Nanoparticle-doped Polymer Research Articles

Rheological Properties Study of Polymer Dispersed Liquid Crystals Doped by SiO2 Nanoparticles

The present report discusses the development of a novel nano-composite using a polymer dispersed liquid crystal (PDLC) and inorganic silicon dioxide (SiO2) nanoparticles. The aim of this work was to investigate the effect of the SiO2 nanoparticles on the rheological properties of the PDLC films. In our research described in this paper SiO2 nanoparticle-doped polymer dispersed liquid crystal films were made from a mixture of ethylene glycol phenyl ether methacrylate (EGPEMA) pre-polymer, 4-Cyano-4′-pentylbiphenyl (5CB) liquid crystals (LC) and SiO2 nanoparticles by the polymerization induced phase separation (PIPS) process. Doping the PDLC systems with SiO2 improved the rheological properties of these materials; the percolation (network formation) observed reflected the good interfacial adhesion between the nanoparticles, the polymer matrix and the LC. On the other hand, a decrease in the storage modulus (G′) and loss modulus (G″) of the PDLC systems after addition of the SiO2 nanoparticles confirmed their high flexibility and low crystallinity. A slight increase in G′ at 0.05 wt.% SiO2 resulted in the good mechanical strength of the doped PDLC. The viscoelastic behavior of the doped and undoped PDLC systems was confirmed at high frequencies. Thermal characterization by differential scanning calorimetry (DSC) showed a decrease in the glass transition temperature (Tg) of the PDLC with 0.05 wt.% of SiO2 nanoparticles, which showed that we had a more flexible material.

Enhanced thermo-electro-optical and dielectric properties of carbon nanoparticle-doped polymer dispersed liquid crystal based switchable windows

The effect of temperature as well as voltage on switchable smart windows was studied. These smart windows are composites of a polymer and a liquid crystal (LC) and collectively known as polymer dispersed liquid crystal (PDLC) films. In order to enhance the efficiency of the smart windows/PDLC films, the LC material was doped with carbon nano particles (CNP) in various concentrations ranging from 0 to 0.1%. To examine the efficacy and the temperature dependent performance of the CNP doped PDLC (CPDLC) film, firstly morphological and thermo-morphological studies were performed using polarizing optical microscopy (POM). POM in combination with temperature changes allows to record texture changes and the nematic-isotropic transition of the composite films for applied voltage. The complete electro-optical (EO) study comprising of voltage and temperature dependent transmittance, threshold voltage (Vth), saturation voltage (Vsat), contrast ratio (CR) and response time measurement was performed through an assembled EO set-up. To infer intermolecular cooperative processes between polymer and the dipoles of the LC, the relaxation mechanism of the composite films for various temperatures was studied by employing Debye and Cole-Cole models in dielectric spectroscopy. Parameters like dielectric strength and dissipation factor were determined to allow optimization of the CPDLC films.

Novel silver-morphine-functionalized polypropylene (AgPP-mrp) nanocomposite for the degradation of dye removal by multivariate optimization approach.

As a novel adsorbent, an opioid silver-morphine-functionalized polypropylene was synthesized through a one-pot reaction at room temperature and successfully used for the simple one-pot photocatalytic degradation catalyst of methyl orange removal from wastewater. UV spectral analysis reveals a special reference to the excitation of surface plasmon resonance as the main characteristic of the polymer-Ag nanocomposite in toluene solution peak at 420nm in AgPP-mrp catalyst.The 1H NMR spectrum showed no sign of Ag NP peaks revealing small size distribution in the channels of morphine-functionalized polypropylene polymer. The morphology of silver nanoparticle-doped polymer through scanning electron microscopy (SEM-EDX) reveals PP-mrp with continuous matrix and Ag NPs (0.87 wt%). Furthermore, photocatalytic degradation of methyl orange was investigated on AgPP-mrp catalyst spectrophotometrically under solar irradiation in waste effluent, demonstrating high degradation efficiency. According to experimental findings, silver nanoparticles (AgPP-mrp) achieved high degradation capacities of 139mg/g equivalent to 97.4% of photodegradation in a little period of time (35min), as associated with previously stated materials and follow pseudo-second-order kinetic degradation tail of a high regression coefficient (R2 = 0.992). The suggested techniques offer a linear reaction for MO over the pH range of 1.5 to 5 and a degradation temperature of 25 to 60°C. Central composite design and response surface methodology statistics recommend pH of the reaction medium and time as important variables for methyl orange degradation on AgPP-mrp photocatalytic. AgPP-mrp on the photocatalytic phenomenon based on heterojunction catalytic design producing electron holes (e-), as well as superoxides for the successful degradation of methyl orange.

