Preparation and properties of polythiourethane/ZnS nanocomposites with high refractive index

The inorganic–organic crosslinking polythiourethane/ZnS (PTU/ZnS) nanocomposites with high refractive index and transmittance were successfully prepared. The thiol‐capped ZnS nanoparticles with a diameter of about 5 nm were fabricated into the molecular chains of PTU via the formed covalent bonds between the capped ZnS and the matrix. The investigations demonstrated the ZnS nanoparticles were uniformly dispersed in the PTU matrix even at high contents. The optical studies showed the refractive index of the highly transparent nanocomposite films linearly increased from 1.643 to 1.792 with the increase of the ZnS content. The structure, morphology, and other properties were also characterized by FTIR, NMR, AFM, XRD, DSC, TGA, etc. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Studies on syntheses and properties of episulfide‐type optical resins with high refractive index

A series of novel high refractive index episulfide‐type optical resins were prepared by ring‐opening copolymerization of bis(β‐epithiopropylthioethyl) sulfide (BEPTES) with episulfide derivative of diglydicyl ether of bisphenol A (ESDGEBA) and 2,4‐tolylene diisocyanate (TDI), respectively, in the presence of triethylamine as a curing catalyst. The episulfide monomers, BEPTES and ESDGEBA, were synthesized from their corresponding epoxy compounds, respectively. The cured transparent resins exhibit high refractive index (n_d > 1.63) and relatively low dispersion. The refractive index (n_d) and Abbe's number (ν_d) of the BEPTES/ESDGEBA curing system increased linearly with the weight content of BEPTES monomer in the range from 1.633 and 34.0 for the copolymer with 10 wt % of BEPTES to 1.697 and 38.1 for the homopolymer of pure BEPTES. For the BEPTES/TDI curing system, the refractive index and Abbe's number varied linearly with the molar ratio of BEPTES to TDI from 1.652 and 28.7 to 1.669 and 34.6. High glass‐transition temperatures (T_g > 130°C) of the cured BEPTES/TDI resins were observed, which indicate that the cured BEPTES/TDI resins possess a good heat resistance. The optical, physical, and thermal properties of the episulfide‐type cured optical resins were also discussed in this study. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2426–2430, 2003     

Development of optically transparent ZnS/poly(vinylpyrrolidone) nanocomposite films with high refractive indices and high Abbe numbers

A series of optically transparent ZnS‐poly(vinylpyrrolidone) (PVP) nanocomposite films with high refractive indices and high Abbe numbers have been prepared. Mercaptoethanol (ME) capped ZnS nanoparticles (NPs) were introduced into the PVP polymer matrix via simple blending with high nanophase contents. ME‐ZnS NPs of around 3 nm were prepared from zinc acetate and thiourea precursors in N,N‐dimethylformamide using ME as a capping agent. Transparent nanocomposite films with high refractive indices and high Abbe numbers can be easily prepared by a conventional film casting method. TGA results indicated that the ZnS/PVP nanocomposite films exhibit good thermal stability and the measured contents of ZnS NPs in the films agree well with the theoretical values. The refractive indices and the Abbe numbers of the ZnS/PVP nanocomposite films range from 1.5061 to 1.7523 and 55.6 to 20.4 with the content of ME‐ZnS NPs varied between 0 and 80 wt %, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of ZnS/hyperbranched polyester nanocomposite and its optical properties

The ZnS/hyperbranched polyester nanocomposite with higher refractive index was prepared by incorporating the acrylated 2-(2-mercapto-acetoxy)-ethyl ester-capped ZnS nanoparticles into the acrylated Boltorn™ H20 (H20). The acrylated 2-(2-mercapto-acetoxy)-ethyl ester-capped colloidal ZnS nanoparticles were synthesized by the reaction of zinc acetate with thioacetamide in N,N-dimethylformamide. The acrylated hyperbranched polyester was obtained by reacting acryloyl chloride with hydroxyl group of H20. The acrylated H20 plays an important role in stabilizing and dispersing ZnS nanoparticles with a diameter of 1-4 nm. The refractive indices of ZnS/hyperbranched polyester nanocomposites, depending on ZnS content, were determined to be in the ranges of 1.48-1.65.     

