdS binary nanoparticles having defect sites at the interface between metal and CdS.     

紫外光固化漆酚镧聚合物(PULa)的性能与表征

由漆酚和氯化镧的酒精溶液,采用紫外光固化制备漆酚镧聚合物(PULa),用紫外可见光谱,红外光谱,热重分析等手段进行结构表征和性能测试。结果表明:紫外光固化得到的漆酚镧聚合物(PULa)膜具有良好的柔韧性能、抗冲击性、热稳定性能和抗溶剂性能。     

紫外光固化法制备漆酚铁聚合物涂料的研究

通过紫外光固化法快速便捷地由漆酚和三氯化铁制备了色泽乌黑、表面平整光亮的漆酚铁聚合物。当漆酚和氯化铁的物质的量比为3∶1,紫外光辐照20s时,漆膜具有优良的常规物理机械性能:光泽度132%,硬度6H,冲击强度50kg.cm,柔韧性0.5mm,附着力1级;良好的抗紫外线性能:紫外光辐照1200h以后,其失光率仅为4.85%;良好的耐热性能:受热320℃时失重5%;优异的抗化学介质性能。     

Synthesis of CdS nanoparticles dispersed within amphiphilic poly(urethane acrylate‐co‐styrene) films

CdS nanoparticles were prepared using amphiphilic urethane acrylate nonionomer (UAN) precursor chains having a poly(propylene oxide)‐based hydrophobic segment and a hydrophilic poly(ethylene oxide) segment. Cadmium salts were first dissolved in UAN/styrene solutions, and then the solutions were copolymerized to obtain poly(urethane acrylate‐co‐styrene) films containing dissolved cadmium salts. After reduction with H₂S gas, freestanding films containing CdS nanoparticles were obtained. Transmission electron microscopy images of the films showed that 9.67‐nm CdS nanoparticles were dispersed within the poly(urethane acrylate‐co‐styrene) matrix. The formation of CdS nanoparticles was also confirmed with UV absorption spectra and photoluminescence emission spectra of the films. Transmission electron microscopy and dynamic mechanical analysis measurements confirmed that hydrophilic/hydrophobic microphase separation in UAN/styrene solutions occurred during the dissociation of the cadmium salts, and the microphase‐separated structures were locked in by crosslinking copolymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2357–2363, 2005     

Effect of Quasi‐nanometer zirconium carbide on the physical characterization of zirconium carbide/polyurethane composite films irradiated under ultraviolet light

We used quasi‐nanometer zirconium carbide (ZrC) and a polyurethane (PU) resin under roller pressure to form a composite film and found that the tensile strength at break, elongation at break, and modulus gradually decreased with increasing ultraviolet (UV)‐irradiation time for films of both PU and the PU/ZrC composite. However, this phenomenon was significantly higher for the PU film than for the ZrC/PU composite film. The construction of the PU film changed after UV irradiation, but that of the PU/ZrC composite film was almost unchanged. The degradation of PU molecules occurred in the absence of ZrC particles after irradiation with UV light but almost did not occur in the presence of ZrC particles. This was confirmed with Fourier transform infrared spectroscopy and gel permeation chromatography analyses. It was suggested that polymer radicals which formed through the photooxidation of UV irradiation and free radicals which formed through the photoreduction of nanometer ZrC/UV irradiation interacted to form a dead polymer to stop the degradation; simultaneously, the chemical bonding between polymer molecules could be re‐formed from free radicals created by photooxidation and photoreduction and thus reduce the mobility of PU molecules, thereby raising the glass‐transition and melting temperatures of the soft segment. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4842–4849, 2006     

Photocatalytic Preparation of Encapsulated Gold Nanoparticles by Jingle-bell-shaped Cadmium Sulfide–silica Nanoparticles

Gold (Au) nanoparticles were deposited inside silica: (SiO₂) shells containing cadmium sulfide (CdS) nanoparticles through photocatalytic reduction of potassium dicyanogold(I) by CdS. Photocatalytic Au deposition occurred only when core-shell nanoparticles having a void space between the core and shell, i.e., a jingle-bell-shaped structure, were used. These core-shell nanoparticles were prepared by size-selective photoetching of SiO₂ -covered CdS nanoparticles. The size of Au nanoparticles could be controlled by adjustment of the void space in SiO₂-covered CdS. Dissolution of CdS by acid treatment from the Au-deposited jingle-bell nanoparticles did not have any effect on the surface-plasmon absorption by Au. These facts indicate that Au nanoparticles of adjustable size can be prepared in an SiO₂ shell that prevents mutual coalescence of Au nanoparticles but allows permeation of molecules and ions.     