Thermal Conductivity and Phase-Change Properties of Boron Nitride-Lead Oxide Nanoparticle-Doped Polymer Nanocomposites.

Thermally conductive phase-change materials (PCMs) were produced using the crosslinked Poly (Styrene-block-Ethylene Glycol Di Methyl Methacrylate) (PS-PEG DM) copolymer by employing boron nitride (BN)/lead oxide (PbO) nanoparticles. Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA) methods were used to research the phase transition temperatures, the phase-change enthalpies (melting enthalpy (ΔHm), and crystallization enthalpies (ΔHc)). The thermal conductivities (λ) of the PS-PEG/BN/PbO PCM nanocomposites were investigated. The λ value of PS-PEG/BN/PbO PCM nanocomposite containing BN 13 wt%, PbO 60.90 wt%, and PS-PEG 26.10 wt% was determined to be 18.874 W/(mK). The crystallization fraction (Fc) values of PS-PEG (1000), PS-PEG (1500), and PS-PEG (10,000) copolymers were 0.032, 0.034, and 0.063, respectively. XRD results of the PCM nanocomposites showed that the sharp diffraction peaks at 17.00 and 25.28 °C of the PS-PEG copolymer belonged to the PEG part. Since the PS-PEG/PbO and the PS-PEG/PbO/BN nanocomposites show remarkable thermal conductivity performance, they can be used as conductive polymer nanocomposites for effective heat dissipation in heat exchangers, power electronics, electric motors, generators, communication, and lighting equipment. At the same time, according to our results, PCM nanocomposites can be considered as heat storage materials in energy storage systems.

Phase change n-Octadecane microencapsulated in titanium dioxide nanoparticle-doped polymer for photothermal conversion and photocatalysis

We microencapsulated the n-Octadecane (ODE) with titanium dioxide (TiO2) nanoparticle-doped styrene–divinylbenzene copolymer (SDB) via the suspension polymerization. The TiO2 was grafted with 3-Glycidoxypropyltrimethoxysilane (KH560) to obtain amphiphilic properties in order to enhance their anchoring capability at the oil-aqueous interface. Emphasis is placed on analyzing how the TiO2 nanoparticles affect the multiple functions of the prepared microcapsules for heat storage, photothermal conversion, and photodegradation. Under scanning electron microscope, the microcapsules show generally spherical shapes with rough surface and good dispersibility. The thermophysical property of the microcapsules was examined via the differential scanning calorimetry and thermogravimetric analyzer. The microcapsules prepared with 4.0 wt% TiO2 had the highest thermal storage capacity with molten andcrystallized enthalpies of 105.3 ± 0.3 and 102.4 ± 0.7 J/g, respectively. The microcapsules with 4.0 wt% TiO2 achieved 48.0 ± 0.4% encapsulation. The doped-TiO2 nanoparticles improved the thermal stability of microcapsule samples. The initial decomposition temperature of the microcapsule sample with 4.0 wt% TiO2 is increased to 167.6 °C as compared to 115.1 °C for pure ODE. In the solar thermal conversion and photocatalytic tests, the microcapsule sample with 4.0 wt% TiO2 exhibited the best performance as well, with 42.80% photothermal conversion efficiency and 90.92% degradation rate. The multifunctional phase change microcapsules have broad application prospects as heat storage and depollution materials.

Radiative Cooling Nanofabric for Personal Thermal Management.