Preparation and properties of acrylic melamine hard coating

Melamine resin polymers exhibit high transmittance, high pencil hardness, and high refractive index. However, high temperatures and long reaction times are required to obtain the desired condensation products. In this study, acrylic‐modified melamine resins were synthesized that were cured by irradiation with ultraviolet (UV) light. The synthesized acrylic‐modified melamine resins could be cured rapidly due to the radical reaction of the acrylic groups and retained high transparency and high refractive index as features of the melamine resin polymers. The polymerized film by UV curing had low shrinkage and high refractive index. Compared with general multifunctional moiety‐type acrylic monomers such as pentaerythritol triacrylate and dipentaerythritol hexaacrylate, the acrylic‐modified melamine resins had the same degree of hardness. In addition, flexibility, a feature of the urethane moiety, was imparted to the polymer by the reaction of residual hydroxyl groups with isocyanate. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci 000: 000–000, 2010     

Preparation in presence of urushiol and properties of acrylate latex with interparticle bridges

Acrylate latices were prepared by seeded emulsion polymerization of methyl methacrylate (MMA) and butyl acrylate (BA) in presence of urushiol with multifunctional groups (0–6 wt%). The emulsion polymerization was strongly influenced by the urushiol content. With increasing urushiol content, the conversion rate of the monomers first increased then decreased, the stability of emulsion polymerization gradually declined, the average particle size of the latex increased from 115.9 to 175.3 nm, and a change from mono- to bimodal particle size distribution occurred. Interestingly, transmission electron microscopy (TEM) showed that some particles were connected by linear bridges in presence of urushiol. Based on results of ¹H nuclear magnetic resonance (NMR) analysis, such formation of interparticle bridges is due to participation of urushiol in the emulsion polymerization of the acrylate monomers. The content of urushiol also affected the properties of latex films. With increasing urushiol content from 0 to 3 wt%, the adhesion, pencil hardness, and contact angle were markedly improved from grade 6 to grade 2, from B to 3H, and from 22° to 61°, respectively, due to formation of interparticle bridges. When the content of urushiol exceeded 3 wt%, the adhesion and pencil hardness remained unchanged, but the water contact angle markedly declined because of higher surface roughness of the latex film. Furthermore, addition of urushiol enhanced the thermal stability of the latex films.     

Surface mechanical properties of transparent poly(methyl methacrylate)/zirconia nanocomposites prepared by in situ bulk polymerization

Poly(methyl methacrylate)/zirconia (PMMA/ZrO₂) nanocomposites with ZrO₂ content as high as 15 wt% were prepared by modifying non-aqueous synthesized ZrO₂ nanoparticles with methacryloxypropyltrimethoxysilane (MPS) in tetrahydrofuran, dispersing MPS-functionalized ZrO₂ nanoparticles in MMA and following in situ bulk polymerization with controlled pre-polymerization time. The MPS-functionalized ZrO₂ nanoparticles showed an efficient crosslinking role in the polymerization, leading to a complete gel of PMMA at 5 wt% of ZrO₂ content. Homogeneous dispersion of the ZrO₂ nanoparticles at primary particle size level was observed in all nanocomposites, which results in good clarity of the obtained nanocomposites. Hardness tests (pendulum hardness tests and indentation tests) and anti-scratch tests (abrasion tests and nano scratch tests) were employed to probe the surface mechanical properties of the nanocomposites. The properties of nanocomposites as a function of ZrO₂ content, revealing from various characterization techniques, are not consistent and discussed in detail. At low ZrO₂ content, the mechanical properties are enhanced by the formed crosslinking structure. However, remarkable improvements of hardness and scratch resistance of PMMA were achieved when 15 wt% of ZrO₂ content was embedded.     

Preparation and photocatalytic activity of zinc sulfide/polymer nanocomposites

ZnS nanoparticles were prepared on the surface of polyacrylonitrile (PAN) and methyl methacrylate (MMA)/butyl methacrylate (BMA)/acrylic acid (AA) copolymer nanofibers. The MMA–BMA–AA copolymer was synthesized by bulk radical polymerization using 2,2′‐azobisisobutyronitrile as the initiator. The PAN and MMA–BMA–AA copolymer nanofibers were prepared by electrospinning. Zinc ions were introduced onto the surface of the nanofibers by coordination with the carboxyl of AA. Then, sulfide ions were added to react with zinc ions to form ZnS nanoparticles. The average diameter of the nanofibers was about 300 nm, and the diameter of the ZnS nanoparticles was about 10 nm. The band position of the photoluminescence spectrum of the ZnS/PAN and MMA–BMA–AA nanocomposites had an 80‐nm blueshift in comparison with that of the corresponding bulk ZnS sample. The ZnS/PAN and MMA–BMA–AA nanocomposites had high photocatalytic activity for the degradation of phenol under ultraviolet irradiation; the photocatalytic activity changed indistinctively after it was used repeatedly (6 times). The nanofibers of PAN and MMA–BMA–AA not only dispersed but also stabilized the ZnS nanoparticles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Transparent dispensible high‐refractive index ZrO2/epoxy nanocomposites for LED encapsulation