Formation of metal-polymer hybrid nanostructures during radiation-induced reduction of metal ions in poly(acrylic acid)-poly(ethylenimine) complexes

The formation of nanoparticles during the radiation-induced chemical reduction of silver ions, copper ions, and nickel ions in films based on poly(acrylic acid)-poly(ethylenimine) complexes are studied via electron microscopy. This approach allows preparation of composites containing nanoparticles that are randomly distributed in the polymer matrix and materials with a regular spatial distribution of nanoparticles across the film thickness and in subsurface layers. The structure of metal-polymer hybrid materials is dependent on the irradiation conditions, the type of reduced metal ions, and their initial content in polymer matrices. The ratio between the rate of nucleation and the rate of growth of nanoparticles in the matrices of interpolyelectrolyte complexes depends on the intensity of the absorbed dose and on the mechanisms of reduction of metal ions and formation of clusters. The IR spectroscopic studies reveal the effect of nanoparticles on the chemical structure of the polymer matrix.     

漆酚缩甲醛聚合物微球的制备及其吸附性能

本文利用悬浮缩聚的方法合成漆酚缩甲醛聚合物微球,考察悬浮缩聚过程中单体的预分散、分散剂用量、单体的预聚、油水比例、催化剂用量、反应温度以及搅拌速度等对微球的形貌结构与性能的影响。结果表明,漆酚单体经预聚合后,在Mg(OH)2分散剂的作用下分散于甲醛水溶液中;在弱碱催化剂NH3·H2O的作用下,当油水比R=0.163时,搅拌速度r=300r/min时,于80℃～85℃进行悬浮缩聚反应,可以得到粒径为300μm,内部为多孔结构的聚合物微球。微球可以吸附废水中的重金属离子Cu2+、Pb2+和Cd2+等,其吸附选择性为Pb2+(21.9mg/g)Cu2+(21.3mg/g)Cd2+(7.1mg/g)。     

ZnO/CdS复合光催化剂的制备及降解四环素类抗生素

利用单晶Si辅助水热法低温合成了ZnO/CdS复合光催化剂,采用XRD、SEM、Dr-UV-vis等技术对材料结构和形貌进行表征,并对四环素类抗生素进行光催化降解研究。结果表明,当锌源与镉源的物料摩尔比为25:1、反应时间10h条件下,可获得形貌最佳的ZnO/CdS复合物,即尺寸为1μm的具有孔结构的棒状ZnO骨架表面黏附了尺寸在几十纳米的CdS粒子。CdS的复合明显降低ZnO/CdS的带隙能至2.87eV,在日光照射下反应120min,对盐酸四环素(TC)、土霉素(OTC)和强力霉素(DC)3种四环素类抗生素的光催化降解率分别达到81.65%、70.68%和54.61%,降解反应速率很快,符合一级反应动力学方程;在紫外光照射下几乎可以完全降解这3种抗生素,证明了该复合材料的高催化效率。     

Synthesis,characterization and photocatalytic activity of CdS–montmorillonite nanocomposites

Nanocomposites based on cadmium sulfide (CdS) and Na-montmorillonite (Na⁺-Mt) were prepared by a hydrothermal method using Cd[NH₂CSNH₂]SO₄ complex as precursor of CdS which was derived from cadmium sulfate and thiourea. These nanocomposites were characterized by X-ray diffraction (XRD), Fourier transform infrared spectra (FTIR) and X-fluorescence (XF). The nanocomposites consist of nanosized CdS pillars, which tend to increase in size as the amount of complex precursor increases. The CdS crystals have a hexagonal symmetry. The photocatalytic activity of the obtained CdS–Mt nanocomposites is improved significantly compared to that of the Mt and pure CdS. The resulting CdS–Mt nanocomposites could degrade methylene blue and rhodamine 6G under near UV–visible irradiation.     

Preparation of cadmium sulfide/poly(methyl methacrylate) composites by precipitation with compressed CO2

Cadmium sulfide (CdS) nanoparticles and poly(methyl methacrylate) (PMMA) were first synthesized in methyl methacrylate (MMA)/sodium bis(2‐ethylhexyl) sulfosuccinate (AOT) microemulsion, in which MMA acts as the solvent and monomer. Then compressed CO₂ was used as an antisolvent to precipitate the CdS and PMMA simultaneously. Using this method, a CdS/PMMA composite was successfully prepared. The CdS nanoparticles dispersed in the polymer matrices were characterized by transmission electron microscopy. The higher pressure is favorable to producing CdS nanoparticles of smaller size. The phase structure of the obtained composite was characterized by X‐ray diffraction, which reveals that cubic CdS particles were formed. The FTIR spectra of the composite showed that there is no chemical bonding or strong interaction between CdS and PMMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1643–1648, 2004     

Facile synthesis of CdS nanoparticles photocatalyst with high performance

A simple one-step solid-state reaction has been introduced to synthesize CdS nanoparticles. The as-prepared CdS product was characterized by X-ray powder diffraction (XRD), BET surface area measurement, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), particle size distribution (PSD) and UV–vis absorption spectrum. The experiment results reveal that the CdS product was composed of nanoparticles about 60 nm in diameter, of which specific surface area is 78.02 m²/g. The photocatalysis results indicate that the CdS nanoparticles exhibit excellent photocatalytic activity for the degradation of rhodamine B under UV irradiation. Nearly 95% of rhodamine B was degraded after 60 min of irradiation, higher than that of P25, which is due to the large specific surface area and mesoporous structure.