A wearable textile that is engineered to reflect incoming sunlight and allow the transmission of mid-infrared radiation simultaneously would have a great impact on the human body's thermal regulation in an outdoor environment. However, developing such a textile is a tough challenge. Using nanoparticle-doped polymer (zinc oxide and polyethylene) materials and electrospinning technology, we have developed a nanofabric with the desired optical properties and good applicability. The nanofabric offers a cool fibrous structure with outstanding solar reflectivity (91%) and mid-infrared transmissivity (81%). In an outdoor field test under exposure of direct sunlight, the nanofabric was demonstrated to reduce the simulated skin temperature by 9 °C when compared to skin covered by a cotton textile. A heat-transfer model is also established to numerically assess the cooling performance of the nanofabric as a function of various climate factors, including solar intensity, ambient air temperature, atmospheric emission, wind speed, and parasitic heat loss rate. The results indicate that the nanofabric can completely release the human body from unwanted heat stress in most conditions, providing an additional cooling effect as well as demonstrating worldwide feasibility. Even in some extreme conditions, the nanofabric can also reduce the human body's cooling demand compared with traditional cotton textile, proving this material as a feasible solution for better thermoregulation of the human body. The facile fabrication of such textiles paves the way for the mass adoption of energy-free personal cooling technology in daily life, which meets the growing demand for healthcare, climate change, and sustainability.

Polymer dispersed liquid crystals doped with CeO2 nanoparticles for the smart window

ABSTRACT In this paper, rare earth oxide CeO2 nanoparticle-doped polymer dispersed liquid crystal (PDLC) films were prepared by the polymerisation induced phase separation (PIPS) process. The effects of the crosslinking agent TMPTA content, liquid crystal (LC) content and the CeO2 content on the polymer structures and electro-optical properties of the as-made PDLC films were investigated systematically. It has been found that by changing the TMPTA content, LC content and doping a small amount of CeO2 nanoparticles, the electro-optical properties of PDLC films can be optimised. After adding a low concentration of CeO2 nanoparticles, the electro-optical properties of the PDLC film have been well optimised: after adding 0.8% CeO2, Vth decreased from 26.6 V to 16.8 V, and CR increased from 89.5 to 137.6. Consequently, this work offers a meaningful approach to optimise the electro-optical properties of PDLC films, which indeed can form a wonderful footstone for the wide application of PDLC.

Preparation and Characterization of Nanoparticle-Doped Polymer Inclusion Membranes. Application to the Removal of Arsenate and Phosphate from Waters.

Nanoparticle-doped polymer inclusion membranes (NP-PIMs) have been prepared and characterized as new materials for the removal of arsenate and phosphate from waters. PIMs are made of a polymer, cellulose triacetate (CTA), and an extractant, which interacts with the compound of interest. We have used the ionic liquid (IL) trioctylmethylammonium chloride (Aliquat 336) as the extractant and have investigated how the addition of nanoparticles can modify membrane properties. To this end, inorganic nanoparticles, such as ferrite (Fe3O4), SiO2 and TiO2, and multiwalled carbon nanotubes (MWCNTs), were blended with the polymer/extractant mixture. Scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), and contact angle measurements have been used to characterize the material. Moreover, PIM stability was checked by measuring the mass loss during the experiments. Since Aliquat 336 acts as an anion exchanger, the NP-PIMs have been explored in two different applications: (i) as sorbent materials for the extraction of arsenate and phosphate anions; (ii) as an organic phase for the separation of arsenate and phosphate in a three-phase system. The presence of oleate-coated ferrite NP in the PIM formulation represents an improvement in the efficiency of NP-PIMs used as sorbents; nevertheless, a decrease in the transport efficiency for arsenate but not for phosphate was obtained. The ease with which the NP-PIMs are prepared suggests good potential for future applications in the treatment of polluted water. Future work will address three main aspects: firstly, the implementation of the Fe3O4-PIMs for the removal of As(V) in real water containing complex matrices; secondly, the study of phosphate recovery with other cell designs that allow large volumes of contaminated water to be treated; and thirdly, the investigation of the role of MWCNTs in PIM stability.