In this study, we report a facile ex situ approach to preparing transparent dispensible high‐refractive index ZrO₂/epoxy nanocomposites for LED encapsulation. Highly crystalline, near monodisperse ZrO₂ nanoparticles (NPs) were synthesized by a nonaqueous approach using benzyl alcohol as the coordinating solvent. The synthesized particles were then modified by (3‐glycidyloxypropyl)trimethoxysilane (GMS) ligand. It was found that, with tiny amount of surface‐treating ligand, the modified ZrO₂ NPs were able to be easily dispersed in a commercial epoxy matrix because of the epoxy compatible surface chemistry design as well as the small matrix molecular weight favoring mixing. Transparent thick (1 mm) ZrO₂/epoxy nanocomposites with a particle core content as high as 50 wt % and an optical transparency of 90% in the visible light range were successfully prepared. The refractive index of the prepared composites increased from 1.51 for neat epoxy to 1.65 for 50 wt % (20 vol %) ZrO₂ loading and maintained the same high‐Abbe number as the neat epoxy matrix. Compared with the neat epoxy encapsulant, an increase of 13.2% in light output power of red LEDs was achieved with the 50 wt % ZrO₂/epoxy nanocomposite as the novel encapsulant material. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3785–3793, 2013     

Refractive index tuning of highly transparent bismuth containing polymer composites

A new method for the preparation of transparent bismuth containing composites is reported. With the organic ligands 2,3-Dihydroxypropylmethacrylate (HMA) and 2-(Methacryloyloxy)-ethylacetoacetate (AcMA), bifunctional monomers with a functional group for metal complexation on the one hand and a reactive group for polymerization on the other hand were found. By integrating up to 20 wt-% bismuth in the monomer mixtures, an increase of the refractive index of 4.0% (?n = 0.058) is determined. The metal complexation was observed via infrared spectroscopy (AcMA) and NMR spectroscopy (HMA). Subsequent addition of trimethylolpropane triacrylate (TMPTA) as cross-linking agent and 2,4,6-trimethyl-benzoyldiphenylphosphine oxide (TPO) as photoinitiator to the bismuth containing monomers Bi-HMA and Bi-AcMA lead to a UV-curable liquid. Photoinduced polymerization was used to generate transparent bismuth containing hybrid materials with increased refractive index. The polymers were characterized by UV/VIS spectroscopy, ellipsometry and DTA/TG. The materials show a high transmission (>80% in 2 mm thick plates) in the visible spectral range, and an increased refractive index with increasing bismuth content.     

Fabrication of highly refractive barium‐titanate‐incorporated polyimide nanocomposite films with high permittivity and thermal stability

Crystalline nanoparticles of barium titanate (BT) are incorporated into polyimide (PI) to fabricate highly refractive, anti‐UV‐degradable nanocomposite films with high permittivity and thermal stability. For homogeneous incorporation of BT nanoparticles into the PI matrix, the BT nanoparticles are surface modified by phthalimide with the aid of a silane coupling agent as a scaffold. The PI nanocomposites are prepared by in situ polymerization in which a diphthalic anhydride and a diamine are used to form the PI matrix in the presence of the surface‐modified nanoparticles. The refractive index of the transparent nanocomposite films reaches 1.85 at a nanoparticle content of 59 vol% with a high dielectric constant of ε = 37 and thermal stability up to 460 °C. Copyright © 2012 Society of Chemical Industry     

Preparation of exfoliated high‐impact polystyrene/MMT nanocomposites via in situ polymerization under controlling viscosity of the reaction medium

Exfoliated high‐impact polystyrene (HIPS)/montmorillonite (MMT) nanocomposites were prepared via in situ polymerization of styrene in the presence of polybutadiene, using an intercalated cationic radical initiator‐MMT hybrid (organoclay). In the solution polymerization in toluene, the silicate layers of the clay were well exfoliated, due to the low extra‐gallery viscosity that can facilitate the diffusion of styrene monomers into the clay layers during the polymerization. The exfoliated HIPS/MMT nanocomposites were also successfully prepared by controlling the viscosity of the reaction medium with prolong swelling of the organoclay in styrene, prior to bulk polymerization. The HIPS/MMT nanocomposites, obtained from bulk polymerization, exhibited a significant improvement in thermal stability, compared to those obtained from solution polymerization as well as the pure polymer counterparts. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Bulk synthesis of homogeneous and transparent bulk core/multishell quantum dots/PMMA nanocomposites with bright luminescence