Manufacture of Contact Lens of Nanoparticle-Doped Polymer Complemented with ZEMAX.

Many people suffer from myopia or hyperopia due to the refractive errors of the cornea all over the world. The use of high refractive index (RI), Abbe number (νd), and visible light transmittance (T%) polymeric contact lenses (CLs) holds great promise in vision error treatment as an alternative solution to the irreversible laser-assisted in situ keratomileusis (LASIK) surgery. Titanium dioxide nanoparticles (TiO2 NPs) have been suggested as a good candidate to rise the RI and maintain high transparency of a poly(methyl methacrylate) (PMMA)-TiO2 nanocomposite. This work includes a preparation of TiO2 NPs using the sol gel method as well as a synthesis of pure PMMA by free radical polarization and PMMA-TiO2 CLs using a cast molding method of 0.005 and 0.01 w/v concentrations and a study of their effect on the aberrated human eye. ZEMAX optical design software was used for eye modeling based on the Liou and Brennan eye model and then the pure and doped CLs were applied. Ocular performance was evaluated by modulation transfer function (MTF), spot diagram, and image simulation. The used criteria show that the best vision correction was obtained by the CL of higher doping content (p < 0.0001) and that the generated spherical and chromatic aberrations in the eye had been reduced.

Influence of SiO2 nanoparticles on electro-optical and thermophysical properties of polyacrylate/liquid crystal composites

ABSTRACTIn this paper, SiO2 nanoparticle-doped polymer dispersed liquid crystal (PDLC) lenses are made from a mixture of prepolymer, 5CB liquid crystal and SiO2 nanoparticles by the polymerisation induced phase separation (PIPS) process. The effect of SiO2 nanoparticles on the electro-optical properties of PDLC films are studied. It is established that SiO2 nanoparticles affect the microstructure of PDLC films significantly because of the formed agglomerates of SiO2 nanoparticles. Results show an improvement in the electro-optical properties and a decrease in the response time for doped systems with small amount of SiO2 nanoparticles. We also observe a shift of nematic–isotropic transition temperature as a function of SiO2 nanoparticle contents. A good agreement between the electro-optical study and thermophysical properties is reached.

Surface-enhanced fluorescence in metal nanoparticle-doped polymer nanofibers via waveguiding excitation

We report a waveguiding excitation-based approach for surface-enhanced fluorescence. As high as 17-fold enhanced fluorescence intensity of Rhodamine 6G molecules is realized by gold nanoparticles embedded in polymer nanofibers. The enhancement results not only from the spatial confinement of light by the nanofibers but also from the wavelength match among the excitation laser, the localized surface plasmon resonance of nanoparticles, and the absorption band of dyes. On the basis of the enhancement and high-efficient waveguiding regime, the required excitation power for detectable fluorescence is decreased to the 20 nW level, which is about 50 times lower than that by free-space excitation. These fluorophore/nanoparticle-doped nanofibers may find applications in compact and energy-efficient optical devices of chemical analysis and biosensing.

Fabrication of Composite Polymer Foam Films at the Liquid/Liquid Interface through Emulsion-Directed Assembly and Adsorption Processes

The foam films of polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-b-PAA-b-PS) doped with Cd(II) or Pb(II) species were fabricated at the planar liquid/liquid interfaces between a DMF/chloroform (v/v: 1/1) solution of the polymer and aqueous solutions containing cadmium acetate or lead acetate at ambient temperature. Optical microscopic observation shows the thin film is uniform on a larger length scale. Transmission electron microscopic (TEM) investigations reveal that the foam films are made up of microcapsules with the size of several hundreds of nanometers to micrometers. The walls of the microcapsules have a layered structure decorating with nanofibers and hollow nanospheres, where numerous inorganic fine nanoparticles are dispersed homogeneously. The film formation is a result of emulsion droplet-templated assembly and adsorption of the formed microcapsules at the planar liquid/liquid interface. Because of the miscibility of DMF with chloroform and water, DMF migrates to the aqueous phase while water migrates to the organic phase across the interface, resulting in the formation of a W/O emulsion, as revealed by optical microscopic observation, freeze fracture transmission electron microscopic (FF-TEM) observation, and dynamic laser scattering (DLS) investigation. The triblock copolymer molecules and the inorganic species adsorb and self-assemble around the emulsion drops, leading to the formation of the composite microcapsules. X-ray photoelectron spectroscopic (XPS) and FTIR spectroscopic results indicate that two kinds of Cd(II) or Pb(II) species, metal oxide or hydroxide, resulting from the hydrolysis of the metal ions and the coordinated metal ions to the carboxyl groups coexist in the formed thin films, which transform to metal sulfide completely after treating with hydrogen sulfide to get metal sulfide nanoparticle-doped polymer thin films.

Surface-enhanced Raman scattering (SERS) chips made from metal nanoparticle-doped polymer fibers

We employed an electrospinning method to prepare metal nanoparticle (NP) doped polymer nanofiber mats, which can be easily cut to size and fixed on slides or in microfluidic channels for surface-enhanced Raman scattering (SERS) measurements.

Inorganic/Organic Hybrid Nanocomposite and its Device Applications

VI semiconductors are promising nanomaterials for applications as window layers in low-cost and high-efficiency thin film solar cells. These nanoparticles are considered to be the model systems for investigating the unique optical and electronic properties of quantum-confined semiconductors. The electrical and optical properties of polymers are improved by doping with semiconductor materials and metal ions. In particular, nanoparticle-doped polymers are considered to be a new class of organic materials due to their considerable modification of physical properties. In this paper, I review the present status of these types of Inorganic/Organic hybrid nanocomposite materials. CdSe nanorods dispersed in polyvinyl alcohol (PVA) matrix have been prepared by chemical routes. Different characterization techniques like structural, optical and electrical have been used to characterize these nanocomposites. The devices like Schottky diodes and MOS structures have been fabricated and the results have been discussed in this review. The results have been compared with the reported literature by other groups also. Table of Contents

Efficient photo-thermal activation of gold nanoparticle-doped polymer plasmonic switches

We report on the photo-thermal activation of dielectric loaded plasmonic switches comprised of gold nanoparticle-doped polymer deposited onto a gold film. The plasmonic switches rely on a multi-mode interferometer design and are fabricated by electron beam lithography applied to a positive resin doped with gold nanoparticles at a volume ratio of 0.52%. A cross-bar switching is obtained at telecom wavelengths by pumping the devices with a visible beam having a frequency within the localized surface plasmon resonance band of the embedded nanoparticles. By comparing the switching performances of doped and undoped devices, we show that for the modest doping level we consider, the power needed to activate the doped switches is reduced by a factor 2.5 compared to undoped devices. The minimization of activation power is attributed to enhanced light-heat conversion and optimized spatial heat generation for doped devices and not to a change of the thermo-optic coefficient of the doped polymer.

Synthesis and assembly of catalytically active platinum-doped polymer nanocomposites at the liquid/liquid interface

Platinum nanoparticle-doped polymer foam-like thin films were prepared via a synthesis and assembly process at the liquid/liquid interface of a chloroform solution of poly(2-vinylpyridine) and an aqueous solution of chloroplatinic acid hydrate and a subsequent UV-light irradiation process. Transmission electron microscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy investigations indicated that the foam-like thin films formed at the interface were composed of polymer molecules, and Pt(II) and Pt(IV) ions. Platinum nanoparticles with average diameter of 2.70 ± 0.35 nm appeared after UV-light irradiation, which were embedded in and adsorbed on the walls of the foams. The formation of the composite nanostructures at the interface was attributed to self-assembly of the polymer molecules at the liquid/liquid interface, reduction of PtCl 6 2−, and interaction between PtCl 6 2−/intermediate PtCl 4 2− ions and the protonated pyridine groups. The catalytic activity of the composite film for the reduction of methylene blue by potassium borohydride in aqueous solutions was evaluated. The apparent rate constant decreased gradually with increasing the number of runs due to the partially leaching of Pt nanoparticles and became stable after the fifth cycle, indicating that the composite film can be used as an effective, stable and reusable catalyst.