Core/multishell CdSe/CdS/CdS/Cd_0.75Zn_0.25S/Cd_0.5Zn_0.5S/Cd_0.25 Zn_0.75S/ZnS/ZnS QDs/PMMA bulk nanocomposites were successfully synthesized. To achieve a homogeneous and stable dispersion in MMA monomers, QDs were first modified with amphiphilic polymer of poly(ethylene glycol)‐oleate (PEG‐oleate). Subsequently, the transparent and homogeneous bulk composites were obtained by photopolymerization. The TEM analysis of ultramicrotome cut of composite demonstrates that QDs are well dispersed in the PMMA matrix. UV–vis transmission spectra show the nanocomposites still maintain high transmittance even with QDs content of up to 6 wt %. The thermogravimetric analysis (TGA) reveals the incorporation of the QDs significantly improves the thermal stability of composites, as evidenced by the retardation of a degradation initiation by 60°C. Photoluminescence spectra suggest that the nanocomposites exhibit bright fluorescence under UV excitation. X‐ray excited luminescence spectra show they have response to X‐ray. All of the experimental results indicate the great promising applications of core/multishell QDs/PMMA nanocomposites in optical communication devices and radiation detectors. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1548–1553, 2013     

Filled polymers with high nanoparticles concentration—Synthesis and properties

High refractive index optical compositions based on polymer matrices filled with high concentrations of ZnS nanoparticles were developed. These materials have good optical properties and processability like usual polymers, and they are suitable for factory scale use. At 25 vol % ZnS nanoparticles concentration an increase in refractive index up to 0.25 in 150 um transparent film was obtained. A process was develope for formation of polymeric compositions consisting of polymer filled with high concentrations of inorganic crystalline nanoparticles. Effects connected to high concentration of nanoparticles in the polymer were discussed. Optical properties of these materials were investigated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Microwave irradiation synthesis and characterization of RGO‐AgNPs/polystyrene nanocomposites

Polystyrene and reduced graphene oxide/silver (PSTY/RGO/AgNPs) nanocomposites were prepared via an in situ bulk polymerization method using two different preparation techniques. In the first approach, a mixture of silver nitrate, hydrazine hydrate, and polystyrene containing graphene oxide (PSTY/GO) were reduced by microwave irradiation (MWI) to obtain R‐(PSTY‐GO)/AgNPs nanocomposites. In the second approach, a mixture of the (RGO/AgNPs) nanocomposite, which was produced via MWI, and STY monomers were polymerized using an in situ bulk polymerization method to obtain PSTY‐RGO/AgNPs nanocomposites. The two nanocomposites were compared and characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, high‐resolution transmission electron microscopy, Differential scanning calorimetry, and thermogravimetric analysis. The results indicate that the nanocomposites obtained using the first approach, which involved MWI, exhibited a better morphology and dispersion with enhanced thermal stability compared to the nanocomposites prepared without MWI. POLYM. COMPOS., 35:2318–2323, 2014. © 2014 Society of Plastics Engineers     

Preparation and properties of UV-curable di-functional sulfur-containing thioacrylate and thiourethane acrylate monomers with high refractive indices

We synthesized UV-curable di-functional sulfur-containing thioacrylate and thiourethane acrylate with high refractive indices. The structures of monomers were confirmed by nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FT-IR). The formulation of UV-curable coating film was prepared by thioacrylate monomer, thiourethane acrylate monomer, α-hydroxy-α-methylpropiophenone as the photoinitiator, and bisphenol A epoxy acrylate as the oligomer. The cured coating films were investigated using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), Taber abraser tests, transmittance, and refractive index. The value of refractive index for all coating films increased after UV-curing. Transparent, photocurable coating films with high abrasion resistance were prepared. The monomers showed high refractive index. The refractive indices of synthesized monomers (thioacrylate and thiourethane acrylate monomer) are 1.623 and 1.577, respectively.     