Synthesis and assembly of gold nanoparticle-doped polymer solid foam films at the liquid/liquid interface and their catalytic properties

Gold nanoparticle-doped poly(2-vinylpyridine) (P2VP) microcapsules and foam films were synthesized and assembled at the P2VP chloroform solution/HAuCl4 aqueous solution interface at 25°C. It was found that Au nanoparticles with the average diameter of 2.1nm were homogeneously embedded in and adsorbed on the walls of the capsules and foams, the nanoparticles were composed of Au(0) and Au(III) with the molar ratio of about 75/25, and the mass percent of Au elements was measured to be 19.65%. The formation of the nanostructures was attributed to the self-assembly of P2VP at the liquid/liquid interface, the simultaneous reduction of AuCl4- ions by a small amount of ethanol in the chloroform and adsorption of AuCl4- ions. After irradiated by UV-light for 1h, the average diameter of the nanoparticles was found to be 2.2nm, and the AuCl4- ions were transformed to Au(0) completely. The catalytic performance of these composite nanostructures were evaluated by using the reduction of 4-nitrophenol (4-NP) by potassium borohydride in aqueous solutions. The catalytic activity was very high in the first cycle, decreased rapidly and slightly in the second and third cycles, respectively, due to the aggregation of some nanoparticles, and stabilized after the third cycle.

Dual liquid crystal alignment configuration based on nanoparticle-doped polymer films

This paper proposes an approach for producing dual liquid crystal (LC) alignment configuration based on nanoparticle-doped polymer films. Experimental results indicate that illuminating a nanoparticle-doped pre-polymer film, coated onto a substrate with a homogeneous alignment layer, with unpolarized UV light through a photomask causes the polymerization of pre-polymer, ultimately generating homogeneous and vertical alignment layers in unpolymerized and polymerized regions, respectively. The dual LC alignment configuration of the homogeneous (vertical) and hybrid alignments can be achieved by combining the treated substrate with another substrate that has a homogeneous (vertical) alignment layer. Additionally, the applications of the dual LC alignment layer in phase gratings and transflective LC displays are demonstrated.

Influence of Tm+3 concentration on the non-linear optical effects of the BiB3O6 : Tm3+ glass nanoparticle-doped polymer

It is shown that BiB3O6 : Tm3+ glass nanoparticles incorporated into polymethylmethacrylate (PMMA) and polycarbonate (PC) polymer matrices show good second-order susceptibilities under bicolour coherent laser treatment. It is found that only during incorporation into highly polarized PC matrices could one observe an enhancement of the second-order susceptibilities with increasing laser treated power densities. The main increase is observed for all samples at power densities equal to about 0.4 GW cm−2. After passing this value there is a saturation of the output susceptibilities and even an abrupt decrease. The most striking feature is the achievement of second-order susceptibilities equal to about 5 pm V−1 for samples containing 4% nanoparticle (NP) content in the PC matrix. A further increase in the NP concentration to 6% leads to a decrease in susceptibility to 15%. In the case of PMMA matrices these changes do not exceed the background. The same situation is present for the pure BIBO and low-doped Tm materials. The effect is maximal for a low concentration of Tm—about 0.75%. In the case of bulk glasses the intensity dependences of the second-harmonic generation unambiguously show that the achieved maximal values of second-order susceptibilities do not exceed 3 pm V−1 for 0.5% Tm concentration.

Resonant optical scattering in nanoparticle-doped polymer photonic crystals

A broadband hyperspectral technique is used to measure the coherent optical backscatter across a wide spectral bandwidth, showing the resonant suppression of the photon transport mean free path around the photonic bandgap of a shear-assembled polymer photonic crystal. By doping with carbon nanoscale scatterers that reside at specific points within the photonic crystal lattice, the ratio between photon mean free path and optical penetration is tuned from 10 to 1, enhancing forward scatter at the expense of back-scatter. The back-scattering strength of different polarisations is not explained by any current theory.