Fabrication of highly refractive,transparent BaTiO3/poly(methyl methacrylate) composite films with high permittivities

Incorporation of crystalline barium titanate (BT) nanoparticles into poly(methyl methacrylate) (PMMA) was carried out to prepare highly refractive polymer nanocomposite films that have transparency and high permittivities. The BT nanoparticles were prepared by hydrolysis of a barium/titanium complex alkoxide in 2‐methoxyethanol, then surface‐modified with a silane coupling agent (3‐methacryloxypropyltrimethoxysilane) to improve their affinity for PMMA. The incorporation of the surface‐modified nanoparticles into PMMA was performed up to a nanoparticle content almost equivalent to particle close‐packing state. The refractive index of the composite films increased with nanoparticle incorporation, keeping the relative transmittance normalized with PMMA film above 90%. A high refractive index of 1.82 was reached at a nanoparticle content of 53 vol% with a dielectric constant as high as 36 and a dissipation factor as low as 0.05. The results demonstrate that the crystalline BT nanoparticles are useful fillers for effectively increasing both refractive index and dielectric constant of polymer nanocomposites. Copyright © 2011 Society of Chemical Industry     

High-refractive quinolinone-based polymers for ophthalmic devices

Seven novel high refractive index (HRI) acrylic monomers, comprising the quinolinone structural motive, have been synthesized and characterized. Cross-linked homo- as well as copolymers were prepared by photochemical bulk polymerization. The homopolymers show refractive indices at 589 nm (n ₅₈₉) ranging from 1.60 up to 1.68, glass transition temperatures (T _g) from 52 to 76 °C, and Abbe numbers (ν _Abbe) of 19 to 25. Due to these parameters, the homopolymers are not suitable to be used directly for intraocular lens (IOL) manufacture, but the quinolinone monomers may be used as high refractive index components in copolymers. Potential mixtures were calculated theoretically and one example, a copolymer with PEA and PEGPEA, was prepared and characterized. The experimentally found values were T _g?=?24 °C, n ₅₈₉?=?1.593, and ν _Abbe?=?28.3. Interestingly, the quinolinone compound which does not have any spacer between the polymerizable group and the high refractive index group appears to be the most useful one. The lightfastness of the new material fulfills the demands for IOLs. Quinolinone derivatives are promising new comonomers for high refractive index copolymers.     

Facile Fabrication of Pt-Doped Mesoporous ZnS as High Efficiency for Photocatalytic CO2 Conversion

Developing high efficiency, environmentally friendly, and low-cost mesoporous Pt/ZnS photocatalyst for CO₂ conversion to CH₃OH is significant for clean energy conversion. Herein, we described a facile synthesis of mesoporous ZnS framework decorated Pt NPs as high efficiency for CO₂ conversion through visible light illumination. The results indicated that Pt/ZnS nanocomposites showed that the structural and crystallinity integrity of polyhedral heterojunction obviously maintain after incorporating Pt NPs, and they are well-distributed on the ZnS surface with particles size about 3–5 nm. The optimized photocatalyst 1.5% Pt/ZnS nanocomposite could prominently exhibit a high photocatalytic efficiency compared to undoped ZnS. Remarkably, the yield of CH₃OH of 400 µmolg^??1 in 9 h over 1.5% Pt/ZnS nanocomposite indicated a significantly promoted CH₃OH formation, nearly 22-fold greater than that of the undoped ZnS NPs, which substantially verified the great promoting potential for conversion of clean energy. The CH₃OH formation rate over mesoporous 1.5% Pt/ZnS nanocomposite (44.5 µmolg^?1 h^?1) is larger 24 times than that of undoped ZnS NPs (1.86 µmolg^?1 h^?1). The recycled Pt/ZnS photocatalyst does not alter the CH₃OH formation remarkably after five repeating cycles with excellent durability. Electrochemical impedance spectroscopy, photocurrent response, and photoluminescence analyses were investigated to support our results and suggested mechanism for enhancement of CO₂ conversion to CH₃OH.

     

Measurement of hardness and friction properties of pencil leads for quantification of pencil hardness test

We have investigated the various properties of different types of pencil leads in order to quantify a pencil hardness test for reliability. The chemical composition and mechanical properties for different types of pencils (F, 2H, 4H, 6H and 8H) were measured using X-ray diffraction, nano-indentation and a tribometer. The values for nano-indentation hardness of the pencil leads are in the range of 0.3–0.8?GPa. A higher hardness grade in the pencil lead leads to a wider error range. The clay content of the lead seems to be proportional to the hardness of the pencil lead. Different crystalline phases in clays for each grade of pencil lead result in variations in the degree and distribution of the hardness. Consequently, the content of the crystalline phases in the clay affects deviations in the hardness.